High Performance Alloys for Steam Surface Condensers

Ti Grade 2
  

Proven HP Alloys for Nuclear Condensers

Excellent corrosion resistance Poor mechanical properties Good thermal conductivity Excellent corrosion resistance Good mechanical properties Low thermal conductivity High cost Excellent corrosion resistance Best mechanical properties Good thermal conductivity Lowest long term cost

AL6XN
   

SEASEA-CURE
   

Why Consider Alternates to Ti?

1. Ti lead times often unpredictable, could be 18-24 18months 2. Combination of low strength and stiffness limits pull-out pullloads tube to tubesheet leaks are common 3. Low Ti stiffness promotes vibration and cracking 4. Low water droplet resistance is common source of leaks 5. Low mechanical properties create handling problems 6. Low hardness allows premature sand erosion failures (very common in China!) 7. Price variability is significant

TVA Nuclear


Watts Bar
Spring City, TN PWR Unit #1 1996; Unit #2 under construction 1210 MW each 965,000 m; 1 (25.4mm) x 0.028 (0.7mm) Unit #1 in 1999, Unit #2 in 2008 Replace 90/10 due to Cu transport SEASEA-CURE tubes are 115 (34.9 m) long


  

Browns Ferry Nuclear also replaced in June 2003 with SEASEA-CURE

Pitting & Crevice Corrosion

PREn = %Cr+ 3.3%Mo+ 16%N  PREn vs. resistance is also related to crystal structure  For similar PREn, ferritics have higher resistance than duplex, and duplex have higher than austenitics


Relative Pitting Resistance, PREN and G 48 C

Cr 439 304L 304L 316L 316L Old 316 ALAL-6XN SEASEA-CURE 18 18 16.5 17.5 28.5 27.5 Mo <0.5 <0.5 2.0 2.6 6.4 3.8 N 0 <0.05 <0.05 <0.05 0.20 0 PREN 18 20 23 26 45 40 Critical Pitting T 15 C 20 C 25 C 35 C 65 C 75 C

Typical Mechanical & Physical Properties

Property UNS Number UTS (MPa) Yield (MPa) Elongation Hardness (convert) Mod of Elast ( x 103 MPa) Density (g/cc) Thermal Exp. (/C x 10-6) (/ Thermal Cond. (W/m(W/m-C) Fatigue limit (MPa) Admiralty Brass C44300 365 150 60% RB 25 110 90/10 Cu/Ni C70600 300 110 40% RB 20 124 439 S43035 480 345 40% RB 80 200 304L/ 304L/ 316L S30403 620 415 55% RB80 195 ALAL-6XN N08367 725 380 45% RB 95 195 SEASEACURE S44660 655 515 30% RB 95 215 Ti gr 2 (High O) R50400 515 345 25% RB 70 105 Ti gr 2 (Low O) R50400 415 275 30% RB 60 105

8.53 20.2 110

8.94 17.1 45

7.75 10.1 21.1

8.00 15.3 14.8/14. 0 200

8.06 15.5 11.7

7.70 9.7 18.0

4.51 8.3 21.8

4.51 8.3 21.8

110

100

140

240

240

170

140

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

Since 1999, 14 plants have been supplied with 0.5 or 0.55 mm SEASEA-CURE condenser tubing! Two more plants are in our backlog

Hoop Strength of Thin Wall Tubes

How Much Pressure Can It Take?

Tube Material Ti Grade 2 SEA-CURE SEA-CURE

Wall Yield Pressure Burst Strength 0.5 mm 10.9 MPa 13.7 MPa 0.4 mm 14.2 MPa 18.6 MPa 0.5 mm 17.8 MPa 23.2 MPa

Based on ASTM minimum requirements, 25.4 mm OD

Typical Pullout Loads

Without Weld
 

725 kg is considered to be minimum level for a reliable condenser Ti Grade 2 in Ti tubesheet

  

25.4 mm x 0.7 mm 500 kg 25.4 mm x 0.5 mm 250 kg Welding is necessary! 25.4 mm x 0.7 mm 2000 kg 25.4 mm x 0.5 mm 1000 kg Welding is not needed!

SEASEA-CURE in duplex tubesheet

  

Handling & Maintenance

 Ti
  

Grade 2
Low strength = Easy denting Low modulus = Easily bent and kinked OD cannot be measured with a micrometer Highest strength = Handling resistance Highest modulus = Less kinking and greater vibration resistance

 SEA-CURE SEA 

Water Droplet / Steam Impingement Erosion

Relative Resistance to Water Droplet Erosion

Alloy Ti Grade 2 S30400/S31600 Ti Grade 12 S31254 Ti Grade 9 S44660 S32750 Hardness HV 145HV 145HV 165 HV 190 HV 200 HV 215 HV 240 HV 290 HV Relative Erosion Resistance 1.0 2.0 3.6 7.0 6.2 7.2 9.4

Peake Method of Vibration Span

L = 9.5 [(E I) / p v2 D)] 1/4 [(E I = Pi / 64 (D4 - ID4)
Where: L = E = I = p = v = D = ID = Length in Inches Modulus of Elasticity (psi) Moment of Inertia (in4) Turbine Exhaust Density (lb/ft3) Average Exhaust Steam Velocity at Condenser Inlet Tube Outside Diameter Tube Inside Diameter

Vibration Span Thin Wall Ti vs Span SEASEA-CURE

Alloy
Wall Peake Span HEI Sonic Vel. Span HEI M.-F. Span mm mm mm mm

Ti Gr 2
0.5 1075 739 720

S44660
0.4 1213 847 792

S44660
0.5 1282 884 821

Based on identical condenser performance requirements using 25.4 mm OD tubing

Thermal Conductivity
Condensing Studies at Rochester Institute of Technology

Hydrogen Embrittlement
 

Both Ti and SEA-CURE may embrittle in SEApresence of atomic hydrogen May occur when cathodic protection systems are more negative than -0.750 Volts (Both Ti and SEASEACURE are the same)


Can be caused by Mg sacrifical anodes!

SEASEA-CUREs ductility is restored by rising temperature to 90o C for an hour, or to 27o C for a day. (Titanium hydriding is not reversible)
Two Nuclear Ti Condensers are now being replaced!!!
 

Turkey Point 2 NB Power Point Lepreau

Annua Ave a e
25 000

Sp nge P ce

20 000

15 000

10 000

Historical Price Trends for Sponge

1970 1975 1980 1985 ea 1990 1995 2000 2005 2010

P ce ($ t n)

5 000

0 1965

Mostly sold on contract  Thinly traded market  No standard market price



Amount of Ti in Applications


Over the years Ti usage in aircraft has grown

 

Fraction of plane weight from 10% to over 30% Total weight from 10T to 64T per plane

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


Remainder is all other commercial, helicopter and military

Aircraft grades sell for 5 times prices

CP

Commercial Wide Body Usage

Boeing Plane 747 777 787 Airbus A340et.al. A380 916 201 24 146 21,984 29,346 51,330 Orders 109 262 847 Ti/unit (MT) 60 58 91 Total Ti (MT) 6,540 15,196 77,077 98,813 gross

How Many Planes?

 Build
   

rates are climbing

Early 2000 s 100-120 planes/year 100Peak of 194 in 2009 2010 deliveries est 140 Aim
200/year in 2012 300/year by 2016

Current orders will support this rate through 2025

Ti Tubing s Competition Planes vs. Power Plants

300 wide body s/year x 64MT/plane = 19,000MT of Ti/year in wide bodies, or about 27,000MT/yr in all aerospace  This exceeds the total US melt capacity


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

 

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

Forecast of demand and price



Prices and delivery lead-time expected to leadincrease slowly through 2012

 

Aircraft build rate is slowly increasing Expected to reach a sponge price of $12-18/kg $12 same as in 2006-2008, mill products >$40/kg 2006-

Desalination market forced from Cu/Ni due to environmental discharge concerns



One recent desal unit = 60% of annual grade 2 tube strip Many more needed!

Development of Super-ferritic SuperAlloys



First generation alloys

  

Developed in 1970s by chemical companies Based on 446, straight 26% Cr grade Difficult to manufacture
Used expensive melting and refining methods Poor mechanical properties

Second generation alloys

 

Developed in late 1970s by steel companies Utilized modern AOD melting methods and stabilization with Ti and/or Nb Designed to replace Ti in seawater application
Improved performance
 

Excellent corrosion resistance Improved mechanical properties

History of SEA-CURE Stainless SEA

 

Today, more than 98,000,000 ft (29,000,000 m) for power plant condensers - 110,000,000+ ft (33,500,000 m) overall 154 condensers overall First installations in 1980
 

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

 

25% of all SEA-CURE in service longer than 20 SEAyears All SEA-CURE installations are still using the SEAoriginal tubes

Cumulative Global HP Stainless Condenser Tube Usage

usteniti erriti u le ll

Cumulative Stainless Usage

Year

Feet

Ti Condenser Tubing
Advantages  Excellent corrosion resistance  35 year track record  Good thermal conductivity  Multiple tube sources Concerns  Lowest vibration resistance  Marginal water droplet erosion resistance  Marginal sand resistance  Difficult to handle without damage  Low tube-to-tubesheet pullout tube-toloads  Welds not cold worked  Susceptible to H embrittlement  Lowest practical wall is 0.5 mm  Potentially long strip lead time and other competitive strip markets

SEASEA-CURE Condenser Tubing

Advantages  Excellent corrosion resistance  30 Year track record  High pressure tolerance  Good water droplet and sand erosion resistance  Highest stiffness and vibration resistance  Highest tube-to-tubesheet tube-topullout loads  Welds are fully cold worked  Tolerant to handling damage  Never been re laced! Concerns  Susceptible to H embrittlement (but reversible!)  Limited sources

Tube Sheet Materials

 New


Units

 Retubing


Fresh or low conductivity water

2205 317L or 904L

Existing Condenser
Coat tube sheet in high conductivity water

Brackish or seawater
6% Mo- AL6XN, Mo254SMO, 25-6Mo 25 Super Duplex -2507, Zeron 100, DP 3W

What is Special About SEA-CURE? SEAOur Process!



ASTM G48-C Corrosion Test G48   

Poor Quality Competitive Matl

72 hours Must pass at 65oC Once per heat Test in as-shipped condition as-

     

The weld is fully cold worked using tooling on both ID and OD It is not bright annealed Dangerous for embrittlement It is chemically passivated for optimal corr. resistance Air-underAir-under-water 250 psi (1.7 MPa) minimum Long performance record, long term experience Special chemistry and process is proven other supersuperferritics have failed in multiple condensers

Tube Price Trends

Relative prices of condenser candidates
A roximate values as of Dec. 2010, Nickel at $26.00/kg on LME, FerroMolybdenum at $36.30/kg, Co er at $9.35/kg

Grade TP 304 TP 316 TP 439 TP 317 2205

Wall 0.7 mm 0.7 mm 0.7 mm 0.7 mm 0.7 mm 0.5 mm 0.7 mm 1.24 mm 0.9 mm 1.24 mm 0.5 mm 0.7 mm 0.7 mm 0.9 mm

Relative Price 1.0 1.3 1.2 1.9 2.0

S44660 S44660
Al Brass 90/10 Cu/Ni 90/10 Cu/Ni Ti Grade 2 Ti Grade 2 N08367 70/30 Cu/Ni

2.1 2.4
2.5 2.3 2.8 2.3 2.8 4.0 4.5