1

Plating Rounds WorkshopPlenary SessionSt. John’s, NewfoundlandSeptember 12, 2018

2

1. Electroplating

2. Plating Rounds

3. Introducing Plating Rounds to Customers

4. Going Forward

3

Electroplating

4

What is nickel electroplating?

The electrolytic deposition of nickel onto a substrate to enhanceproperties.

Requires the movement of a direct current between 2 electrodes in aaqueous solution of salts.

The flow of electrons causes one electrode (anode) to dissolve and theother electrode (cathode) to become covered with metal.

-- --

Rectifier

--

Ni++ ionreceiving

twoelectrons-

Ni atomgiving up

twoelectrons

-

Ni++

-

+ -Anode Cathode

Ni++

Ni++

Ni++

Nickelbasket

Parts beingelectroplated withnickel

Ni++

Ni++

Ni++

5

Anode Reactions

Ni ® Ni++ + 2e-+

+

Ni++

Ni++

-Ni++

Ni

Ni--

Other reactions can occur:

2Cl- ® Cl2­ + 2e-

2H2O ® O2­ + 4H+ + 4e-

If pH is decreasing:- Cl- levels / passivated nickel- Is there enough anode/cathode area- bridging/voids

6

Cathode Reactions

Ni++ + 2e- ® NiSide reaction that will occur:

2H+ + 2e- ® H2­

-pH goes up, acid is required-Ni++ concentration in bath increasingdue to difference in efficiencies atcathode and anode – balanced bysome Ni drag out with parts

Ni++

-

---

--

Ni++

Ni++

Ni

Ni

-

7

Secondary Reactions2H+ + 2e- ® H2­

2Cl- ® Cl2­ + 2e-

2H2O ® O2­ + 4H+ + 4e-

Cathode

-Good agitation will help Ni++ diffuseto part surface and away from nickelanode

-agitation also help liberate any H2gas bubbles from the part

Anode

Anode-

-- --

Rectifier

H+

H+

H2

H2

Cathode

-

Cl-

+

Cl-

Cl2

Cl2

AnodeH2O

H2O

O2 -

--

8

Faraday’s LawTheoretical nickel deposited

The amount of nickel plated at the cathode and dissolved at the anode areproportional to the electrical current x time.

If you pass 1 ampere (Amp) of current thru a plating cell for 1 hour you willdeposit 1.095 grams of nickel.

In practice, some current will do things other than plate nickel:• side reactions like hydrogen evolution• leaks to ground• short circuits

Weight =96,500 coulombs

atomic weightcharge X current X time

These are the onlyindependent variables

9

Metal Distribution in a plating cellElectrical flux between anodes andcathode impact plated thickness

Distance and relative direction tonickel anodes impact thickness ofdeposit.

Lack of nickel in the basket will have asimilar impact if part direct opposite

Current density and the rate ofmetal deposition are lower inrecessed areas.

Opposite is true in high currentdensity areas.

10

Corrosion resistance of multilayered nickelcoatings

Bright nickel contains sulphurand will corrode faster thansemi-bright nickel whichcontains no sulphur

Semi-bright layer is thicker &resists corrosion effects

By increasing the number ofcracks/pores in the chromecoating, corrosion is spreadacross more locations, slowingthe depth of corrosion

No sulphur

High sulphur

11

Multi-layered and micro-cracking platingA number of layered plating regimes exist, ranging from a few to all of the following:• Copper/nickel strike• Semi-bright• High Sulphur nickel• Bright nickel• Chrome

12

Titanium basketsAnode baskets for nickel plating are fabricatedfrom titanium, which has excellent propertiesof lightness and strength

The thickness of the basket should be largeenough to allow the nickel pieces to settlefreely during anodic dissolution in a workingbasket. Hammering or ramming the nickeldown may damage the basket.

The tray at the bottom of the basket isdesigned to hold the final small pieces ofnickel and nickel fines, maintain electricalcontact and thus enable dissolution

13

Baskets fitted with bagsMust be fitted with bags toprevent nickel fines ornickel sulphide residuesentering the platingsolution.

Bags should be tight fittingso all fines receive currentand can dissolve. Thereshould be no 'billowing' ofthe anode bags, whichwould allow nickel fines tofall outside the basket.

14

Plating Rounds

Vale nickel – typical chemical analysis (wt%)

Rounds Chips P-PelletChemicalAnalysis

(wt%)

Thompson LongHarbour

Copper Cliff Clydach Copper Cliff Clydach

Ni* >99.90 >99.95 >99.98 >99.98 >99.98 >99.98

Co <0.08 <0.030 <0.00002 <0.00002 <0.00002 <0.00002

Cu <0.0009 <0.0002 <0.00004 <0.0001 <0.00004 <0.0001

C <0.0035 <0.008 <0.007 <0.007 <0.007 <0.011

Fe <0.0002 <0.002 <0.0006 <0.004 <0.0006 <0.004

S <0.0002 <0.005 <0.0001 <0.0002 <0.0001 <0.0002

Pb <0.0003 <0.0001 <0.000002 <0.000003 <0.000002 <0.00001

Zn <0.0002 <0.0002 <0.00002 <0.00002 <0.00002 <0.00002*Nickel determined by difference

Plating Rounds are typical of other Vale plating products..

Convenient size, shape and packagingPlating Rounds Chips P-Pellet

Form

DiameterThickness

Button Shaped

~25-29mm~6mm

Round shape

~17-25mm~4-5mm

Spherical

~8-12mm

Packaging 10 kg bags /5 bags per box

250kg drum

10 kg bags /5 bags per box

250kg drum

2000kg bag

10 kg bags /5 bags per box

1000kg bag

2000kg bag

For reference – Thompson R-Rounds (23mm x 8mm)

Competitive nickel – typical chemical analysis (wt%)

wt% PlatingRounds

ThompsonR-Rounds

GlencoreCrowns

SMMcathode

Norilsk1x1 Jinchuan

Ni* >99.95 >99.90 >99.98 >99.98 >99.96 >99.97

Co <0.030 <0.08 <0.0002 <0.001 <0.025 <0.0030

Cu <0.0002 <0.0009 <0.0001 <0.0002 <0.0006 <0.0025

C <0.008 <0.0035 <0.002 <0.002 <0.003 <0.002

Fe <0.002 <0.0002 <0.001 <0.0001 <0.001 <0.003

S <0.005 <0.0002 <0.0002 <0.0001 <0.002 <0.0005

Pb <0.0001 <0.0003 <0.0002 <0.0001 <0.0003 <0.0006

Zn <0.0002 <0.0002 <0.0002 - <0.0005 <0.0006

*Nickel determined by difference**Competitor typical values from sample assays received.

Thompson R-Rounds is a market leading product in high qualityapplications but R-Rounds were not the most pure. Performance is key.

18

Carbon & Sulphur LevelsSulphur under control since troubleshooting primary source in July 2018. Trackingconsistently in the 10-12ppm range.

Carbon levels also substantially more stable.

Carbon and Sulphur are currently specified as 0.010% max. Opportunity to refine.

020406080

100120140

Carbon and Sulphur (ppm)

S

C

Lower since early July

19

Laboratory testing of Plating RoundsEarly development work performedin Vale laboratory

THOMPSON LONGHARBOUR

20

Packing Density

ProductPackingDensity

(g/cm3)

PlatingRoundsWeight

P-Pellets 5.3 -28%Chips 5.0 -24%1x1 4.6 -17%

R-Rounds 4.3 -12%4x4 4.0 -5%

PlatingRounds 3.8 ---

Plating Rounds havelower packing density –meaning decreasedinventory costs inbaskets

Lower nickel inventory inbasket, means nickellevel lower or morefrequent basket top up

21

Rounds Voltage comparisonPlating Rounds have lower voltage than cut cathode = powersavings.

— Plating Rounds— 1x1— P-Pellets— Chips

Chips

P-Pellets

1x1

Plating Rounds

Power = Voltage (V) x Current (I)

22

Performance – packing density vs nickel voids

• P-Pellets provide best coverage, they do so with a high packing density

Plating Rounds provide low packing density yet provideexcellent coverage in a titanium basket.

23

Effect of Bridging on Deposit Quality

Anode Deposit

Current

ThinnerDeposit

§ Bridging can affect uniformity of deposit thickness§ Bridging can cause baskets to “burn-out” at voids

Uniform settling promotes high qualitydeposits and longer basket life

Titanium basket after electrochemicalattack where no nickelwas dissolving.

24

Review of Imperfections

25

Honeycombs and Green Salts

Honeycombing: gas bubbles prevent nickel from plating until such time as thebubble is displaced. This would not cause any issue of concern to plating baths.

Green Salts: Green salts can be a residue left over from poor rinsing after the roundsare pulled from the tanks. These would contain nickel sulphate and nickel chloride.Both exist in nearly all non-activated nickel applications. This can also be nickelhydroxide which will dissolve in the acidic plating bath.

Thickness variation

Varying thickness of Rounds

Rounds are harvested on a 5.5-6 day cycle.Thickness of rounds can vary based on a number of factors including:

-activity of inert anode opposite Rounds location-dropped rounds with new growth lower than normal cycle-concentration gradients / agitation.

These foreign materials were firstencountered upon startup buthave been virtually eliminated.

Red edge tape – replaced with inkpainting. Currently only used whenrequired.

Mandrel ink stuck to back side ofrounds – adjustment of mandrelroughness

Crystals and Foreign objects –proper rinsing and handlingprocedures

Previous Quality Improvements

Red EdgeTape

MandrelInk

ForeignMaterials Sulphate

crystals

28

Quality process

Refinery Quality Management & ISO 9001:2015

ISO Certification Schedule

SeekRegistration!

2019

Q1 2019

Official Internal QMS LaunchSecond Internal Audit(External Led)Address Outstanding Gaps

Confirm SIMs ListDraft Maintenance SLAImplement ManagementReviewConfirm Quality PolicyConfirm Quality Objectives

Q4 2018

Q3 2018

Complete Context/SWOT/PESTLEConfirm QMS ScopeDocument and Training ReviewDraft CTQ CharacteristicsDevise Awareness StrategyInternal Audit Training and Execution

Map Production ProcessesConfirm Action LimitsDraft Quality ManualImplement CAPAR System

Q2 2018

30 Typical Lots shipped from Long Harbour are about 100 mt.

MeltGrade

Element % wt.Ni 99.8Co 0.15As ˂0.005Bi ˂0.005C 0.03Cd -Cu 0.02Fe 0.02Mg -Mn ˂0.005P ˂0.005Pb ˂0.005S 0.01Sb ˂0.005Si ˂0.005Sn ˂0.005Zn ˂0.005

Premium MeltGrade

Element % wt.Ni >99.9Co <0.1As <0.001Bi <0.0003C <0.01Cd <0.0005Cu <0.001Fe <0.01Mg <0.0005Mn <0.0005P <0.0005Pb <0.0005S <0.01Sb <0.0005Si <0.0005Sn <0.0005Zn <0.001

ElectroplatingGrade

Element % wt.Ni >99.9Co <0.1As <0.0005Bi <0.00004C <0.010Cd <0.0005Cu <0.001Fe <0.002Mg -Mn <0.0002P <0.0001Pb <0.00025S <0.010Sb <0.00002Si <0.0005Sn <0.00002Zn <0.0005

Product Chemical Specifications

31

Specification ElementsElement Lot Assay

(Lot Sample)Monthly Assays

(Composite Sample)

Co X -

As* X X

Bi* X X

C X -

Cd X -

Cu X -

Fe X -

Mn* X X

Pb* X X

S X -

Sb* X X

Sn* X X

Zn X -

Se* X X

Mg** - X

P** - X

Si** - X

Trace ElementsElement Monthly Assays

(Composite Sample)

Ag X

Al X

B X

Be X

Ca X

Ce X

Cr X

Ga X

K X

La X

Mg X

Mo X

Na X

Te X

Ti X

Tl X

V X

Assay Frequency

32

IntroducingPlating Roundsto Customers

33

Timeline of trials and adoption (Aug 2017 – Today)

Aug 2017

Plating onPlastics

Automotive

Successfulconversion

Nov 2017

Plating onMetals

Auto, furniture

Successfulconversion

Dec 2017

Broad-basedsamplingglobally

Jan-Jun 2018

Increasingtrials/adoption

All segments

Globaldistribution

Sep 2018

OFFICIALLAUNCH

Long Harbour Plating Rounds Trials

Product Improvements

34

Segments trialedAutomotive – metals & plasticsDecorative – castings, metalElectronics – reel-to-reel, PCBFunctional – structural parts

Trial Locations

Concerns• Dissolve different from R-Rounds• Sulphur and Carbon• Green crystals

Plating trials feedback

Positive feedbackü Quality plating – physical and visualü No bridgingü Easy loading into basketsü Approved for use – no difference when

compared to R-Roundsü Used in semi-bright, bright, satin,

microporous applications

Plating Rounds volumes >1300mt worldwide

35

Plating RoundsFrequently Asked Questions

36

Sulphur is more elevated than in Thompson R-Rounds, will this have abenefit similar to sulphur in S-Pellets and S-Rounds?

Sulphur content vs Limiting currentS-activated nickelwere designed around0.02%-0.03% sulphurand for good reason!

With Sulphur levels lowerthan 0.010% (100ppm), thebenefits of increasedactivity are small.

Evidence shows that, likeS-Rounds, there is nonegative impact of Sulphuron nickel deposits.

The impact of sulphur levels in nickel and ability to dissolve.

0

50

100

150

200

250

0.00 0.01 0.02 0.03 0.04 0.05 0.06

Sulfur Content (%)

Lim

iting

Cur

rent

Den

sity

(mA

/sq.

cm) (NiSO4 soln. with less than 0.5 g/l of Cl ion at 55C)

Source: INCO Plating Lab Research

S-Pellets &S-Roundsrange ofsulphur

37

Plating Rounds have higher sulphur than R-Rounds, does this affect the partquality?

Sulphur content has shown no impact on plated parts

No increased sulphurcontent in plated partsin Vale lab testing

Customer testing haspassed end-user(OEM/Tier 1)specifications –including CASS

Plating Rounds used inall nickel applicationsincluding sulphursensitive Semi-Bright

Vale labtesting

PlatingRounds

qualified

CASStesting Ductility

…Numerouscustomer

testingresults

Sulphurcontent in

layers

AdhesionChisel test

Cut test

38

Plating Rounds have much higher carbon that R-Rounds, this must meanmuch more residue? Black sludge?

Carbon content Carbon relative to nickel isvery small (45g/mt Ni).

>95% of residue are nickelfines and not carbon, despitethe black appearance

High likelihood of basketmaintenance ahead of thisaccumulation of carbon givennumber of turnovers required

Based on 3.8g/cm3 packing density

Carbon LevelsPlating Rounds 80 ppmThompson R-Rounds 35 ppmDifference 45ppm

Industry Basket (cm) Ni Weight TurnoversMetal / PoP 100 x 6 x 20 50kg 20Electronics 40 x 5 x 15 12kg 88

39

Do the Plating Rounds dissolve differently than Thomson R-Rounds? Couldthis creating more residue?

Nickel finesThompson was best-in-classso can expect questions fromcustomers on residue.

This is mostly small nickelpieces that have fallen fromthe main piece of nickel. It isnot carbon even if it is black.

Basket design with tray at thebottom and tight fitting bagswill hold the fines in electricalcontact minimizing the effect.

.Residue is actually finesdislodged from the nickel.

Sample Ni (%) C (%) S (%)

P-Pellets 96.9 0.73 0.1

Chips 99.4 0.5 0.1

R-Rounds 95 2.6 2.4

S-Pellets 13 2.8 14.8

Nickel

40

Plating Rounds are dissolving more quickly!• Faraday’s Law – directly proportional to time and electrical current• Packing Density – less nickel in the basket, level will drop more quickly• Preferential plating – if mixing baskets with Plating Rounds and 1x1, the lower

resistance in the Plating Rounds will have higher current = increased dissolution• Constant current plating – most common, lower resistance with same current,

means lower voltage, so power savings.• Constant voltage plating – lower resistance, higher current, means more plating

for the same amount of time – chance of over-plating

VR2 I2xR1 I1x

PlatingRounds

1 x 1

Preferential plating can also occur if mixing S-activated nickel with non-activated

41

Long Harbour Plating Rounds are not as bright as Thompson’s R-Rounds.Why?

Brightness This is a surfacesmoothness issue.

Organics can beadded to increasesmoothness butwould increasecarbon content.

The organic moleculesaccumulate at areasclosest to the anodepreventing acceleratedgrowth at peaks andforcing growth in valleys.

Smoothness has noimpact on performance.

Organics can be added to electrolyte to smooth the surface.

Organics molecule

42

Plating RoundsKey conversion tips

43

Customer conversion tips

Start small. Grow trial with increasing amounts of Plating Rounds.

Mixing Plating Rounds with current nickel anode is ok. Builds confidence.

Change all baskets in one tank to avoid preferential plating.

Remind customer not to hammer the nickel down, it will settle unlike cut cathode.

The lower packing density means lower in process inventory and cost but need towatch basket levels.

If the Plating Rounds are dissolving differently than previously used nickel but haveno problems, leave it alone.

Explain the relative impact of carbon and sulphur levels if required

Monitor for a drop in voltage or electrical power – adjust & calculate savings.

Plating Rounds vs cut cathode competition

44

*Subject to customer evaluation

Advantages

Safe handling

Quality plating

No bridging

No hammering

Lower inventory

Lower electrical costs

Challenges

Carbon

Sulphur

…

45

Going forward

46

Delivery from Long Harbour via Port Colborne

PackagedLots

Lot1523

Lot1643

Lot1586

Plating GradeLotsLong

HarbourRefinery

50kg boxes 250kgdrums

Packaging Process1. Long Harbour Refinery selects Lots that

meets Plating Quality Specification

2. Rounds are shipped to Port Colborne forprocessing and packaging

3. Multiple Lots are mixed for packaging ona campaign basis

4. Port Colborne ships Plating Rounds tocustomers for Long Harbour Refinery

5. Certificate of Conformance availableensuring Plating Rounds specification ismet.

47

Plating Rounds Packaging

10kg bag/50kg box

250kgdrums

48

RoHS TestingEasily passes RoHS requirements

49

50

Plating products for the future

Plating ChipsTMP-PelletsTM

S-PelletsTM Plating RoundsTM

51