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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
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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
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33
Molten Metal Handling System withMolten Metal Handling System
withSubmerged HardwareSubmerged Hardware
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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
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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
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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
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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
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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)
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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
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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)
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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
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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
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1313
Dross Buildup in Galvanize BathDross Buildup in Galvanize
Bath
Dross
Zn bath
SS316L
Stabilizer Roll from California Steel
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1414
Dross in Galvalume BathDross in Galvalume Bath
Samples from Wheeling-Nisshin
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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.
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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
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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
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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
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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
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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
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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
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2222
l i i
i i
Ana ys s of F reline TCON Samples
Mechan cal Test ng
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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
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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
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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 =
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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
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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
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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
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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
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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.
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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.
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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
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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
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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
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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
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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