11

MultiMulti--functional Metallic and Refractory functional Metallic and Refractory Materials for Energy Efficient Handling for Materials 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, James Sikka, James HemrickHemrick

Oak Ridge National LabOak Ridge National LabWilliam William 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 ApplicantWest Virginia University

UniversitiesUniversity of Missouri-Rolla

National Laboratory ParticipantOak Ridge National Laboratory

Industry ParticipantsAK Steel Corporation Duraloy Technologies, Inc.California Steel Industries Metaullics Systems Co. ISG-Weirton Deloro Stellite Company, Inc. Nucor - Berkeley Vesuvius McDanelNucor – Crawfordsville Praxair Surface Technologies, Inc. The Techs Allen Engineering Wheatland Tube Co. Fireline Co.Wheeling-Nisshin MORCO RefractorisPechiney Rolled Products BlaschSturm Rapid Response Center Emhart Glass Special Metals Co. Allied Minerals Harbison-Walker

Monofrax RE Moore & Associates

Research OrganizationsILZROEnergy Industries of OhioSecat Inc.

State of West VirginiaIndustries of the Future – WV

33

Molten Metal Handling System with Molten Metal Handling System with Submerged 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 Survey Industrial Survey –– Pot HardwarePot Hardware

Surveys were written through collaboration with research organizations and investigators, distributed to the partnersMolten 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 6Average campaign time : 14-30 days (GI); 4 days (GL)Reason for stoppage:

Freezing or lock up of stabilizer rollsCracking of bearings when worn thinEffects of drossRapid wear of dross scraping devices for higher aluminum baths

88

Industrial Survey Industrial Survey -- RefractoriesRefractories

Average process temperaturesAverage process temperatures1350-1450 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 encounteredThermal

cycling, shock (in Al melters)Chemical

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

fracture due to impact, vibration, bending load, wearProcessing

refractory inclusions (centrifugal castings)

99

Failure AnalysisFailure Analysis

Sites visitedSites visitedWheelingWheeling--Nisshin, Wheatland Tube, California Steel, The Nisshin, Wheatland Tube, California Steel, The Techs, NucorTechs, Nucor--Berkeley, Special Metals, SturmBerkeley, Special Metals, Sturm

Samples collected: Samples collected: Wheatland Tube (Batch galvanizing): top plate, bottom Wheatland Tube (Batch galvanizing): top plate, bottom plate, push arm, kettle drossplate, push arm, kettle drossCalifornia Steel (GI& GA): skimmed top dross, dross California Steel (GI& GA): skimmed top dross, dross buildup at contact & nonbuildup at contact & non--contact areascontact areasWheelingWheeling--Nisshin (GL): top dross, bottom dross, dross on Nisshin (GL): top dross, bottom dross, dross on the rig, dross on the rollthe rig, dross on the rollSturm (Metal casting): refractories from crucible and ladleSturm (Metal casting): refractories from crucible and ladleSpecial Metals (Superalloys) refractories from VIM & VARSpecial Metals (Superalloys) refractories from VIM & VARRefractories from an Al melting furnaceRefractories from an Al melting furnace

1010

Failure Analysis Failure Analysis –– ContCont’’dd

Sites visitedSites visitedWheelingWheeling--Nisshin, Wheatland Tube, California Steel, The Nisshin, 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 in Schematic Describing Refractory Damage in an Aluminum Melting Furnacean Aluminum Melting Furnace

Corundum mushroom

Unaltered refractory lining

Metal penetration Refractory reduction zone

Aluminum Alloy

Internal corundum growth

Air/atmosphe

1212

Aluminum melting furnace InspectionAluminum melting furnace Inspection

The crown of the furnace has lifted The crown of the furnace has lifted 66--8" due to expansion of the wall 8" due to expansion of the wall refractories.refractories.

The cut at the metal line and The cut at the metal line and corundum growth above the metal corundum 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 by can be observed by cathodoluminescence. It is cathodoluminescence. It is difficult to observe antidifficult to observe anti--wetting agents with other wetting agents with other methods.methods.

Kyanite (AlKyanite (Al22OO33--SiOSiO22) may be ) may be a better aggregate material a better aggregate material than alumina (Althan alumina (Al22OO33) or ) or mullite mullite (3 Al(3 Al22OO33--2 SiO2 SiO22) as it does ) as it does not react with aluminum not react with aluminum metal as rapidly.metal as rapidly.

Corundum (AlCorundum (Al22OO33) growth is ) growth is accompanied by spinel accompanied by spinel (Al(Al22OO33--MgO) in concentric MgO) in concentric layers in Mg containing layers in Mg containing aluminum alloys. This may aluminum alloys. This may lead to a a path for inlead to a a path for in--situ situ formation of a dense layer on formation of a dense layer on the hot face.the hot face.

1616

Testing of Current MaterialsTesting of Current Materials

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

1717

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

Equipments developedEquipments developedORNL dynamic corrosion testerORNL dynamic corrosion testerORNL thermal conductivity testerORNL thermal conductivity testerUMR finger testerUMR finger tester

HeatedSample

Chamber

IR Lamp

HeatedSample

Chamber

IRCamera

1818

Testing of Current MaterialsTesting of Current Materials

LabLab--scale testingscale testingStatic dross formation: 460C, up to 140 hours Static 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 speed various time and speed Wear testing: Wear testing: FirelineFireline TCON materialsTCON materials

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

InIn--plant testingplant testingBatch Galvanizing (corrosion): TBatch Galvanizing (corrosion): T--400C, T400C, T--800, W, W800, W, W--20Mo20MoContinuous 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 hours Static dross formation: 460C, up to 140 hours various 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

TEST 4 (0.1743 %Al, 0.0296 %Fe)TEST 3 (0.1776 %Al, 0.0480 %Fe)[1] (0.1500 %Al, 0.0008 %Fe)TEST 6TEST 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 43Dross 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

Analysis of Fireline TCON Samples

• Samples subjected to a submerged finger test in molten aluminum alloy for 100 to 1000 hours (static) and a rotating finger test (dynamic) planned for 1000 hours

• Static testing samples showed no noticeable corrosion by metalSharp edges of samples retainedSignificant non-wetting behavior exhibitedTesting underway in more aggressive aluminum alloy

• Thermal shock was found to be an issue for these materials• Cracking seen in samples, although metal was not found to

penetrate into samples through cracks• Dynamic testing being set up using more aggressive aluminum

alloy

2222

Analysis of Fireline TCON Samples

Mechanical Testing

2323

Dynamic Corrosion/Dross Buildup Dynamic Corrosion/Dross Buildup ModelingModeling

Hypothesis:Hypothesis:In the case of nonIn the case of non--coated specimen like 316L, the coated specimen like 316L, the dross builddross build--up is assisted by the formation of a up is assisted by the formation of a corrosion layer on the surface of the specimen that is corrosion layer on the surface of the specimen that is similar in characteristics to the dross in the bathsimilar in characteristics to the dross in the bath

Hence, the determination of dynamic corrosion rate is Hence, the determination of dynamic corrosion rate is vital 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--Co Co coating, hydrodynamic conditions play a more coating, hydrodynamic conditions play a more important role on dross buildimportant role on dross build--upup

2424

Dynamic Dross Buildup ModelingDynamic Dross Buildup Modeling

Corrosion by mass transferCorrosion by mass transferGoverning phenomena is diffusion of Fe from the roll specimen inGoverning phenomena is diffusion of Fe from the roll specimen into Al in to Al in the baththe bathCorrosion rate influenced by thickness of diffusion boundary layCorrosion rate influenced by thickness of diffusion boundary layererHigh value for Sc(= n / D) implies that the diffusion layer willHigh value for Sc(= n / D) implies that the diffusion layer will be thin and be thin and its formation will be fasterits formation will be faster

Corrosion by phase transportCorrosion by phase transportGoverning phenomena is the wetting of the roll specimen surface Governing phenomena is the wetting of the roll specimen surface by the by the liquid Znliquid Zn--Al alloy Al alloy Wetting: corrosive Zn bath contacts roll surface, adheres to it Wetting: corrosive Zn bath contacts roll surface, adheres to it and then and then corrodes itcorrodes itCorrosion rate influenced by rotational speed of the specimenCorrosion rate influenced by rotational speed of the specimen

AggregationAggregationCollision of dross particles onto the rotating roll specimen is Collision of dross particles onto the rotating roll specimen is a function a function of shear gradient of fluid velocity in the bathof shear gradient of fluid velocity in the bathWhether dross particles stick to the roll after collision dependWhether dross particles stick to the roll after collision depends on s on collision efficiencycollision efficiencyCollision efficiency is enhanced by turbulent flowCollision efficiency is enhanced by turbulent flow

2525

Thermodynamic Calculation Thermodynamic Calculation -- Dross FormationDross Formation

ConditionConditionTemperature: 460Temperature: 460--500C500CAl contents: 0.14 Al contents: 0.14 –– 0.22 wt%0.22 wt%

Nucleation Nucleation Energy Barrier:Energy Barrier:Critical radius:Critical radius:

GrowthGrowthInitial Growth Initial Growth –– Diffusion controlDiffusion control““OswardOsward RipeningRipening””AgglomerationAgglomeration

0 500 1000 1500 2000 2500 3000 35006

8

10

12

14

16

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

dros

s si

ze (m

icro

ns)

time (minutes)

p/l*

v

2γr = = 2.14E-10 m∆G

( )3

23( )

p/l*

v

16π γ∆G = 0.45 eV

∆G=

2626

Thermodynamic Calculation Thermodynamic Calculation -- RefractoriesRefractories

Predict the phase formation Predict the phase formation when liquid metal comes in when liquid metal comes in contact with the refractory contact with the refractory liningliningModel will be used to predict Model will be used to predict the phase formation for the phase formation for currently used materialscurrently used materialsModel output, once verified, Model output, once verified, will also be used to explore will 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

250 450 650 850 1050 1250 1450 1650

Tempe rature(K)∆G

(J)

BaAl2O4

LiAlO2

MgAl2O4+Na2CO3=2NaAlO2+MgO+CO2

MgAl2O4

2727

LongLong--Term Corrosion Data Led to Term Corrosion Data Led to Three Materials for Commercial Three Materials for Commercial ApplicationApplication

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 Testing New Materials Development and Testing --PotPot--Hardware Hardware

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

ght C

hang

e (m

g/cm

2 )

500h Static test

Zn-0.16Al at 465o C

2828

Methods of Applications for Identified Methods of Applications for Identified MaterialsMaterials

Casting of Wear PartsCasting of Wear PartsWeld Overlaying of Tribaloy 800 or Alloy 2020 on Weld Overlaying of Tribaloy 800 or Alloy 2020 on Type 316L for Wear ApplicationType 316L for Wear ApplicationWeld Overlay of Tribaloy 800, Alloy 2020, and Al Weld Overlay of Tribaloy 800, Alloy 2020, and Al on Type 316L for Roll Applicationon Type 316L for Roll Application

Weld overlays of Tribaloy 800 and Alloy 2020 Weld overlays of Tribaloy 800 and Alloy 2020 to be used in asto be used in as--machined conditionmachined conditionWeld overlay with Al requires Weld overlay with Al requires preoxidationpreoxidation for for protective surface oxideprotective surface oxide

2929

Materials Selection CriteriaMaterials Selection Criteria

PerformanceWear

Alloy 2020 and Tribaloy 800Corrosion

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

DemonstrationWeld overlay developed for Al and preoxidation (confirmed on a roll)Weld overlay steps identified and further optimization needed for corrosion applicationWeld overlay steps identified for wear application; application ready in near future

3030

New Refractory Material DevelopmentNew Refractory Material Development

Started development of castables using Started development of castables using micronizedmicronized kyanite instead of fumed silica.kyanite instead of fumed silica.

Fumed silica has been shown to be detrimental to Fumed silica has been shown to be detrimental to aluminum contact refractories, but is required for aluminum contact refractories, but is required for flow during installation.flow during installation.

MicronizedMicronized kyanite may be used to increase flow kyanite may be used to increase flow without 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 TCON Laminates based on TCON FirelineFireline material.material.

TCON TCON FirelineFireline material showed near zero aluminum material showed near zero aluminum adhesion and corrosion.adhesion and corrosion.

TCON TCON FirelineFireline could be used as a hot face laminate could be used as a hot face laminate over an insulating backup.over an insulating backup.

The insulating backup must be capable of containing The insulating backup must be capable of containing the freeze plane.the freeze plane.

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

3232

Component TestingComponent Testing

Weld overlay of AlWeld overlay of Al--enriched layer on 316L enriched 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 two Crawfordsville for two weeksweeksThe roll has been shipped to Duraloy, and the post mortem The roll has been shipped to Duraloy, and the post mortem analysis will be carried out by both WVU and ORNLanalysis will be carried out by both WVU and ORNLRecommendation on improving the process will be provided Recommendation on improving the process will be provided after the post mortem analysis is doneafter the post mortem analysis is done

3333

Energy AssessmentEnergy Assessment

Sites visitedSites visitedWheelingWheeling--Nisshin, California Steel, The TechsNisshin, California Steel, The Techs

A survey form and associated energy estimation A survey form and associated energy estimation spreadsheet are designed to collect relevant spreadsheet are designed to collect relevant information about the energy consuming information 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 changeNew partners: NucorNew partners: Nucor--Berkeley, NucorBerkeley, Nucor--Crawfordsville, Wheatland Tube, WheelingCrawfordsville, Wheatland Tube, Wheeling--Nisshin, The TechsNisshin, The Techs

Meetings and reportsMeetings and reportsThree review meetingsThree review meetingsPresentations: 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 Current Static & Dynamic Testing of Current Materials in ProgressMaterials in ProgressStarted Thermodynamic & Dynamic Started Thermodynamic & Dynamic ModelingModelingNew Materials under DevelopmentNew Materials under DevelopmentIndustrial Trials InitiatedIndustrial Trials Initiated