11

MultiMulti--functional Metallic and Refractoryfunctional Metallic and RefractoryMaterials for Energy Efficient Handling forMaterials for Energy Efficient Handling for

Molten MetalsMolten Metals

Progress ReportProgress Report

DOE-ITP: DE-FC36-04GO14038

Xingbo Liu, Ever Barbero, Bruce Kang, Thomas Damiani,Xingbo Liu, Ever Barbero, Bruce Kang, Thomas Damiani,BhaskaranBhaskaran GopalakrishnanGopalakrishnan, Carl Irwin, Carl Irwin

West Virginia UniversityWest Virginia UniversityVinodVinod Sikka, JamesSikka, James HemrickHemrick

Oak Ridge National LabOak Ridge National LabWilliamWilliam HeadrickHeadrick, Jeff Smith,, Jeff Smith, MusaMusa KarakusKarakus

University of MissouriUniversity of Missouri--RollaRollaFrank E. GoodwinFrank E. Goodwin

ILZROILZROSubodhSubodh DasDas

SECATSECATLarry BoydLarry Boyd

EIOEIO

22

Primary Applicant West Virginia University

Universities University of Missouri-Rolla

National Laboratory Participant Oak Ridge National Laboratory

Industry Participants AK Steel Corporation Duraloy Technologies, Inc. California Steel Industries Metaullics Systems Co. ISG-Weirton Deloro Stellite Company, Inc. Nucor - Berkeley Vesuvi us McDanel Nucor – Crawfords ville Praxair Surface Technologies, Inc. The Techs Allen Engi neering Wheatland Tube Co. Fireline Co. Wheeling-Nisshin MORCO Refractoris Pechiney Rolled Products Blasch Sturm Rapid Response Center Emhart Glass Special Metals Co. Allied Minerals Harbison-Walker

Monofrax RE Moore & Associates

Research Organizations ILZRO Energy Industries of Ohio Secat Inc.

State of West Virginia Industries of the Future – WV

33

Molten Metal Handling System withMolten Metal Handling System withSubmerged HardwareSubmerged Hardware

44

Research TopicsResearch Topics

Corrosion and wear in GA/GICorrosion and wear in GA/GIDross buildup in GA/GIDross buildup in GA/GICorrosion & dross in GLCorrosion & dross in GLRefractory for Al alloys handlingRefractory for Al alloys handlingHighHigh--temperature refractory for steel &temperature refractory for steel &superalloys handlingsuperalloys handling

55

Program ObjectiveProgram Objective

Extend the molten metal containment and submerged hardware life by an order of magnitude and improvement of thermal efficiency with energy savings of 333 trillion BTU/year and cost savings of approximately $1 billion/year by 2020

66

Research TasksResearch Tasks

Industrial Survey and AssessmentIndustrial Survey and AssessmentTesting Current MaterialsTesting Current MaterialsDynamic ModelingDynamic ModelingThermodynamic CalculationThermodynamic CalculationDeveloping New MaterialsDeveloping New MaterialsTesting New MaterialsTesting New MaterialsComponent TestingComponent TestingEnergy AssessmentEnergy AssessmentProject ManagementProject Management

77

Industrial SurveyIndustrial Survey –– Pot HardwarePot HardwareSurveys were written through collaboration with research organizations and investigators, distributed to the partners Molten metal temperature range: 860 F (GI)Molten metal temperature range: 860 F (GI) –– 1100 F (GL)1100 F (GL)Roll materials: CF3M, WCRoll materials: CF3M, WC--coatingcoatingBearing materials: Coated CF3M, Stellite 6 Average campaign time : 14-30 days (GI); 4 days (GL) Reason for stoppage: Freezing or lock up of stabilizer rolls Cracking of bearings when worn thin Effects of dross Rapid wear of dross scraping devices for higher

aluminum baths

88

Industrial SurveyIndustrial Survey -- RefractoriesRefractories

Average process temperaturesAverage process temperatures 1350-1450 F (Aluminum production) 2100-3100 F (Alloy/superalloy production)

Total cost of refractory materials consumptionTotal cost of refractory materials consumption $5.72 million/year

Cost of energy consumptionCost of energy consumption $15.34 million/year

Refractory problems encounteredRefractory problems encountered Thermal

cycling, shock (in Al melters) Chemical

attack (Cl), absorption into melt (Cr,Na,C,Ca), erosion/corrosion Mechanical

fracture due to impact, vibration, bending load, wear Processing

refractory inclusions (centrifugal castings)

99

Failure AnalysisFailure Analysis

Sites visitedSites visited WheelingWheeling--Nisshin, Wheatland Tube, California Steel, TheNisshin, Wheatland Tube, California Steel, The

Techs, NucorTechs, Nucor--Berkeley, Special Metals, SturmBerkeley, Special Metals, SturmSamples collected:Samples collected: Wheatland Tube (Batch galvanizing): top plate, bottomWheatland Tube (Batch galvanizing): top plate, bottom

plate, push arm, kettle drossplate, push arm, kettle dross California Steel (GI& GA): skimmed top dross, drossCalifornia Steel (GI& GA): skimmed top dross, dross

buildup at contact & nonbuildup at contact & non--contact areascontact areas WheelingWheeling--Nisshin (GL): top dross, bottom dross, dross onNisshin (GL): top dross, bottom dross, dross on

the rig, dross on the rollthe rig, dross on the roll Sturm (Metal casting): refractories from crucible and ladleSturm (Metal casting): refractories from crucible and ladle Special Metals (Superalloys) refractories from VIM & VARSpecial Metals (Superalloys) refractories from VIM & VAR Refractories from an Al melting furnaceRefractories from an Al melting furnace

1010

Failure AnalysisFailure Analysis –– ContCont’’dd

Sites visitedSites visited WheelingWheeling--Nisshin, Wheatland Tube, California Steel, TheNisshin, Wheatland Tube, California Steel, The

Techs, NucorTechs, Nucor--Berkeley, Special Metals, SturmBerkeley, Special Metals, Sturm

Erosion of kettle around dross line (General galvanizing)

Kettle dross (General galvanizing)

1111

Schematic Describing Refractory Damage inSchematic Describing Refractory Damage inan Aluminum Melting Furnacean Aluminum Melting Furnace

Corundum mushroom

Unaltered refractory lining

Metal penetration Refractory reduc tion zone

Aluminum Alloy

Internal corundum growth

Air/atmosphe

1212

Aluminum melting furnace InspectionAluminum melting furnace Inspection

The crown of the furnace has liftedThe crown of the furnace has lifted66--8" due to expansion of the wall8" due to expansion of the wall refractories.refractories.

The cut at the metal line andThe cut at the metal line andcorundum growth above the metalcorundum growth above the metal line are visibleline are visible

1313

Dross Buildup in Galvanize BathDross Buildup in Galvanize Bath

Dross

Zn bath

SS316L

Stabilizer Roll from California Steel

1414

Dross in Galvalume BathDross in Galvalume Bath

Samples from Wheeling-Nisshin

1515

Refractories from Al Melting FurnaceRefractories from Al Melting FurnaceAntiAnti--wetting agents (CaFwetting agents (CaF22)) can be observed bycan be observed bycathodoluminescence. It iscathodoluminescence. It isdifficult to observe antidifficult to observe anti--wetting agents with otherwetting agents with othermethods.methods.

Kyanite (AlKyanite (Al22OO33--SiOSiO22) may be) may be a better aggregate materiala better aggregate materialthan alumina (Althan alumina (Al22OO33) or) ormullitemullite(3 Al(3 Al22OO33--2 SiO2 SiO22) as it does) as it does not react with aluminumnot react with aluminummetal as rapidly.metal as rapidly.

Corundum (AlCorundum (Al22OO33) growth is) growth isaccompanied by spinelaccompanied by spinel(Al(Al22OO33--MgO) in concentricMgO) in concentriclayers in Mg containinglayers in Mg containingaluminum alloys. This mayaluminum alloys. This maylead to a a path for inlead to a a path for in--situsituformation of a dense layer onformation of a dense layer on the hot face.the hot face.

1616

Testing of Current MaterialsTesting of Current Materials

Equipments developedEquipments developed WVU labWVU lab--scale dynamics corrosion/dross buildup testerscale dynamics corrosion/dross buildup tester WVU labWVU lab--scale wear testerscale wear tester WVU fullWVU full--scale GL scraper testerscale GL scraper tester

1717

Testing of Current MaterialsTesting of Current Materials –– ContCont’’dd

Equipments developedEquipments developed ORNL dynamic corrosion testerORNL dynamic corrosion tester ORNL thermal conductivity testerORNL thermal conductivity tester UMR finger testerUMR finger tester

Heated Sample

Chamber

IR Lamp

Heated Sample

Chamber

IR Camera

1818

Testing of Current MaterialsTesting of Current Materials

LabLab--scale testingscale testing Static dross formation: 460C, up to 140 hoursStatic dross formation: 460C, up to 140 hours

various Al & Fe contents,various Al & Fe contents, Dynamic dross buildup: 460C,Dynamic dross buildup: 460C, CCAlAl = 0.17wt%= 0.17wt%

various time and speedvarious time and speed Wear testing:Wear testing: FirelineFireline TCON materialsTCON materials

Water testing of 316L & Stellite 6Water testing of 316L & Stellite 6 Finger testing:Finger testing: FirelineFireline TCON materialsTCON materials

InIn--plant testingplant testing Batch Galvanizing (corrosion): TBatch Galvanizing (corrosion): T--400C, T400C, T--800, W, W800, W, W--20Mo20Mo Continuous Galvanizing (dross buildup): CF3M, WCContinuous Galvanizing (dross buildup): CF3M, WC--Co coatingsCo coatings

1919

LabLab--scale Testingscale Testing

Static dross formation: 460C, up to 140 hoursStatic dross formation: 460C, up to 140 hoursvarious Al & Fe contents,various Al & Fe contents,

0

5

10

15

20

25

30

35

40

45

50

0 20 40 60 80 100 120 140 160

Time (hours)

Effe

ctiv

e D

iam

eter

of D

ross

Par

ticle

s (m

icro

n

TE ST 4 (0.1743 %Al, 0.0296 %Fe) TE ST 3 (0.1776 %Al, 0.0480 %Fe) [1] (0.1500 %Al, 0.0008 %Fe) TE ST 6 TE ST 50

2

4

6

8

10

12

2 4 5 6 7 8 9 10 11 12 13 14 15 17 18 23 24 28 43 Dross Particle Size (microns)

Num

ber o

f Par

ticle

s

Particle size distribution at t=60 minutes for Test 3

Dross particle size vs. Time

2020

LabLab--scale Testingscale Testing

Dynamic dross buildup:Dynamic dross buildup: 460C,460C, CCAlAl = 0.17wt%= 0.17wt%various time and speedvarious time and speed

60rpm, 1 day 60 rpm, 5 days

2121

l i i

• i i li l i ing

fi i• i i l i l i l

l iSi i i

i i i ll• l i ials • i i l l

l• i i i l i

all

Ana ys s of F reline TCON Samples

Samples subjected to a submerged f nger test n mo ten alum num al oy for 100 to 1000 hours (stat c) and a rotatnger test (dynam c) planned for 1000 hours

Stat c test ng samp es showed no not ceab e corros on by metaSharp edges of samp es reta ned

gnif cant non-wett ng behavior exhibited Test ng underway n more aggressive alum num a oy Therma shock was found to be an ssue for these materCrack ng seen n samp es, although meta was not found to penetrate into samp es through cracks Dynam c test ng being set up us ng more aggressive a um num

oy

2222

l i i

i i

Ana ys s of F reline TCON Samples

Mechan cal Test ng

2323

Dynamic Corrosion/Dross BuildupDynamic Corrosion/Dross Buildup ModelingModeling

Hypothesis:Hypothesis: In the case of nonIn the case of non--coated specimen like 316L, thecoated specimen like 316L, the

dross builddross build--up is assisted by the formation of aup is assisted by the formation of a corrosion layer on the surface of the specimen that iscorrosion layer on the surface of the specimen that issimilar in characteristics to the dross in the bathsimilar in characteristics to the dross in the bath

Hence, the determination of dynamic corrosion rate isHence, the determination of dynamic corrosion rate isvital in understanding dross buildvital in understanding dross build--upup

In the case of coated specimen like 316L with WCIn the case of coated specimen like 316L with WC--CoCocoating, hydrodynamic conditions play a morecoating, hydrodynamic conditions play a moreimportant role on dross buildimportant role on dross build--upup

2424

Dynamic Dross Buildup ModelingDynamic Dross Buildup Modeling

Corrosion by mass transferCorrosion by mass transfer Governing phenomena is diffusion of Fe from the roll specimen inGoverning phenomena is diffusion of Fe from the roll specimen into Al into Al in

the baththe bath Corrosion rate influenced by thickness of diffusion boundary layCorrosion rate influenced by thickness of diffusion boundary layerer High value for Sc(= n / D) implies that the diffusion layer willHigh value for Sc(= n / D) implies that the diffusion layer will be thin andbe thin and

its formation will be fasterits formation will be fasterCorrosion by phase transportCorrosion by phase transport Governing phenomena is the wetting of the roll specimen surfaceGoverning phenomena is the wetting of the roll specimen surface by theby the

liquid Znliquid Zn--Al alloyAl alloy Wetting: corrosive Zn bath contacts roll surface, adheres to itWetting: corrosive Zn bath contacts roll surface, adheres to it and thenand then

corrodes itcorrodes it Corrosion rate influenced by rotational speed of the specimenCorrosion rate influenced by rotational speed of the specimen

AggregationAggregation Collision of dross particles onto the rotating roll specimen isCollision of dross particles onto the rotating roll specimen is a functiona function

of shear gradient of fluid velocity in the bathof shear gradient of fluid velocity in the bath Whether dross partic les stick to the roll after collision dependWhether dross particles stick to the roll after collision depends ons on

collision efficiencycollision efficiency Collision efficiency is enhanced by turbulent flowCollision efficiency is enhanced by turbulent flow

2525

Thermodynamic CalculationThermodynamic Calculation -- Dross FormationDross Formation

ConditionCondition Temperature: 460Temperature: 460--500C500C Al contents: 0.14Al contents: 0.14 –– 0.22 wt%0.22 wt%

NucleationNucleation Energy Barrier:Energy Barrier: Critical radius:Critical radius:

GrowthGrowth Initial GrowthInitial Growth –– Diffusion controlDiffusion control ““OswardOsward RipeningRipening”” AgglomerationAgglomeration

0 500 1000 1500 2000 2500 3000 3500 6

8

10

12

14

16

y = a + b*x 0̂.5 C hi^2/DoF = 0.39989 R ̂ 2 = 0.96102 a 6.33177 ±0.42463 b 0.14909 ±0.01343 c 0.5 ±0

dros

s si

ze (m

icro

ns)

time (minutes)

p/l *

v

2γ r = = 2.14E-10 m∆G

( ) 3 23( )

p/l *

v

16π γ ∆G = 0.45 eV

∆G =

2626

Thermodynamic CalculationThermodynamic Calculation -- RefractoriesRefractories

Predict the phase formationPredict the phase formationwhen liquid metal comes inwhen liquid metal comes incontact with the refractorycontact with the refractoryliningliningModel will be used to predictModel will be used to predictthe phase formation forthe phase formation forcurrently used materialscurrently used materialsModel output, once verified,Model output, once verified,will also be used to explorewill also be used to explore new materials.new materials.

0.0E+00

1.0E+05

2.0E+05

3.0E+05

4.0E+05

5.0E+05

6.0E+05

250 450 650 85 0 10 50 1250 1 450 1650

T empe rature(K) ∆G

(J)

BaAl2 O4

LiAlO2

MgAl2 O4 +Na2 CO3 =2NaAlO2 +MgO+CO2

MgAl2 O4

2727

LongLong--Term Corrosion Data Led toTerm Corrosion Data Led toThree Materials for CommercialThree Materials for CommercialApplicationApplication Tribaloy 800 (Deloro Stellite)Tribaloy 800 (Deloro Stellite)

Wear partsWear partsRoll surfaceRoll surface

Alloy 2020 (Metaullics)Alloy 2020 (Metaullics)Wear partsWear partsRoll surfaceRoll surface

Alloy 4 (ORNL Developed)Alloy 4 (ORNL Developed)Roll surfaceRoll surface

New Materials Development and TestingNew Materials Development and Testing --PotPot--HardwareHardware

0

16

32

48

64

80

SS 3

16L

Stel

lite

6

2012

2012

xt

2020

T-40

0

T-80

0

61.

9

61 .6

4.0

5 7.5

7

1. 62 3

.97

0.2

7

Wei

g ht C

h ang

e (m

g/cm

2 )

500h Static test

Zn-0.16Al at 465o C

2828

Methods of Applications for IdentifiedMethods of Applications for IdentifiedMaterialsMaterials

Casting of Wear PartsCasting of Wear PartsWeld Overlaying of Tribaloy 800 or Alloy 2020 onWeld Overlaying of Tribaloy 800 or Alloy 2020 onType 316L for Wear ApplicationType 316L for Wear ApplicationWeld Overlay of Tribaloy 800, Alloy 2020, and AlWeld Overlay of Tribaloy 800, Alloy 2020, and Alon Type 316L for Roll Applicationon Type 316L for Roll Application Weld overlays of Tribaloy 800 and Alloy 2020Weld overlays of Tribaloy 800 and Alloy 2020

to be used in asto be used in as--machined conditionmachined condition Weld overlay with Al requiresWeld overlay with Al requires preoxidationpreoxidation forfor

protective surface oxideprotective surface oxide

2929

Materials Selection CriteriaMaterials Selection Criteria

Performance Wear

Alloy 2020 and Tribaloy 800 Corrosion

Alloy 2020, Tribaloy 800, and Al weld overlay (preoxidized) Cost

Alloy 2020 and Al weld overlay are more cost desirable as compared to Tribaloy 800

Demonstration Weld overlay developed for Al and preoxidation (confirmed on a roll) Weld overlay steps identified and further optimization needed for

corrosion application Weld overlay steps identified for wear application; application ready

in near future

3030

New Refractory Material DevelopmentNew Refractory Material Development

Started development of castables usingStarted development of castables usingmicronizedmicronized kyanite instead of fumed silica.kyanite instead of fumed silica.

Fumed silica has been shown to be detrimental toFumed silica has been shown to be detrimental toaluminum contact refractories, but is required foraluminum contact refractories, but is required forflow during installation.flow during installation.

MicronizedMicronized kyanite may be used to increase flowkyanite may be used to increase flowwithout leading to increased corrosion rates.without leading to increased corrosion rates.

Energy Savings due to reduced downtime.Energy Savings due to reduced downtime.

3131

New Refractory Material DevelopmentNew Refractory Material Development

Laminates based on TCONLaminates based on TCON FirelineFireline material.material.

TCONTCON FirelineFireline material showed near zero aluminummaterial showed near zero aluminumadhesion and corrosion.adhesion and corrosion.

TCONTCON FirelineFireline could be used as a hot face laminatecould be used as a hot face laminateover an insulating backup.over an insulating backup.

The insulating backup must be capable of containingThe insulating backup must be capable of containingthe freeze plane.the freeze plane.

Energy Savings due to reduced downtime andEnergy Savings due to reduced downtime andincreased thermal efficiency during operation.increased thermal efficiency during operation.

3232

Component TestingComponent Testing

Weld overlay of AlWeld overlay of Al--enriched layer on 316Lenriched layer on 316L The stabilizer roll was fabricated by Duraloy TechnologiesThe stabilizer roll was fabricated by Duraloy TechnologiesInIn--line trial was carried out at Nucorline trial was carried out at Nucor--Crawfordsville for twoCrawfordsville for twoweeksweeksThe roll has been shipped to Duraloy, and the post mortemThe roll has been shipped to Duraloy, and the post mortemanalysis will be carried out by both WVU and ORNLanalysis will be carried out by both WVU and ORNLRecommendation on improving the process will be providedRecommendation on improving the process will be providedafter the post mortem analysis is doneafter the post mortem analysis is done

3333

Energy AssessmentEnergy Assessment

Sites visitedSites visited WheelingWheeling--Nisshin, California Steel, The TechsNisshin, California Steel, The TechsA survey form and associated energy estimationA survey form and associated energy estimationspreadsheet are designed to collect relevantspreadsheet are designed to collect relevantinformation about the energy consuminginformation about the energy consuming equipmentequipmentInformation was collected on motors, furnaces,Information was collected on motors, furnaces,pot hardware, production quantities, run times,pot hardware, production quantities, run times,and support hardwareand support hardware

3434

Spread Sheet for CalculationSpread Sheet for Calculation

MMBtu/tonMMBtu/tonEnergy consumption per ton of steel producedEnergy consumption per ton of steel producedtons/yeartons/yearTotal Annual ProductionTotal Annual ProductionMMBtu/yearMMBtu/yearTotal Annual energy consumptionTotal Annual energy consumptionMMBtuMMBtuEnergy consumed by plant during shutoffEnergy consumed by plant during shutoffMMBtuMMBtuEnergy consumed by plant during productionEnergy consumed by plant during productionhourshoursTotal Idle time (during shutoff)Total Idle time (during shutoff)hourshoursTotal Production timeTotal Production timeshutdowns/yearshutdowns/yearThe number of maintenance shutdowns per yearThe number of maintenance shutdowns per yearhourshoursTotal operating hoursTotal operating hourshourshoursShutdown duration in hoursShutdown duration in hoursweeksweeksOperating weeks per yearOperating weeks per yearMMBtuMMBtuZn Pot energy consumption for production weeksZn Pot energy consumption for production weeksMMBtuMMBtuMiscMisc motor energy consumption for production weeksmotor energy consumption for production weeksMMBtuMMBtuFurnace energy consumption for production weeksFurnace energy consumption for production weekstonstonsProduction in given weeksProduction in given weeksweeksweeksNo. of weeks operated before shutdownNo. of weeks operated before shutdown

3535

Project ManagementProject Management

Partners changePartners change New partners: NucorNew partners: Nucor--Berkeley, NucorBerkeley, Nucor--

Crawfordsville, Wheatland Tube, WheelingCrawfordsville, Wheatland Tube, Wheeling--Nisshin, The TechsNisshin, The Techs

Meetings and reportsMeetings and reports Three review meetingsThree review meetings Presentations: GalvtechPresentations: Galvtech’’04, Gal. Ass.04, Gal. Ass.’’04,04,

AISTAIST’’05, ILZRO05, ILZRO--GAP meetingsGAP meetings

3636

SummarySummary

Completed Industrial SurveyCompleted Industrial SurveyCompleted Post Mortem AnalysisCompleted Post Mortem AnalysisStatic & Dynamic Testing of CurrentStatic & Dynamic Testing of CurrentMaterials in ProgressMaterials in ProgressStarted Thermodynamic & DynamicStarted Thermodynamic & DynamicModelingModelingNew Materials under DevelopmentNew Materials under DevelopmentIndustrial Trials InitiatedIndustrial Trials Initiated

Progress ReportResearch TopicsProgram ObjectiveResearch TasksIndustrial SurveyFailure AnalysisTesting of Current MaterialsLab--scale TestingAnayss of Fireline TCON SamplesDynamic Corrosion/Dross BuildupNew Materials Development and TestingMethods of ApplicationsMaterials Selection CriteriaComponent TestingEnergy AssessmentSpread Sheet for CalculationProject ManagementSummary