High Performance Alloys High Performance Alloys for Steam Surface for Steam Surface

CondensersCondensers

Proven HP Alloys for Nuclear Proven HP Alloys for Nuclear CondensersCondensers

Ti Grade 2Ti Grade 2 Excellent corrosion resistanceExcellent corrosion resistance Poor mechanical properties Poor mechanical properties Good thermal conductivityGood thermal conductivity

AL6XN®AL6XN® Excellent corrosion resistanceExcellent corrosion resistance Good mechanical propertiesGood mechanical properties Low thermal conductivityLow thermal conductivity High cost High cost

SEA-CURE®SEA-CURE® Excellent corrosion resistanceExcellent corrosion resistance Best mechanical propertiesBest mechanical properties Good thermal conductivityGood thermal conductivity Lowest long term costLowest long term cost

Why Consider Alternates to Ti?Why Consider Alternates to Ti?

1. 1. TiTi lead times often unpredictable, could be 18-24 lead times often unpredictable, could be 18-24 monthsmonths

2. Combination of low strength and stiffness limits pull-out 2. Combination of low strength and stiffness limits pull-out loads – tube to tubesheet leaks are commonloads – tube to tubesheet leaks are common

3. Low Ti stiffness promotes vibration and cracking3. Low Ti stiffness promotes vibration and cracking4. Low water droplet resistance is common source of leaks4. Low water droplet resistance is common source of leaks5. Low mechanical properties create handling problems5. Low mechanical properties create handling problems6. Low hardness allows premature sand erosion failures – 6. Low hardness allows premature sand erosion failures –

(very common in China!)(very common in China!)7. Price variability is significant7. Price variability is significant

TVA NuclearTVA Nuclear Watts BarWatts Bar

• Spring City, TNSpring City, TN• PWRPWR• Unit #1 1996; Unit #2 under constructionUnit #1 1996; Unit #2 under construction• 1210 MW each1210 MW each

965,000 m; 1” 965,000 m; 1” (25.4mm)(25.4mm) x 0.028” x 0.028” (0.7mm)(0.7mm) Unit #1 in 1999, Unit #2 in 2008Unit #1 in 1999, Unit #2 in 2008 Replace 90/10 due to Cu transportReplace 90/10 due to Cu transport SEA-CURE tubes are 115’ (34.9 m) longSEA-CURE tubes are 115’ (34.9 m) long

Brown’s Ferry Nuclear also replaced in June 2003 with Brown’s Ferry Nuclear also replaced in June 2003 with SEA-CURE®SEA-CURE®

Pitting & Crevice Pitting & Crevice CorrosionCorrosion

PREn = %Cr+ PREn = %Cr+ 3.3%Mo+ 16%N3.3%Mo+ 16%N

PREn vs. resistance is PREn vs. resistance is also related to crystal also related to crystal structurestructure

For similar PREn, For similar PREn, ferritics have higher ferritics have higher resistance than resistance than duplex, and duplex duplex, and duplex have higher than have higher than austenitics austenitics

Relative Pitting Resistance,Relative Pitting Resistance,PREN and G 48 CPREN and G 48 C

CrCr MoMo NN PRENPREN Critical Critical Pitting TPitting T

439439 1818 <0.5<0.5 00 1818 15 15 CC

304304LL 1818 <0.5<0.5 <0.05<0.05 2020 20 20 CC

316316LL 16.516.5 2.02.0 <0.05<0.05 2323 25 25 CC

Old 316Old 316 17.517.5 2.62.6 <0.05<0.05 2626 35 35 CC

AL-6XNAL-6XN 28.528.5 6.46.4 0.200.20 4545 65 65 CC

SEA-CURESEA-CURE 27.527.5 3.83.8 00 4040 75 75 CC

Typical Mechanical & Physical PropertiesTypical Mechanical & Physical Properties

PropertyPropertyAdmiralty Admiralty

BrassBrass90/10 90/10

Cu/NiCu/Ni439439 304304L/L/

316L316LAL-6XNAL-6XN SEA-SEA-

CURECURETi gr 2Ti gr 2

(High O)(High O)Ti gr 2Ti gr 2

(Low O)(Low O)

UNS NumberUNS Number C44300C44300 C70600C70600 S43035S43035 S30403S30403 N08367N08367 S44660S44660 R50400R50400 R50400R50400

UTS (MPa)UTS (MPa) 365365 300300 480480 620620 725725 655655 515515 415415

Yield (MPa)Yield (MPa) 150150 110110 345345 415415 380380 515515 345345 275275

ElongationElongation 60%60% 40%40% 40%40% 55%55% 45%45% 30%30% 25%25% 30%30%

Hardness Hardness (convert)(convert)

RB 25RB 25 RB 20RB 20 RB 80RB 80 RB80RB80 RB 95RB 95 RB 95RB 95 RB 70RB 70 RB 60RB 60

Mod of ElastMod of Elast ( x 10( x 1033 MPa) MPa)

110110 124124 200200 195195 195195 215215 105105 105105

Density (g/cc)Density (g/cc) 8.538.53 8.948.94 7.757.75 8.008.00 8.068.06 7.707.70 4.514.51 4.514.51

Thermal Exp.Thermal Exp. (/°C x 10(/°C x 10-6-6))

20.220.2 17.117.1 10.110.1 15.315.3 15.515.5 9.79.7 8.38.3 8.38.3

Thermal Thermal Cond.Cond.

(W/m-C)(W/m-C)

110110 4545 21.121.1 14.8/14.14.8/14.00

11.711.7 18.018.0 21.821.8 21.821.8

Fatigue limit Fatigue limit (MPa)(MPa)

110110 100100 140140 200200 240240 240240 170170 140140

Can We Use Thin Wall High Can We Use Thin Wall High Performance Stainless Performance Stainless Tubing in Condensers?Tubing in Condensers?

Since 1999, 14 plants have been supplied Since 1999, 14 plants have been supplied with 0.5 or 0.55 mm with 0.5 or 0.55 mm

SEA-CURE® condenser tubing!SEA-CURE® condenser tubing!

Two more plants are in our backlog Two more plants are in our backlog

Hoop Strength of Thin Wall TubesHoop Strength of Thin Wall TubesHow Much Pressure Can It Take?How Much Pressure Can It Take?

Based on ASTM minimum requirements, 25.4 mm ODBased on ASTM minimum requirements, 25.4 mm OD

Tube Material WallTi Grade 2 0.5 mmSEA-CURE 0.4 mmSEA-CURE 0.5 mm

Yield Pressure Burst Strength10.9 MPa 13.7 MPa14.2 MPa 18.6 MPa17.8 MPa 23.2 MPa

Typical Pullout Loads Typical Pullout Loads Without WeldWithout Weld

725 725 kg is considered to be minimum level for a kg is considered to be minimum level for a reliable condenserreliable condenser

Ti Grade 2 in Ti tubesheetTi Grade 2 in Ti tubesheet 25.4 mm x 0.7 mm – 500 kg25.4 mm x 0.7 mm – 500 kg 25.4 mm x 0.5 mm – 250 kg25.4 mm x 0.5 mm – 250 kg Welding is necessary! Welding is necessary!

SEA-CURE in duplex tubesheetSEA-CURE in duplex tubesheet 25.4 mm x 0.7 mm – 2000 kg25.4 mm x 0.7 mm – 2000 kg 25.4 mm x 0.5 mm – 1000 kg25.4 mm x 0.5 mm – 1000 kg Welding is not needed!Welding is not needed!

Handling & MaintenanceHandling & Maintenance

Ti Grade 2Ti Grade 2 Low strength = Easy dentingLow strength = Easy denting Low modulus = Easily bent and kinkedLow modulus = Easily bent and kinked OD cannot be measured with a micrometer OD cannot be measured with a micrometer

SEA-CURESEA-CURE Highest strength = Handling resistanceHighest strength = Handling resistance Highest modulus = Less kinking and greater Highest modulus = Less kinking and greater

vibration resistance vibration resistance

Water Droplet /Water Droplet /Steam Impingement ErosionSteam Impingement Erosion

Relative Resistance to Water Relative Resistance to Water Droplet ErosionDroplet Erosion

AlloyAlloy Hardness HVHardness HV Relative Erosion ResistanceRelative Erosion Resistance

Ti Grade 2Ti Grade 2 145145HVHV 1.01.0

S30400/S31600S30400/S31600 165 165 HVHV 2.02.0

Ti Grade 12Ti Grade 12 190 190 HVHV 3.63.6

S31254S31254 200 200 HVHV 7.07.0

Ti Grade 9Ti Grade 9 215 215 HVHV 6.26.2

S44660S44660 240 240 HVHV 7.27.2

S32750S32750 290 290 HVHV 9.49.4

Peake Method of Vibration SpanPeake Method of Vibration Span

L = 9.5 [(L = 9.5 [(EE I) / I) / pp v v22 D)] D)] 1/41/4

I = Pi / 64 (DI = Pi / 64 (D44 - ID - ID44))Where:Where:LL == Length in InchesLength in InchesEE == Modulus of Elasticity (psi)Modulus of Elasticity (psi)II == Moment of Inertia (inMoment of Inertia (in44))pp == Turbine Exhaust Density (lb/ftTurbine Exhaust Density (lb/ft33))vv == Average Exhaust Steam Velocity at Condenser InletAverage Exhaust Steam Velocity at Condenser InletDD == Tube Outside DiameterTube Outside DiameterIDID == Tube Inside DiameterTube Inside Diameter

Vibration Span– Thin Wall Ti vs Vibration Span– Thin Wall Ti vs SEA-CURE® SEA-CURE®

Alloy Ti Gr 2 S44660 S44660

Wall mm 0.5 0.4 0.5Peake Span mm 1075 1213 1282

HEI Sonic Vel. Span mm 739 847 884HEI M.-F. Span mm 720 792 821

Based on identical condenser performance requirements using 25.4 mm OD tubing

Thermal Thermal ConductivityConductivity

Condensing Condensing Studies at Studies at Rochester Rochester Institute of Institute of TechnologyTechnology

Hydrogen EmbrittlementHydrogen Embrittlement

Both Ti and SEA-CURE may embrittle in Both Ti and SEA-CURE may embrittle in presence of atomic hydrogenpresence of atomic hydrogen

May occur when cathodic protection systems are May occur when cathodic protection systems are more negative than -0.750 Volts more negative than -0.750 Volts (Both Ti and SEA-(Both Ti and SEA-CURE are the same)CURE are the same)

Can be caused by Mg sacrifical anodes!Can be caused by Mg sacrifical anodes!

SEA-CURE’s ductility is restored by rising SEA-CURE’s ductility is restored by rising temperature to 90temperature to 90oo C for an hour, or to 27 C for an hour, or to 27oo C for C for a day. a day. (Titanium hydriding is not reversible)(Titanium hydriding is not reversible)

Two Nuclear Ti Condensers are now being replaced!!!Two Nuclear Ti Condensers are now being replaced!!! Turkey Point 2Turkey Point 2 NB Power Point LepreauNB Power Point Lepreau

Annual Average Ti Sponge Price

0

5,000

10,000

15,000

20,000

25,000

1965 1970 1975 1980 1985 1990 1995 2000 2005 2010

year

Pri

ce

($

/to

n)

Historical Price Historical Price Trends for Trends for SpongeSponge

Mostly sold on Mostly sold on contractcontract

Thinly traded Thinly traded marketmarket

No standard No standard ‘market price’‘market price’

Amount of Ti in ApplicationsAmount of Ti in Applications

Over the years Ti usage in aircraft has grownOver the years Ti usage in aircraft has grown Fraction of plane weight from 10% to over 30%Fraction of plane weight from 10% to over 30% Total weight from 10T to 64T per planeTotal weight from 10T to 64T per plane

Within aerospace commercial wide body planes Within aerospace commercial wide body planes (777, 747, 787, A340/350, A380) account for 70% (777, 747, 787, A340/350, A380) account for 70% of Ti usageof Ti usage Remainder is all other commercial,Remainder is all other commercial,

helicopter and militaryhelicopter and military Aircraft grades sell for 5 times CP Aircraft grades sell for 5 times CP

prices prices

Commercial Commercial Wide Body Wide Body

UsageUsage

BoeingBoeing PlanePlane OrdersOrders Ti/unit Ti/unit (MT)(MT)

Total Ti Total Ti (MT)(MT)

grossgross

747747 109109 6060 6,5406,540

777777 262262 5858 15,19615,196

787787 847847 9191 77,07777,077

98,81398,813

AirbusAirbus

A340et.al.A340et.al. 916916 2424 21,98421,984

A380A380 201201 146146 29,34629,346

51,33051,330

How Many Planes?How Many Planes?

Build rates are climbingBuild rates are climbing Early 2000’s 100-120 planes/yearEarly 2000’s 100-120 planes/year Peak of 194 in 2009Peak of 194 in 2009 2010 deliveries est 1402010 deliveries est 140 AimAim

• 200/year in 2012200/year in 2012• 300/year by 2016300/year by 2016

Current orders will support this rate Current orders will support this rate through 2025through 2025

Ti Tubing’s CompetitionTi Tubing’s CompetitionPlanes vs. Power PlantsPlanes vs. Power Plants

300 wide body’s/year x 64MT/plane = 19,000MT of 300 wide body’s/year x 64MT/plane = 19,000MT of Ti/year in wide bodies, or about 27,000MT/yr in all Ti/year in wide bodies, or about 27,000MT/yr in all aerospaceaerospace

This exceeds the total US melt capacityThis exceeds the total US melt capacity

Main steam condenser in a 1,400MW nuclear plant Main steam condenser in a 1,400MW nuclear plant will use 200MTwill use 200MT

Only as much as three planesOnly as much as three planes One years aerospace usage would build 130 nuclear main One years aerospace usage would build 130 nuclear main

steam condenserssteam condensers

Forecast of demand and priceForecast of demand and price

Prices and delivery lead-time expected to Prices and delivery lead-time expected to increase slowly through 2012increase slowly through 2012 Aircraft build rate is slowly increasingAircraft build rate is slowly increasing Expected to reach a sponge price of $12-18/kgExpected to reach a sponge price of $12-18/kg

• same as in 2006-2008, mill products >$40/kgsame as in 2006-2008, mill products >$40/kg

Desalination market forced from Cu/Ni due to Desalination market forced from Cu/Ni due to environmental discharge concernsenvironmental discharge concerns One recent desal unit = 60% of annual grade 2 One recent desal unit = 60% of annual grade 2

tube striptube strip Many more needed! Many more needed!

Development of Super-ferritic Development of Super-ferritic AlloysAlloys

First generation alloysFirst generation alloys Developed in 1970’s by chemical companiesDeveloped in 1970’s by chemical companies Based on 446, straight 26% Cr gradeBased on 446, straight 26% Cr grade Difficult to manufactureDifficult to manufacture

• Used expensive melting and refining methodsUsed expensive melting and refining methods• Poor mechanical propertiesPoor mechanical properties

Second generation alloysSecond generation alloys Developed in late 1970’s by steel companiesDeveloped in late 1970’s by steel companies Utilized modern AOD melting methods and Utilized modern AOD melting methods and

stabilization with Ti and/or Nbstabilization with Ti and/or Nb Designed to replace Ti in seawater applicationDesigned to replace Ti in seawater application

• Improved performanceImproved performance Excellent corrosion resistanceExcellent corrosion resistance Improved mechanical propertiesImproved mechanical properties

History of SEA-CUREHistory of SEA-CURE®® Stainless Stainless

Today, more than 98,000,000 ft (29,000,000 m) for Today, more than 98,000,000 ft (29,000,000 m) for power plant condensers - 110,000,000+ ft power plant condensers - 110,000,000+ ft (33,500,000 m) overall(33,500,000 m) overall

154 condensers overall154 condensers overall First installations in 1980First installations in 1980

FP&L, Port Everglades #4FP&L, Port Everglades #4 HL&P, Greens Bayou #4HL&P, Greens Bayou #4

25% of all SEA-CURE in service longer than 20 25% of all SEA-CURE in service longer than 20 years years

All SEA-CURE installations are still using the All SEA-CURE installations are still using the original tubesoriginal tubes

Cumulative Global HP Stainless Condenser Cumulative Global HP Stainless Condenser Tube UsageTube Usage

Cumulative Stainless Usage

0

20,000,000

40,000,000

60,000,000

80,000,000

100,000,000

120,000,000

140,000,000

160,000,000

180,000,000

Year

Feet

Austenitic

Ferritic

Duplex

All

80% of All Global

Ferritics are SEA-CURE

Ti Condenser Tubing Ti Condenser Tubing AdvantagesAdvantages Excellent corrosion resistanceExcellent corrosion resistance 35 year track record35 year track record Good thermal conductivityGood thermal conductivity Multiple tube sourcesMultiple tube sources

ConcernsConcerns Lowest vibration resistanceLowest vibration resistance Marginal water droplet erosion Marginal water droplet erosion

resistanceresistance Marginal sand resistanceMarginal sand resistance Difficult to handle without Difficult to handle without

damagedamage Low tube-to-tubesheet pullout Low tube-to-tubesheet pullout

loadsloads Welds not cold workedWelds not cold worked Susceptible to H embrittlementSusceptible to H embrittlement Lowest practical wall is 0.5 mmLowest practical wall is 0.5 mm Potentially long strip lead time Potentially long strip lead time

and other competitive strip and other competitive strip marketsmarkets

SEA-CURE® Condenser Tubing SEA-CURE® Condenser Tubing AdvantagesAdvantages Excellent corrosion resistanceExcellent corrosion resistance 30 Year track record30 Year track record High pressure toleranceHigh pressure tolerance Good water droplet and sand Good water droplet and sand

erosion resistanceerosion resistance Highest stiffness and vibration Highest stiffness and vibration

resistanceresistance Highest tube-to-tubesheet Highest tube-to-tubesheet

pullout loadspullout loads Welds are fully cold workedWelds are fully cold worked Tolerant to handling damageTolerant to handling damage Never been replaced!Never been replaced!

ConcernsConcerns Susceptible to H embrittlement Susceptible to H embrittlement

(but reversible!)(but reversible!) Limited sourcesLimited sources

Tube Sheet MaterialsTube Sheet Materials

New UnitsNew Units Fresh or low Fresh or low

conductivity waterconductivity water • 22052205

• 317L or 904L317L or 904L Brackish or seawaterBrackish or seawater

• 6% Mo- AL6XN, 6% Mo- AL6XN, 254SMO, 25-6Mo254SMO, 25-6Mo

• Super Duplex -2507, Super Duplex -2507, Zeron 100, DP 3WZeron 100, DP 3W

Retubing Existing Retubing Existing CondenserCondenser Coat tube sheet in Coat tube sheet in

high conductivity high conductivity waterwater

What is Special About SEA-CURE®? What is Special About SEA-CURE®? Our Process!Our Process!

ASTM G48-C Corrosion TestASTM G48-C Corrosion Test 72 hours72 hours Must pass at 65Must pass at 65ooCC Once per heatOnce per heat Test in as-shipped conditionTest in as-shipped condition

The weld is fully cold worked using tooling on both ID The weld is fully cold worked using tooling on both ID and ODand OD

It is not bright annealed – Dangerous for embrittlementIt is not bright annealed – Dangerous for embrittlement It is chemically passivated for optimal corr. resistanceIt is chemically passivated for optimal corr. resistance Air-under-water 250 psi (1.7 MPa) minimumAir-under-water 250 psi (1.7 MPa) minimum Long performance record, long term experienceLong performance record, long term experience Special chemistry and process is proven – other super-Special chemistry and process is proven – other super-

ferritics have failed in multiple condensersferritics have failed in multiple condensers

Poor Quality Competitive Mat’l

Tube Price Tube Price TrendsTrends

Relative prices of Relative prices of condenser candidatescondenser candidates

Approximate values as of Dec. 2010, Nickel at $26.00/kg on LME, Ferro-Molybdenum at $36.30/kg, Copper at $9.35/kg

With China’s demand, every day is a new day!!!

GradeGrade WallWall Relative Relative PricePrice

TP 304TP 304 0.7 0.7 mmmm 1.01.0

TP 316TP 316 0.7 0.7 mmmm 1.31.3

TP 439TP 439 0.7 0.7 mmmm 1.21.2

TP 317TP 317 0.7 0.7 mmmm 1.91.9

22052205 0.7 0.7 mmmm 2.02.0

S44660S44660 0.5 0.5 mmmm 2.12.1

S44660S44660 0.7 0.7 mmmm 2.42.4

Al BrassAl Brass 1.24 1.24 mmmm 2.52.5

90/10 90/10 Cu/NiCu/Ni 0.9 0.9 mmmm 2.32.3

90/10 90/10 Cu/NiCu/Ni 1.24 1.24 mmmm 2.82.8

Ti Grade 2Ti Grade 2 0.5 0.5 mmmm 2.32.3

Ti Grade 2Ti Grade 2 0.7 0.7 mmmm 2.82.8

N08367N08367 0.7 0.7 mmmm 4.04.0

70/30 70/30 Cu/NiCu/Ni 0.9 0.9 mmmm 4.54.5