New Concepts Non Cyanide Alkaline Zinc

New Concepts in Non Cyanide
Alkaline Zinc Plating

Dr. Rolf Jansen SurTec GmbH D-64673 Zwingenberg
B Old Problems and Their Causes
B New Concepts:
1 ZincProcessoftheThirdGeneration
2 Anodes
3 ZincGenerator
4 ElectrochemicalProcessControl
1
SurTec GmbH
RJ@SurTec.com
http://www.SurTec.com/Presentations/
Copyright, 25. August 2000
Delayed Blistering
O thedepositedzinclayeriscorrect,theparts
aredelivered,aftertwoorthreeweeksthe
zinclayerburstsoffinsmallflakes.
0 wrongdosageoftheadditives
O electrolytetemperaturetoolow
O foreignmetalsembrittlezincdeposits
O (pretreatment)
Chromatability of Non Cyanide Zinc Deposits
O spotted,yellowishbluechromating;
greyish,heavilyiridescentyellow
chromating
0 incorporationofforeignmetals(iron!)
O overdosageoftheadditives
O badlyadjustedactivation/chromating
Problems with Bath Control
O constantzinccontent
currentdistributionintheelectrolytetank
enrichmentofforeignmetals
bathcontrolperHullcell
B zincgeneratornoteffectiveortoosmall
B anodes(solubleandinert)getspassive
B semistrongcomplexingagentsinthebath
B misbalancedadditivesystems
Old Problems and Their Causes 2
SurTec GmbH
RJ@SurTec.com
-1700 -1500 -1300 -1100 -900
160
120
80
40
0
-40
U
SHE
/mV
I/mA
Currentvoltagecurves,20mV/s,rotatingAudiskelectrode,0.196cm
2
,
1600rpm,noncyanidealkalineelectrolyte(10g/lZn,120g/lNaOH)
withconventionalcarrier withoutadditive
Zn
Zn
c
x
c
0
Nernsts
diffusionlayer
Zn
Plating Range Y Burnings A Deposition in the Diffusion Limiting Current 3
SurTec GmbH
RJ@SurTec.com
R
el
R
el
poor and good
throwingpower
35 % 19 % R
Pk
R
Pk
R
Pa
R
Pa
-1700 -1500 -1300 -1100 -900
160
120
80
40
0
-40
U
SHE
/mV
I/mA
Throwing Power Y Electrolyte Conductivity Y Polarisation Resistance 4
SurTec GmbH
RJ@SurTec.com
Currentvoltagecurves,20mV/s,rotating
Audiskelectrode,0.196cm
2
,1600rpm,
noncyanidealkalineelectrolyte
(10g/lZn,120g/lNaOH)
newgenerationcarrierSurTec704I
withoutadditive
New Non Cyanide Zinc Process
SurTec 704
averagelayerthickness: 3.7 m
lowestvalue: 2.4 m
highestvalue: 7.7 m
variationcoefficient: 28 %
Old Non Cyanide Zinc Process
SurTec 705
lowestvalue: 1.1 m
highestvalue: 12.7 m
Low Cyanide Zinc Process
SurTec 728
lowestvalue: 1.3 m
highestvalue: 8.8 m
Chloride Zinc Process
SurTec 758
lowestvalue: 1.4 m
highestvalue: 14.7 m
LCD
HCD
LCD
HCD
LCD
HCD
LCD
HCD
Comparison of Throwing Power at Hull Cell Panels 5
SurTec GmbH
RJ@SurTec.com
Y X-raydiffractionshowsthatzinccrystallitesfromnoncyanidealkalinezincprocesses
comparedtoacidzincarestronglyorientedintothedirectionoftheelectricalfield
duringdeposition.
Y Evenatroomtemperature,the
orientationinthedepositedlayer
breaksbytime(someweeksorso).
Y Finally,thezinccrystallitestake
moreplaceandinduceapressure
tensioninthelayerwhichleadsto
blistering.
Delayed Blistering Y Layer Texture Y Recrystallisation 6
SurTec GmbH
RJ@SurTec.com
0
200
400
600
800
1000
1200
1400
30 40 50 60 70 80 90
2 Theta []
Intensitt [Impulse]
cyanidfrei
cyanidisch
Zn-Pulver acidzincundZn-powder
alkalinecyanidezinc
alkalinenoncyanidezinc
(oldgeneration)
zinccrystallsinany
orientation
Intensity
Thesodium zincate electrolyteismorecheapatmake-up
Thepotassium zincate electrolyteoffersabetterelectrolyteconductivityandtherefore:
B betterthrowingpower
B highercurrentefficiency(apprx.80%at30-35C)
B higherburninglimit
B higherdepositionrate
B moreductileandwhiterzinclayers
B about0.5to0.75Vlowercellvoltage:
Example: rackplatinglinewith10000A,10racksperhourand0.5ldragoutperrack
10g/lZinc,120g/lNaOH,40g/lNa
2
CO
3
comparedto10g/lZinc,170g/lKOH,50g/lK
2
CO
3
cost of chemicals Na electrolyte: 10/h0.5l(0.12+0.03)kg/l0.51DM/kg =0.38 DM/h
K electrolyte: 10/h0.5l(0.17+0.04)kg/l1.00DM/kg =1.05 DM/h
=0.67 DM/h
savings of electrical energy K electrolyte: 0.5V10kAh/h0.15DM/kWh =0.75 DM/h
B potassiumelectrolyteforrackplating,sodiumelectrolyteforbarrelplating
Sodium or Potassium Electrolyte? 7
SurTec GmbH
RJ@SurTec.com
100
80
60
40
20
0
5 4.5 4 3.5 3 2.5 2 1.5 1 0.5
current density in A/dm
2
0 g/l Na
2
CO
3
10 g/l
20 g/l
30 g/l
40 g/l
50 g/l
60 g/l
70 g/l
80 g/l
90 g/l
100 g/l
current efficiency in %
SurTec 704SodiumZincateElectrolyte,10g/lZinc,120g/lNaOH,0to100g/lNa
2
CO
3
SurTec GmbH
RJ@SurTec.com
100
80
60
40
20
0
5 4.5 4 3.5 3 2.5 2 1.5 1 0.5
current density in A/dm
2
0 g/l K
2
CO
3
30 g/l
60 g/l
90 g/l
120 g/l
150 g/l
180 g/l
current efficiency in %
SurTec 704PotassiumZincateElectrolyte,10g/lZinc,170g/lKOH,0to180g/lK
2
CO
3
SurTec GmbH
RJ@SurTec.com
Y Currentefficiencyfortheanodiczincdissolutionstaysabout100%uptoananodic
currentdensityofabout3A/dm
2
.
Y Aboveananodiccurrentdensityof3A/dm
2
,thezincanodeiscoveredwithasemi
conductivebarrierlayerofzincoxide(happensalsoinpurebaseelectrolyteswithout
organics)...
B thecellvoltagerisesimmediatelyby3to4V
B theanodebecomesblack
B theanodiccurrentefficiencydropsdownto2-5%,
infavourof95-98%O
2
evolution
B Thereforeitisextremelyhardtocontrolthezinccontentoftheelectrolytebychanging
theanodearea.Theanodicc.e.iseithertoohighortoolow,thereisnointermediate
rangeofoperation.Thismeans,anodesmustberemovedorreinsertedveryfrequently.
Thisleadsofcoursetoapoorcurrentdistributionintheplatingtank.
B Operationwithmixedtypesofanodes(solubleandinert)isveryproblematicandat
leastforrackplatingnotsuitableatall.
Using Soluble Zinc Anodes in the Plating Tank? 10
SurTec GmbH
RJ@SurTec.com
Y Colourgenerallyresultsfromabsorptionoflightatcertainwavelengths.
Y Certainwavelengthsareabsorbedbecauseofelectrontransitionsbetweendiscrete
energylevelsinthematter.
Y Normally,zincoxideiswhite,becausethereisnodistancebetweenitsoccupiedand
nonoccupiedenergylevelswhichfitsfortherangeofwavelengthsofvisiblelight.
Y Zincoxideatapassivezincanodehasbeenrunninglowonelectronsandisthereforea
p-semiconductor(positiveholeconductioncomparedtonegativeelectronconduction).
Y Thesepositiveholesarestatisticallydistributed,empty,intermediateenergylevels.
B ThisresultsinanabsorptionoflightatallwavelengthsBlack!
Why Soluble Zinc Anodes Become Black 13
SurTec GmbH
RJ@SurTec.com
Y Usuallynoncyanidealkalinezincprocessesaredrivenwithinertanodesincombination
withanexternalzincgeneratorforthereplenishmentofzinc.
Y Inertsteelanodesaremostcommonlyused.
Y Butsteelanodesare,incontrarytocommonbelief,not100%stable.Thismeans,iron
isdissolved!
Y Therearesomecyanidefreezincelectrolyteswhichcontainmoreironthansome
standardzinc/ironelectrolytes.
Y Ofcourse,dissolvedironisco-depositedwiththezinc.Dependentontheamount,the
troublesomediscolourationofthechromatinglayeroccurs.
B Steelanodesarefairlyunsuitablefornoncyanidealkalinezincplating.Coatedsteel
anodesaremuchsuperior.
B Stainlesssteelanodesaretotallyunsuitable,becauseitanodicallyreleaseschromium(VI)
intotheelectrolyte.
Operation with Inert Anodes 14
SurTec GmbH
RJ@SurTec.com
non cyanide alkaline zinc electrolyte: 10 g/lZn,
120 g/lNaOH
with SurTec702(oldgenerationprocess)
cell voltage in a Hull cell at 1 A: 3.21 V(steelanode)
(freshly prepared electrolytes, new anodes) 3.39 V(coatedanode)
iron content of the electrolytesinmg/l(1.8lvolume,operationwith1Aat25C)
start 16 h 40 h 64 h 88 h
steelanode <0.5 2.5 5.0 6.0 7.1
coatedanode <0.5 <0.5 <0.5 <0.5 <0.5
cell voltage at 1 A: 3.39 V(steelanode,brown-blackcoating)
(usedelectrolyte,usedanodes) 3.32 V(coatedanode,blank)
Comparative Investigation of Inert Anodes 15
SurTec GmbH
RJ@SurTec.com
Minimal requirement: 15msemibrightnickelplatedsteel
Better: 15msemibrightnickel+SurTecCatalystcoatingonsteel
Thecatalyticcoatingdecreasestheoxygenovervoltage,therefore:
v bettercurrentdistributionintheplatingtank
v lowercellvoltage(energysavings)
v lowerconsumptionoforganics
Optimum:
Anodesmadeofexpandedmetal(30
mm8piccolomesh,ribwidth6mm
materialthickness2mm)ofmildsteel
(e.g.ST37)platedwith15msemi
brightnickel+aSurTecCatalystfinish.
Theexpandedmetalshouldbeinstalledwiththeribshorizontallyorientedfordrivingthe
gasevolutiontothebackside.Bythisway,abetterelectrolyteconductivityinfrontofthe
anodeisachieved.Anodiccurrentdensityupto20A/dm
2
.
Design of the Anodes 16
SurTec GmbH
RJ@SurTec.com
expanded
metal ribs
Flowofthegasevolution
whenanodesare
correctlyinstalled
b
a
c
k

s
i
d
e
f
r
o
n
t

s
i
d
e

f
a
c
e
d

t
o

t
h
e

p
a
r
t
s

(
c
a
t
h
o
d
e
)
gas
evolution
B Whyaremostzincgeneratorsnoteffectiveenough?
Y Zincappearsintheelectrochemicalseriesofelementsmorenegativethanhydrogen,
andzincisanamphotericelement:
Zn+2H
2
O+2OH
[Zn(OH)
4
]
2
+H
2
Y Thisisatypicalredoxreactionwhichcanbedividedintoananodicoxidationstepand
ancathodicreductionstep:
4 anodic oxidation
Zn+4OH
[Zn(OH)
4
]
2
+2e
4 cathodic reduction
2H
2
O+2e
H
2
+2OH
B Thetwopartialreactionsdependoneachother,bothreactionsmustoccuratthesame
timewiththesamespeed.Thatmeans,thezincdissolutioncannotbeanyfasterthan
thehydrogenevolution.
Zinc Generator 17
SurTec GmbH
RJ@SurTec.com
Y Thehydrogenovervoltageonzincisveryhigh-or-inotherwords,theevolutionof
hydrogenatzincisveryslow.Thismeansthatthezincdissolutionisveryslowtoo.
Y Contactingzincwithametalwhichhasasmallhydrogenovervoltagewillleadtoa
muchfasterhydrogenevolutiononthatmetalcomparedtotheevolutionatzinc.
Y Conventionally,zincdissolutionbasketsaremadeoutofsteel.Thezincisplacedinto
thesebasketsandimmersedintothealkalineelectrolytewhereaslowdissolution
occursbecauseironcomparedtozincexhibitsalower(thoughsignificant)hydrogen
overvoltage.
Y Hydrogencatalystsaremuchbettersuitedasbasketmaterialthanironbecausetheir
hydrogenovervoltageisverylowandtheyenhancethehydrogenevolutionbyfar.
Zinc Generator 18
SurTec GmbH
RJ@SurTec.com
Zincanodes
Catalystor
steelpanel
Magneticstirrer
Zincelectrolyte
Ampre-meter
A
0 1 2 3 4 5 6 7
2.5
2.0
1.5
1.0
0.5
0.0
40
30
20
10
0
current density
in A/dm
2
zinc content
in g/l
stop: 10.8 g/l
start: 10.0 g/l
Iron
SurTec
Catalyst
stop: 35 g/l
time in h
B IncontactwiththeSurTecCatalystzinc,isdissolvedinaveragewith1.5A/dm
2
(catalystarea).Thedissolutionrateisatleast10timeshigherthanatsteel.
Zinc Generator 21
SurTec GmbH
RJ@SurTec.com
Fluessigkeitsstand
waehrend des Betriebes
Fluessigkeitsstand beim
Auffuellen der Zn- Pellets
PP-Platte 10 mm dick,
Perf. , Tlg. 100
mm
96 Stck. Anodenkoerbe
aus Streckgitter
65 x 65 x 900 mm
kont. Umwaelzung
Trennwand
Membran-
schieber
Membran-
schieber
Graugusspumpe
8000 l/h
DN 80
Niveaustand
100 mm
Niveaustand
170 mm
DN 80
Kammerueberlauf
fuer Niveaustand
170 mm
Gitter aus Fl. 30 x 10
PP - Platte 40 mm dick
B
A
2
1
3
1
2
3
Zinc Generator 22
SurTec GmbH
RJ@SurTec.com
SurTec 704, 712 and 715
Size of Zinc Generators with

Catalytically Plated Baskets
for Cyanidefree Alkaline Zinc-
and Zinc Alloy Processes
Input data
Data for determination of the zinc consumption of the line
totally installed rectifier capacity: 12000 A
current efficiency: 70 %
load of the plating line and the rectifiers: 75 %
Data for sizing the catalytical zinc baskets and the generator tank
depth of the zinc generator tank: 1200 mm
length of one side of the tank; result is length of 2.
side:
(input of zero results in a generator tank with a quadratic cross section)
0 mm
basket width (quadratic cross section): 62.5 mm
bulk density of zinc pieces 5 kg/l
Do the Calculation Reset Data
05.09.2000 10:46 Uhr Zinc Generator
Seite 1 von 1 http://www.SurTec.com/SurTec/Zincgenerator.html
SurTec 704, 712 und 715
Size of Zinc Generators width

Catalytically Plated Baskets
for Cyanidefree Alkaline Zinc-
and Zinc Alloy Processes
Input Data
total current: 12000 A
current efficiency: 70 %
load of the plating line and the rectifiers: 75 %
depth of the generator tank: 1200 mm
length of one side: 0 mm
width of the baskets: 62.5 mm
bulk density of the zinc pieces: 5.00 kg/l
Calculation Results
zinc consumption of the plating line: 7.7 kg/h
length of the zinc baskets: 1000 mm
surface area of one basket (inner + outer): 50.8 dm
2
necessary total catalytical surface area: 4200 dm
2
number of catalytical baskets: 83 piece
dimensions of the generator (w x l x h): 925 x 925 x 1200 in mm
stored zinc metal in the generator: 1621 kg
volume of the electrolyte in the generator: 714 l
05.09.2000 10:47 Uhr Layout of the Zinc Generator
Seite 1 von 1 http://www.SurTec.com/SurTec/GeneratorE.acgi
B Theperformancepropertiesandtheinfluencesforazincelectrolyteare:
Properties Relations Influences
throwingpower carrier(SurTec704I) C
brightness brightener(SurTec704II) C
distributionofbrightness zincconcentration C
ductility NaOHorKOHcontent C
adherence/blistering carbonateconcentration I
depositionrate foreignmetals(iron,lead) I
currentefficiency currentdensity P
chromatability temperature P
agitation P
C = Chemical parameter P = Physical Parameter I = Interference
Electrochemical Process Control 25
SurTec GmbH
RJ@SurTec.com
Y Physicalprocessparameterslikecurrent density, temperature, agitationandtime
canbeheldconstanteasilybyrelativelysimplestandardequipment.
Y Interferingforeign metalscanbeavoidedbyusingreallyinertanodes(nosteel
anodes!)incombinationwithanexternalzincgenerator.Leadbeginstointerfere
above1mg/l.Itcomesintotheelectrolytebecausezincmetalisalwayscontaminated
withlead.ItmustbeprecipitatedwithsuitablesulfurcompoundslikeSurTec701.
Y Sodium carbonateinterferesonlyabove70-80g/l.Almostnoconventionalnon
cyanidealkalineinstallationhaseverreachedthisvalue.Thoughitmightbepossible
withheavyrinsewaterrecycling.However,sodiumcarbonatecanbefrozenout.
Potassium carbonatedoesnotinterfereupto180g/l.
Electrochemical Process Control 26
SurTec GmbH
RJ@SurTec.com
Y Sodium or potassium hydroxidecouldbetitratedautomatically.Hydroxideis
consumedbydrag-outandgenerationofcarbonate.Continuousdosageisnecessary
formaintainingtheelectrolyteconductivity.
Y Theconcentrationofzinc couldbedeterminedautomaticallybycomplexometric
titration.Zincisconsumedbydrag-outandofcoursemainlyforthedesiredzinc
deposition.Itisreplenishedpreferablybyazincgenerator.
Y Theadditivescarrierandbrightenerareadjustedwithrespecttotheireffectonthe
zincdeposition(e.g.withtheaidofHullcelltests).But,Hullcelltestsarehardly
automisable.
Y Withexceptionoftheorganicadditives,allprocessparameterscanbeautomatically
controlledbyconventionaltechnicsandequipment.
B For automatic adjustment of the organic additives new different methods
must be found.
Electrochemical Process Control: Measuring Methodes 27
SurTec GmbH
RJ@SurTec.com
Currentvoltagecurves,20mV/s,rotatingAudiskelectrode,0.196cm
2
,1600rpm,noncyanide
alkalinezincelectrolyte(10g/lZn,120g/lNaOH)
-1700 -1500 -1300 -1100 -900 -700
200
150
100
50
0
-50
U
SHE
/mV
I/mA
RDE
RE
WE
CE
U
I(U )
C
with organic additive
without any additive
RDE RotatingDiskElectrode
WE WorkingElectrode
RE ReferenceElectrode
CE CounterElectrode
U ReferenceVoltage(Potential))
U
C
CellVoltage
I Current
Electrochemical Process Control: Electronic Hull cell panel 28
SurTec GmbH
RJ@SurTec.com
Y Currentvoltagecurvesareadirectmeasureforthedepositionconditionsinan
electrolyteandonlyaindirectmeasurefortheconcentrationsofitsingredients.
Y Thedepositionconditionsarethetargetmeasure,nottheconcentrations.
Y Therefore,anautomaticcontrolofelectrolytesonthebasisofcurrentvoltagecurves
seemstobepossible.
Y Theideabehindthisistomeasurecurrentvoltagecurveswhichcharacterisetheactual
electrolyteconditionsandtocomparethemwithadesiredcurrentvoltagecurve.
Y Bythewayoftestinjectionsoftheadditivesintothemeasuringcell,itispossibleto
approachstepwiseiterativelythedesiredconditions.
Electrochemical Process Control: Automation 29
SurTec GmbH
RJ@SurTec.com
-1800 -1600 -1400 -1200 -1000 -800 -600
0.6
0.4
0.2
0.0
-0.2
-0.4
U
SHE
/mV U
SHE
/mV
I/A
actual current voltage curve
desired current voltage curve
Summation
(actual desired)
2
2
2
0 00043 6 =
( )
=
I I
k act k des
k
, ,
. %
d
i
f
f
e
r
e
n
c
e

c
u
r
v
e
Automation: Comparison between Actual and Desired Current Voltage Curve 30
SurTec GmbH
RJ@SurTec.com
Automation: Test Injections into a Measuring Cell 31
SurTec GmbH
RJ@SurTec.com
electrolyteinlet,
gravityfeed,
magneticvalvecontrol
electrolyteout
RDE
RE
WE
CE
potentiostat
additive1 additive2 additive3 additive4
-2000 -1800 -1600 -1400 -1200 -1000 -800 -600 -400
30
20
10
0
-10
-20
I/mA
U/mV
-1350 -1300 -1250
0
-1
-2
-3
B Zinccanbedeterminedbyevaluationofthe
enlargedPeak.Thedeviceregulatestheexchange
flowbetweenplatingtankandzincgeneratoraccordingly.
Automation: Analysis of Zinc, Control of the Zinc Generator 32
SurTec GmbH
RJ@SurTec.com
dc
dt
=

V
c
V
+

V
c
L
V
dc
L
dt
=

V
c
L
V
L
+

V
c
V
L
+

c
l
cA
.
plating
tank
c, V
zinc
generator
cL, VL

V

V
Y Theelectrolyteconductivityismainlydeterminedbysodiumorpotassiumhydroxide.
Y Theelectrolyteconductivityistheaimforthebathcontrol,nottheconcentrations.
0 5 10 15 20 25 30 35 40
100
50
0
-50
-100
-400
-600
-800
-1000
-1200
-1400
-1600
-1800
U/mV I/mA
t/ms
R
el
= 1210 mV/103.8 mA = 11.7
B Thedevicedosesconc.causticsodaorpotashsolutionformaintainingtheelectrolyte
conductivity.
Automation: Determination of NaOH or KOH 33
SurTec GmbH
RJ@SurTec.com
http://www.SurTec.com/Presentations/ Copyright, 25. August 2000
Y Currentvoltagecurvesareadirectmeasureforthe
depositionconditionsinanelectrolyteandonlyanindirect
measureoftheconcentrationsoftheindividualbath
components.Importantarethedepositionconditionsand
nottheconcentrations.
= SurTec
704ZincOperator
B controlsthestatusoftheelectrolyteintotal,notonly
individualfactors
B dosesallorganicadditives
B controlsthezincgeneratorandthealkalinity
B documents
Automatic Electrochemical Process Control: SurTec
704 ZincOperator 34
SurTec GmbH
RJ@SurTec.com
The SurTec 4x Concept for the non cyanide alkaline zinc plating comprises:
0 theoptimal additive systemSurTec
704forbestthrowingpowerwithlowest
affinitytoblisteringandtotherespectivetaskadaptedcomposition
O reallyinert anodeswithadditionalSurTec Catalystcoating
O smallandhighly effective zinc generatorsbecauseoftheSurTec
Hydrogen
Catalyst
O ZinkOperator-automaticelectrochemicalprocesscontrol
Summary 35
SurTec GmbH
RJ@SurTec.com

New Concepts Non Cyanide Alkaline Zinc

Загружено:

Сведения о документе

Авторское право

Доступные форматы

Поделиться этим документом

Поделиться или встроить документ

Параметры публикации

Этот документ был вам полезен?

Это неприемлемый материал?

Авторское право:

Доступные форматы

New Concepts Non Cyanide Alkaline Zinc

Загружено:

Авторское право:

Доступные форматы

New Concepts in Non Cyanide

Alkaline Zinc Plating

Size of Zinc Generators with

Size of Zinc Generators width

Вам также может понравиться