Zirconium Oxide

in Metal Finishing

Bill Gaines

bgaines1@ford.com

Zirconium Oxide in Metal Finishing

The Zr Process

Chemistry Introduced/Chemistry Removed

Zr Water Treatment

Zr Toxicity

Zr Regulations

Phosphate is part of a highly monitored, highly controlled painting process:

Deluge

spray

Cleaner

spray

Cleaner

dip

H20 rinse

dip

Activation

dip

Phosphate

dip

H20 rinse

dip Passivation

dip

DI dip &

virgin

DI spray

E-coat dip-

cream coat

rinse

U/F perm

spray

U/F dip&

virgin

U/F spray

DI water

dip

DI spray &

virgin DI spray

E-coat

oven E-coat

strip

Sealer

deck #0

Robot roof

ditch seal

station

Sealer

deck #1 Sealer gel

oven Sealer gel

cooling E-coat

scuff

Blow

-off Prime Oven

Cooling tunnel Prime

scuff

Enamel

Oven

Enamel

strip Surge

Prime

spray booth

Enamel

Clearcoat booth

Enamel

Basecoat booth Blow - off

Seek & repair

( Low & High Platform )

Wax &

Blackout booth

Spot repair

To trim

Pre-Cleaner

Stage

From body

shop

Sealer

deck #2

PHOSPHATE STAGES 1-7

Times: :27 :27 :27 :37 1:47 :47 :27 :37 1:47 :36 1:47 :47

Stage Description: Stage 1 Stage 2 Stage 3 Stage 4 Stage 5 Stage 6 Stage 7

Zone Description: Spray Cleaner 1 Deluge Spray Cleaner 2 Drain Zone Immersion Cleaner Drain Zone City Water Rinse Drain Zone Immersion Rinse Conditioner Drain Zone Immersion Phosphate Drain Zone

From Body Shop

Shown Compressed

Length in Feet: 20' 8" 20' 8" 20' 8" 28' 9" 82' 10" 36' 4" 20' 8" 28' 8" 82' 4" 28' 5" 82' 10" 36' 5"

Phosphate Conveyor Parameters Spray Cleaner 1 - CK275 Deluge - City Water Spray Cleaner 2 - CK166 / 171 Immersion Cleaner - CK166 / 171 City Water - Spray Rinse Rinse Conditioner - Immersion Phosphate - CF700RcanJob/Hour 74.6 Product ID Chemkleen 275 Fill Make-Up City Water Product ID Chemkleen 166HP Product ID Chemkleen 166HP Entrance Spray Information Source City Total Titanium (PPM) 2.5>ppm Product ID Chemfos 700Rcan

Line Speed 46.3 FPM Product ID 2 N/A Total Alkalinity N/A Product ID 2 Chemkleen 171A Product ID 2 Chemkleen 171A Overhead Nozzles Total Alkalinity 0 - 3.5 Filtereed Titanium (PPM) N/a Free Acidity .65-.90

Conveyor Type OH/P&F Product ID 3 N/A - Product ID 3 N/A Product ID 3 N/A # of Nozzles 30 Ph Range 7-7.9 Ph Range 7-7.9 Total Acidity 13-19

Job Spacing 11'5" Concentration % N/C - Concentration % N/C Concentration % N/C Nozzle Type V-jet 5070 - - Liquid Additive 1.5-2.3

Total Vehicle Length 18'8" to 21'3" Free Alkalinity 1 - 2.4 - Free Alkalinity .5-1.1 Free Alkalinity 1.2-3.0 Pressure N/C - - Test Method: -

Job Pitch 11'5" Total Alkalinity 1.4 Tank Capacity (US Gallons) 8,625 Total Alkalinity N/A Total Alkalinity N/A Flow Rate N/C Tank Capacity (US Gallons) 12,731 Tank Capacity (US Gallons) 44,859 Flouride (PPM) N/A

Total Application Time 32 minutes Ph Range N/A Total Dwell Time 30 secs Ph Range N/A Ph Range N/A Vertical Nozzles Total Dwell Time 30 secs Total Dwell Time 120 secs -

- Temperature Ambient - - # of Nozzles 30 Temperature Ambient Temperature Ambient -

- Overflow Rate 15 gpms - - Nozzle Type V-jet 5070 Overflow Rate 15 gpms Overflow Rate N/A -

Tank Capacity (US Gallons) 3600 GAL Counterflow Rate N/A Tank Capacity (US Gallons) 16,385 Tank Capacity (US Gallons) 84,557 Pressure N/C Counterflow Rate N/A Counterflow Rate N/A Tank Capacity (US Gallons) 112,478

Total Dwell Time 30 secs Over to Drain Rate N/A Total Dwell Time 35 secs Total Dwell Time 120 secs Flow Rate N/C Over to Drain Rate N/A Over to Drain Rate N/A Total Dwell Time 120secs

Temperature Ambient Total Header Rings N/A Temperature 120 - 130 Temperature 120 - 130 Exit Spray Information Total Header Rings V-Jet 5070 Entry Angle 45 degree Temperature 120-130

Overflow Rate N/A Total Number of Nozzles N/A Overflow Rate 15 gpms Overflow Rate N/A Overhead Nozzles Total Number of Nozzles 346 Exit Angle 45 degree Overflow Rate -

Counterflow Rate N/A Total Flow N/C Counterflow Rate N/A Counterflow Rate 20 gpms # of Nozzles 30 Total Flow N/C Total Number of Tank Eductors 24 Counterflow Rate N/A

Over to Drain Rate N/A Total Number of Tank Eductors N/A Over to Drain Rate N/A Over to Drain Rate N/A Nozzle Type V-jet 5070 Total Number of Tank Eductors N/A Header Pressure for Eductors N/C Over to Drain Rate N/A

Total Header Rings N/A Header Pressure for Eductors N/A Total Header Rings 15 Entry Angle N/C Pressure N/C Header Pressure for Eductors N/A Drain Zone Apex Location 10 Feet From End Entry Angle 45 Degree

Total Number of Nozzles 96 Drain Zone Apex Location 8 ft from end Total Number of Nozzles 198 Exit Angle N/C Flow Rate N/C Drain Zone Apex Location 8 Feet From End Tank Turn-Overs per Hour N/C Exit Angle 45 Degree

Total Flow N/C Tank Turn-Overs per Hour N/A Total Flow N/C Total Number of Tank Eductors 44 Vertical Nozzles Tank Turn-Overs per Hour N/A Circulation Total Number of Tank Eductors 28

Total Number of Tank Eductors N/A Circulation Total Number of Tank Eductors N/A Header Pressure for Eductors N/C # of Nozzles 30 Circulation Front End Pump Type Gusher Header Pressure for Eductors N/C

Header Pressure for Eductors N/A Pump Type Gusher Header Pressure for Eductors N/A Drain Zone Apex Location 10 Feet From End Nozzle Type V-jet 5070 Pump Type Gusher Number of Front End Pumps 2 Drain Zone Apex Location 10 Feet From End

Drain Zone Apex Location N/A Number of Pumps 2 Drain Zone Apex Location 10 Feet From End Tank Turn-Overs per Hour N/A Pressure N/C Number of Pumps 3 GPM of Each Front End Pump N/C Tank Turn-Overs per Hour N/C

Tank Turn-Overs per Hour N/A Pump HP 30 Tank Turn-Overs per Hour N/A Circulation Flow Rate N/C Pump HP 50 Pump HP (Each) 40 CirculationCirculation Gallons Per Minute N/C Circulation Front End Pump Type Gusher Maintenance Information Gallons Per Minute N/C Total Gallons per Minute (Front) N/C Front End Pump Type gusher

Pump Type Gusher Risers N/A Pump Type Gusher Number of Front End Pumps 4 Dump Frequency Risers N/C # of Front Eductor Headers 14 Number of Front End Pumps 2

Number of Pumps 2 Filtering Number of Pumps 3 GPM of Each Front End Pump N/C Tank is dumped and cleaned 2 x a year Filtering Exit Pump Type N/A GPM of Each Front End Pump N/C

Pump HP 75 Filter Type Bag filters Pump HP 40 Pump HP (Each) 50 Filter Type Bags Number of Exit Pumps N/A Pump HP (Each) 30

Gallons Per Minute N/C Microns: 400 Gallons Per Minute N/C Total Gallons per Minute (Front) N/C Microns: 200 GPM of Each Exit End Pump N/A Total Gallons per Minute (Front) N/C

Risers N/A Number of Filters: 21 Risers N/C # of Front Eductor Headers 22 Number of Filters: 28 Pump HP (Each) N/A # of Front Eductor Headers 14

Chemical Feed Pump Types # of Vessels: 3 Chemical Feed Pump Types Exit Pump Type N/A # of Vessels: 4 Total Gallons per Minute (Exit) N/A Exit Pump Type Gusher

1 Pulsatron 3 Bags per Vessel: 7 1 N/A 3 Number of Exit Pumps N/A Bags per Vessel: 7 # of Exit Eductor Headers N/A Number of Exit Pumps 2

2 4 Do you use Magnets: No 2 4 GPM of Each Exit End Pump N/A Do you use Magnets: No Chemical Feed Pump Types GPM of Each Exit End Pump N/A

Quick Feed Pumps Present? No Change Point: N/A Quick Feed Pumps Present? No Pump HP (Each) N/A Change Point: N/A 1 Pulsatron 3 Pump HP (Each) 40

Filtering Overhead Nozzles Filtering Total Gallons per Minute (Exit) N/A Heat Exchanger 2 4 Total Gallons per Minute (Exit) N/C

Filter Type bag filter # of Nozzles N/A Filter Type Bag filters # of Exit Eductor Headers N/A Type N/A Quick Feed Pumps Present? No # of Exit Eductor Headers 10

Microns: 400 Nozzle Type N/A Microns: 200 Chemical Feed Pump Types Inlet Pressure N/A Filtering Chemical Feed Pump Types

Number of Filters: 12 Pressure N/A Number of Filters: 30 1 Diaphgram 3 Outlet Pressure N/A Filter Type Bags 1 Pulsatron 3

# of Vessels: 2 Flow Rate N/A # of Vessels: 3 2 4 Cleaning Schedule Basis N/A Microns: 100 2 Pulsatron 4

Bags per Vessel: 6 Vertical Nozzles Bags per Vessel: 10 Quick Feed Pumps Present? No Overhead Nozzles Number of Filters: 6 Quick Feed Pumps Present? No

Do you use Magnets: no # of Nozzles N/A Do you use Magnets: No Filtering # of Nozzles 120 # of Vessels: 1 FilteringChange Point: Pressure Nozzle Type N/A Change Point: Pressure Filter Type Bag Nozzle Type V-jet 5070 Bags per Vessel: 6 Filter Type Filter Press

Heat Exchanger Pressure N/A Heat Exchanger Microns: 200 Pressure N/C Do you use Magnets: No Microns: N/A

Type N/A Flow Rate N/A Type Plate and frame Number of Filters: 28 Flow Rate N/C Change Point: N/A Number of Filters: N/A

Inlet Pressure N/A Floor Nozzles Inlet Pressure 27 psi # of Vessels: 4 Vertical Nozzles Heat Exchanger # of Vessels: N/A

Outlet Pressure N/A # of Nozzles N/A Outlet Pressure 52 psi Bags per Vessel: 7 # of Nozzles 120 Type N/A Bags per Vessel: N/A

Inlet Temperature N/A Nozzle Type N/A Inlet Temperature 120 Do you use Magnets: No Nozzle Type V-jet 5070 Inlet Pressure N/A Do you use Magnets: No

Outlet Temperature N/A Pressure N/A Outlet Temperature 129 Change Point: Pressure Pressure N/C Outlet Pressure N/A Change Point: N/A

Cleaning Schedule Basis N/A Flow Rate N/A Cleaning Schedule Basis Time Heat Exchanger Flow Rate N/C Cleaning Schedule Basis N/A Heat Exchanger

Overhead Nozzles Maintenance Information Overhead Nozzles Type Plate and Frame Floor Nozzles Chemical Feed Harness Type Plate and Frame

# of Nozzles 52 Dump Frequency 1x Weekly # of Nozzles 77 Inlet Pressure 16 psi # of Nozzles 84 Overhead Nozzles Inlet Pressure 20

Nozzle Type 0 degree Dumped & Cleaned Saturday Nozzle Type V-jet 5070 Outlet Pressure 40 psi Nozzle Type V-jet 50150 # of Nozzles 2 Outlet Pressure 34

Pressure N/C Screens are cleaned in Same Schedule Pressure N/C Inlet Temperature 122 Pressure N/C Nozzle Type K-Jet Inlet Temperature 120

Flow Rate N/C Flow Rate N/C Outlet Temperature 125 Flow Rate N/C Pressure NC Outlet Temperature 125

Vertical Nozzles Vertical Nozzles Cleaning Schedule Basis Time Maintenance Information Flow Rate NC Cleaning Schedule Basis Time and/or Pressure

# of Nozzles 40 # of Nozzles 65 Dump Frequency 1x Weekly Vertical Nozzles Exit Spray Information

Nozzle Type 0 degree Nozzle Type V-jet 5070 Tank is Dumped and Cleaned every Saturday # of Nozzles 2 Overhead NozzlesPressure N/C Pressure N/C Screens are cleaned on Same Schedule Nozzle Type K-Jet # of Nozzles 32

Flow Rate N/C Flow Rate N/c Pressure NC Nozzle Type V-jet 5070

Floor Nozzles Floor Nozzles Flow Rate NC Pressure N/C

# of Nozzles 4 # of Nozzles 56 Maintenance Information Flow Rate N/C

Nozzle Type 0 degree Nozzle Type V-jet 50150 Dump Frequency Weekly Vertical NozzlesPressure N/A Pressure N/C Tank is Dumped and Cleaned weekly # of Nozzles 32

Flow Rate N/A Flow Rate N/c Screens are Cleaned Weekly Nozzle Type V-jet 5070

Maintenance Information Maintenance Information Pressure N/C

Dump Frequency 1X Weekly Dump Frequency 1X Weekly Flow Rate N/C

Tank is Dumped and Cleaned every Saturday Tank is Dumped and Cleaned every Saturday Maintenance InformationScreens are Cleaned on the same Schedule Screens are Cleaned on the same Schedule Dump Frequency 1x Yearly

Tank is Decanted and Chemically

Cleaned once a year.

Screens are cleaned weekly

PHOSPHATE STAGES 8-13

Times: :17 :37 1:24 :36 1:47 :47 :27 1:05 1:49 1:47 :37 :09

Stage Description: Stage 8 Stage 9 Stage 10 Stage 11 Stage 12 Stage 13

Zone Description: City Water Spray Drain Zone City Water Immersion Drain Zone Not in Use Drain Zone Recirc. DI Rinse Drain and Observation Area Drain Zone Recirc. DI Water Immersion Drain Zone Virgin DI Rinse

Conveyor Turns To E-Coat

180 Degrees

and Heads in the

Opposite

From Stage 7 Direction Total Time

for Process

27:25

Shown Compressed Shown Compressed Shown Compressed Expanded

Length in Feet: 13' 28' 8" 64' 7" 28' 5" 82' 10" 36' 4" 20' 8" 50' 84' 82' 10" 28' 4" 6' 11"

City Water - Spray Rinse City Water - Immersion Rinse No Immersion Process Recirc DI - Spray Rinse Recirc DI - Immersion Rinse Virgin DI - Spray RinseSource City Source City Entrance Spray Information Source - Fill Source Make-up DI Fill Source Virgin DI Entrance Spray Information Soucre Plant DI

Total Acid 0-1.0 Total Acid 0-1.0 Overhead Nozzles Total Alkalinity - Ph Range N/A Ph Range N/A Overhead Nozzles Ph Range N/A

Ph Range N/A Ph Range N/A # of Nozzles 13 Ph Range - Max Conductivity 500mmhos Max Conductivity 50 mmhos # of Nozzles 32 Max Conductivity 50mmhos

- - Nozzle Type V-jet 5070 - - - Nozzle Type V-jet 5070 -

- - Pressure N/C - - - Pressure N/C -

Tank Capacity (US Gallons) 5711 gals Tank Capacity (US Gallons) 44,859 Flow Rate N/C Tank Capacity (US Gallons) - Tank Capacity (US Gallons) 12,731 Tank Capacity (US Gallons) 44,859 Flow Rate N/C Tank Capacity (US Gallons) N/A

Total Dwell Time 15 secs Total Dwell Time 45secs Vertical Nozzles Total Dwell Time - Total Dwell Time 30secs Total Dwell Time 120 secs Vertical Nozzles Total Dwell Time 10 secs

Temperature ambient Temperature ambient # of Nozzles 14 Temperature - Temperature ambient Temperature ambient # of Nozzles 32 Temperature Ambient

Overflow Rate 15 gpms Overflow Rate N/C Nozzle Type V-jet 5070 Overflow Rate - Overflow Rate 15 gpm Overflow Rate 15 gpm's Nozzle Type V-jet 5070 Overflow Rate N/A

Counterflow Rate N/A Counterflow Rate 20 gpms Pressure N/C Counterflow Rate - Counterflow Rate N/A Counterflow Rate N/A Pressure N/C Counterflow Rate 15 gpm's

Over to Drain Rate N/A Over to Drain Rate N/A Flow Rate N/C Over to Drain Rate - Over to Drain Rate N/A Over to Drain Rate N/A Flow Rate N/C Over to Drain Rate N/A

Total Header Rings 22 Entry Angle 45 degree Exit Spray Information Entry Angle - Total Header Rings 13 Entry Angle 45 degrees Exit Spray Information Total Header Rings 1

Total Number of Nozzles 186 Exit Angle 45 degree Overhead Nozzles Exit Angle - Total Number of Nozzles 356 Exit Angle 45 degrees Overhead Nozzles Total Number of Nozzles 12

Total Flow N/C Total Number of Tank Eductors 24 # of Nozzles 32 Total Number of Tank Eductors - Total Flow N/C Total Number of Tank Eductors 24 # of Nozzles 32 Total Flow 15 gpm's

Total Number of Tank Eductors N/A Header Pressure for Eductors N/C Nozzle Type N/A Header Pressure for Eductors - Total Number of Tank Eductors N/A Header Pressure for Eductors 10 gpm's Nozzle Type V-jet 5070 Total Number of Tank Eductors N/A

Header Pressure for Eductors N/A Drain Zone Apex Location 8 feet from end Pressure N/A Drain Zone Apex Location - Header Pressure for Eductors N/A Drain Zone Apex Location 5 feet from end Pressure N/C Header Pressure for Eductors N/A

Drain Zone Apex Location 10 Feet From End Tank Turn-Overs per Hour N/C Flow Rate N/A Tank Turn-Overs per Hour - Drain Zone Apex Location 10 Feet From End Tank Turn-Overs per Hour N/C Flow Rate N/C Drain Zone Apex Location 10 Feet From End

Tank Turn-Overs per Hour N/A Circulation Vertical Nozzles Circulation Tank Turn-Overs per Hour N/A Circulation Vertical Nozzles Tank Turn-Overs per Hour N/A

Circulation Front End Pump Type gusher # of Nozzles 32 Front End Pump Type - Circulation Front End Pump Type Gushers # of Nozzles 32 CirculationPump Type gusher Number of Front End Pumps 2 Nozzle Type N/A Number of Front End Pumps - Pump Type gusher Number of Front End Pumps 2 Nozzle Type V-jet 5070 Pump Type N/C

Number of Pumps 2 GPM of Each Front End Pump N/C Pressure N/A GPM of Each Front End Pump - Number of Pumps 3 GPM of Each Front End Pump N/C Pressure N/C Number of Pumps N/C

Pump HP 40 Pump HP (Each) 40 Flow Rate N/A Pump HP (Each) - Pump HP 50 Pump HP (Each) 40 Flow Rate N/C Pump HP N/C

Gallons Per Minute N/C Total Gallons per Minute (Front) N/C Maintenance Information Total Gallons per Minute (Front) - Gallons Per Minute N/C Total Gallons per Minute (Front) N/C Maintenance Information Gallons Per Minute N/C

Risers 2 # of Front Eductor Headers 14 Dump Frequency 1X Weekly # of Front Eductor Headers - Risers 3 # of Front Eductor Headers 12 Dump Frequency - Risers N/C

Filtering Exit Pump Type N/A Tank is Dumped and Cleaned Exit Pump Type - Filtering Exit Pump Type N/A Tank is treated with Hydrogen Peroxide FilteringFilter Type Bags Number of Exit Pumps N/A every Saturday Number of Exit Pumps - Filter Type bags Number of Exit Pumps N/A weekly on Saturday Filter Type N/A

Microns: 100 GPM of Each Exit End Pump N/A Screens are cleaned on Same GPM of Each Exit End Pump - Microns: 100 GPM of Each Exit End Pump N/A Screens are cleaned weekly on Saturday Microns: N/A

Number of Filters: 28 Pump HP (Each) N/A Schedule Pump HP (Each) - Number of Filters: 28 Pump HP (Each) N/A Number of Filters: N/A

# of Vessels: 4 Total Gallons per Minute (Exit) N/A Total Gallons per Minute (Exit) - # of Vessels: 4 Total Gallons per Minute (Exit) N/A # of Vessels: N/A

Bags per Vessel: 7 # of Exit Eductor Headers 3 # of Exit Eductor Headers - Bags per Vessel: 7 # of Exit Eductor Headers 12 Bags per Vessel: N/A

Do you use Magnets: No Filtering Filtering Do you use Magnets: No Filtering Do you use Magnets: N/A

Change Point: Pressure Filter Type bags Filter Type - Change Point: Pressure Filter Type bags Change Point: N/A

Heat Exchanger Microns: 100 Microns: - Heat Exchanger Microns: 25 Overhead NozzlesType N/A Number of Filters: 28 Number of Filters: - Type N/A Number of Filters: 21 # of Nozzles 14

Inlet Pressure N/A # of Vessels: 4 # of Vessels: - Inlet Pressure N/A # of Vessels: 3 Nozzle Type V-jet 5070

Outlet Pressure N/A Bags per Vessel: 7 Bags per Vessel: - Outlet Pressure N/A Bags per Vessel: 7 Pressure N/C

Cleaning Schedule Basis N/A Do you use Magnets: No Do you use Magnets: - Cleaning Schedule Basis N/A Do you use Magnets: No Flow Rate 15 gpm's

Overhead Nozzles Change Point: Pressure Change Point: - Overhead Nozzles Change Point: Pressure Vertical Nozzles# of Nozzles 78 Heat Exchanger Heat Exchanger # of Nozzles 136 Heat Exchanger # of Nozzles 14

Nozzle Type V-jet 5070 Type N/A Type - Nozzle Type V-jet 5070 Type N/A Nozzle Type V-jet 5070

Pressure N/C Inlet Pressure N/A Inlet Pressure - Pressure N/C Inlet Pressure N/A Pressure N/C

Flow Rate N/C Outlet Pressure N/A Outlet Pressure - Flow Rate N/C Outlet Pressure N/A Flow Rate 15 gpm's

Vertical Nozzles Cleaning Schedule Basis N/A Cleaning Schedule Basis - Vertical Nozzles Cleaning Schedule Basis N/A Floor Nozzles# of Nozzles 78 Entrance Spray Information # of Nozzles 136 # of Nozzles N/A

Nozzle Type V-jet 5070 Exit Spray Information Nozzle Type V-jet 5070 Nozzle Type N/A

Pressure N/C Maintenance Information Pressure N/C Pressure N/A

Flow Rate N/C Dump Frequency Flow Rate N/C Flow Rate N/A

Floor Nozzles Floor Nozzles Maintenance Information# of Nozzles 40 # of Nozzles 84 Dump Frequency N/A

Nozzle Type V-jet 50151 Nozzle Type V-jet 50100

Pressure N/C Pressure N/C

Flow Rate N/C Flow Rate N/C

Maintenance Information Maintenance InformationDump Frequency 1x Weekly Dump Frequency 1x Weekly

Tank is Dumped and Cleaned every Saturday Tank is Dumped and Cleaned on Saturday

Screens are cleaned on Same Schedule Screens are cleaned on the same schedule

Stage is treated weekly with 25 gallons of

hydrogen peroxide

Inside an Automotive Phosphate Machine

Inside an Automotive Phosphate Machine

STAGE 7 PHOSPHATE DIP

DRAIN

STAGE 8 WATER SPRAY RINSE

TRAVEL TRAVEL

DRAIN

STAGE 9 WATER SPRAY RINSE

DRAIN

STAGE 10 PASSIVATION

SPRAY

DRAIN

STAGE 11 D.I.

SPRAY

DRAIN

STAGE 12 DEIONIZED WATER DIP

(IN/OUT)

DRAIN DRAIN

STAGE 13 VIRGIN D.I.

WATER SPRAY (HALO)

Phosphate Rinse Passivation Rinse

Rinse Dip

Water

Rinse

DI

Rinse

(Spray)

(Spray

)

Or more simply……….

STAGE 1 DELUGE SPRAY WASH

STAGE 3 CLEANER DIP

DRAIN

STAGE 4 WATER SPRAY

DRAIN

STAGE 6 SURFACE

CONDITIONER DIP (IN/OUT)

MANUAL PREWIPE

TRAVEL

VEST./ AIR

SEAL

STAGE 2 HIGH

PRESSURE CAUSTIC SPRAY

DRAIN DRAIN

STAGE 5 WATER RINSE

DRAIN

TRAVEL

Cleaner Rinse Condition

Claimed Zr Benefits

60% reduction in DI rinse water

15% electricity reduction (pumps)

40% energy reduction (heat exchangers)

Reduced complexity

Smaller footprint

Increased throughput

No phosphate incrustation → fewer boil-outs

How Is It Done?

STAGE ELIMINATION

Deluge

spray

Cleaner

spray

Cleaner

dip

H2O rinse

dip

Activation

dip

Phosphate

dip

H2O rinse

dip Passivation

dip

DI dip &

virgin

DI spray

Pre-Cleaner

Stage

Deluge

spray

Cleaner

spray

Cleaner

dip

H2O rinse

dip

Activation

dip

Zirconium

dip

H2O rinse

dip Passivation

dip

DI dip &

virgin

DI spray

Pre-Cleaner

Stage

Replace Zinc Phosphate Zn3(PO4)2

with Zirconium Oxide ZrO2

Zn + P (virtually) eliminated from chemistry!!!

Process control simplified (~100,000-gal

phosphate tank needs temp control of 125+/-3 oF)

• High temp causes excessive formation

• Low temp causes unsatisfactory phosphate/steel reaction

Eliminate activation & passivation stages and their

associated chemistries

Zinc Phosphate Bath Converted to Zr

Zn, Ni, Mn, & P eliminated from coating chemistry!!!

NOTE: SOME P REMAINS IN CLEANER CHEMISTRY

Polycrystalline Zn3(PO4)2 becomes amorphous ZrO2

Lower coating weight leads to shortened processing time

(namely, reduced footprint and increased throughput)

Corrosion Performance

Better on Al – slightly worse for EG

GM 9540P Ford APGE European VDA

621-415

Dirty Little Secrets

• Zirconium was present in some manufacturer’s

passivation steps (though much less)

• Zinc is not eliminated – acidic leaching from

galvanized substrate (though much less)

• Phosphate is not eliminated – still present in some

cleaners (though much less)

• Cu/F remain in some manufacturer’s formulations

Zr Treatment - Transition Metals

Hydroxide precipitation works on:

Zinc Nickel

Chromium Copper

Tin Cobalt

Mercury Aluminum

Iron Cadmium

Silver Arsenic so why not Zirconium???

Hydroxide Precipitation

Precipitating Agents:

Calcium Hydroxide - Ca(OH)2

Magnesium Hydroxide - Mg(OH)2

Sodium Hydroxide - Na(OH)

Zn2+ (aq) + 2OH- (aq) = Zn(OH)2 (s)

Cu2+ (aq) + 2OH- (aq) = Cu(OH)2 (s)

Ni2+ (aq) + 2OH- (aq) = Ni(OH)2 (s)

Solubility Product Constant (KSP)

The amount of any ionic species that can be placed in

solution is determined by it’s solubility expression:

Zn(OH)2 Zn2+ + 2OH-

KZn(OH)2 = [Zn+] [OH-]2

(Which would suggest that the highest pH results in the lowest zinc

concentration – which isn’t the case.)

Compound Formula Ksp (25oC)

Aluminum hydroxide Al(OH)3

3x10-34

Cadmium hydroxide Cd(OH)2

7.2x10-15

Copper (II) hydroxide Cu(OH)2

4.8x10-20

Lead (II) hydroxide Pb(OH)2

1.43x10-20

Lead (IV) hydroxide Pb(OH)4

3.2x10-66

Mercury hydroxide Hg(OH)2

3.2x10-26

Nickel hydroxide Ni(OH)2

5.48x10-16

Zinc hydroxide Zn(OH)2

3x10-17

Zirconium hydroxide Zr(OH)2

6.3x10-49

Zr Treatment

Most metal ions are multivalent so their solubility is proportional to the

power of the hydroxyl ion:

M(OH)x M+x + xOH-

KSP = [M+x] [OH-]x

Zr Treatment

So why isn’t higher pH better?

Zn2+ (aq) + 2OH- (aq) Zn(OH)2 (s) Good thing!

Zn(OH)2 (s) + OH- (aq) Zn(OH)3- (aq) Bad

Zn(OH)3- (aq) + OH- (aq) Zn(OH)4

-2 (aq) Bad

Etc.

Etc.

Hydroxide Precipitation

Zr Treatment – Henkel Laboratory Study

3 Baths Treated:

Fresh 3% laboratory standard

Ford TCAP Zr bath

Ford TCAP bath diluted 3 times

Two Methods Used:

• A: To pH 9.0 with Ca(OH)2, FeCl3, polymer

• B: Acidify to pH 2.0 then method A above

Zr Treatment – Henkel Laboratory Study

Zr Treatment – Henkel Laboratory Study

Zr Treatment – Henkel Laboratory Study

Final zinc blamed on “experimental errors”

Zr Treatment – Ford Field Study

Zr Treatment – StAP WWTP Data Phosphate Batches

Zr Treatment – StAP WWTP Data Zirconium Routine

Zr Treatment – StAP WWTP Data

Zr Treatment – StAP WWTP Data

Began bleeding in cleaner dumps and the majority of

batches didn’t require treatment (compliant coming in).

Stage 7 always required Zn treatment (up to 900 ppm before

stage becomes unuseable).

Zirconium Toxicity

CDC: “ziconium coumpounds posses a low order of toxicity”

(ZrO2 is used for hip replacements)

Zr Inhibition of Activated Sludge? Not here……

Zr Inhibition of Activated Sludge? Not here……

Zr Inhibition of Activated Sludge? Not here……

Zr Inhibition of Activated Sludge?

Zr Inhibition of Activated Sludge?

USEPA ECOTOX Report

Zr Inhibition of Activated Sludge (It’s pretty high)

Abstract Our contribution to Zr environmental hazard, arrived at by means of bioassays

on bacteria, microscopic algae and fish, confirms the hypothesis that Zr

has low toxicity. Toxic effects revealed with the Microtox test may

be attributed to pH rather than specifically to Zr (5 min. EC50

> 4.3 mg/L). Fish assays also confirmed the low toxicity of Zr (96-hr LC50 > 20 mg

L–1; 96 hr minimal stress concentration > 20 mg L–1; Mutagenicity (Fluctuation test) and

genotoxicity (S.O.S. Chromotest) assays failed to show any DNA-related effects linked to

this metal. Only the algal assays (ATP energy stress) demonstrated genuine toxicity at Zr

concentrations between 1.3 and 2.5 mg L–1.

Zirconium Toxicity Assessment using Bacteria, Algae and Fish Assays

P. Couture, C. Blaise, D. Cluis and C. Bastien

1989 The Netherlands

F019 Issue…….

F019 is one of EPA’s RCRA hazardous waste

listings, which include wastes that are generated

from processes such as chromating,

phosphating, metal coloring and/or immersion

plating. F019 wastes are defined as

wastewater treatment sludges from the

chemical conversion coating of aluminum

(except from zirconium phosphating in aluminum

can washing).

F019 Issue…….

The USEPA Office of Resource Conservation and

Recovery made a determination in 2009 that the

zirconium oxide process is not chemical

conversion coating.

Therefore wastewater treatment sludges

generated are not covered by the F019 listing.

Is Zr Regulated?

Is Zr Regulated?

Questions?