Stp quaterly meeting 1015-rev+2.0

University of New Mexico

CHLE (T3,4,5) & Bench test (SNC-001) UpdateSTP Quarterly Progress Meeting

10/15/2013Seung-Jun Kim, Ph.D.


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• Summary of CHLE tests (T1,2,3,4 and T5)– Objectives– Operating condition, system configurations– Preliminary results/ analysis

• Comparative Test matrix with CHLE tests– Prototypical temperature & aluminum condition (LOCA) vs. non-prototypical LCOA temperature & aluminum (100times

more than prototypical) condition: T125 vs T34– NEI-bed vs. blender-bed: T2 vs. T5 or T3/T4– Al precipitation effect vs. zinc source effect : T3 vs. T4– MB LOCA vs. LB LOCA : T1 vs. T2

• Comprehensive analysis for all CHLE tests result T1,2,3,4 and 5– Precipitation map analysis to predict aluminum precipitation

• SNC-001 Bench test Results– Al corrosion/ release rate result– Passivation of Al release from the SNC test result– Proposed new Al release correlation (with passivation)

Overview


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Background and Objectives• UNM’s CHLE tests were designed simulate the corrosion product in the tank,

corrosion product transfer from tank to column, corrosion induced head loss behavior over the 10 or 30 day testing periods.

• 10-day or 30-day chemical effect test simulating LB-LOCA (T2,T5), MB-LOCA (T1), and non prototypical LOCA (T3,T4) with conditions found at South Texas Project Nuclear Operating Company (STPNOC) were conducted to assess the generic safety issue (GSI) 191 chemical effects

• The objectives of those 5 tests were to create conditions that captured the prototypical or non-prototypical temperature profile, corrosion materials, and chemistry conditions in ECCS system, and evaluated the corrosion induced head loss on blender-processed beds and NEI-processed beds over the testing period.


4

CHLE loop schematic diagram

Corrosion tank module

Head loss modules (3 identical columns)


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Experimental set-up• Corrosion tank module

– Corrosion materials (Al, Zn, GS coupons, fiberglass, concrete) were loaded

– Tank temperature was controlled by the set temperature profile (LB-LOCA, MB-LOCA, non-prototypical condition)

– Solution in tank was well mixed with recirculating loop

• Head loss modules– 3 identical columns were linked to tank– Each column was loaded with blender-processed bed or NEI-

processed bed– Pressure drops (head loss) were measured at each column


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Corrosion tank & head loss modules


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Test conditionsT1 T2 T3 T4 T5

Corrosionmaterials

Al scaffoldingFiberglass

Al scaffoldingFiberglassGS, Zn couponsConcrete

Al couponsFiberglassGS, Zn couponsConcrete

Al couponsFiberglass

Al scaffoldingFiberglassGS, Zn couponsConcrete

AV (ft/s) 0.01 0.01 0.01 0.01 0.01

pH 7.22 7.32 7.22 7.22 7.25

Temperature profile

MB-LOCA LB-LOCA Non-prototypical

Non-prototypical

LB-LOCA

Testing period 30-day 30-day 10-day 10-day 10-day

Bed prep. NEI (1)NEI (2)NEI (3)

NEI (1)NEI (2)NEI (3)

Blender(1)NEI(2)Blender(3)

Blender(1)NEI(2)Blender(3)

Blender (1)Blender (2)Blender (3)


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Comparative Test matrix with CHLE tests

1. Prototypical temperature & aluminum condition (LOCA) vs. non-prototypical LCOA temperature & aluminum (100times more than prototypical) condition: T125 vs T34– T1,2, and 5 followed the prototypical LOCA temperature profile with prototypical aluminum material

turbidity kept decreasing over the testing– T3 and T4 temperature condition designed to generate aggressive corrosion product by maintaining

80C for first 5 days turbidity decreased for first 5 days and started increasing after day 62. NEI-bed vs. blender-bed: T2 vs. T5 or T3/T4

– T2 (NEI) vs T5 (blender) showed that blender bed (100’’ of water) indicated significant head loss compared to NEI bed (2’’ of water)

– T3 and T4 also showed that a blender bed is much more sensitive than an NEI bed in the same operating condition

3. Al precipitation effect vs. zinc source effect : T3 vs. T4– When zinc sources are present, initial high turbidity was observed and head loss increased along with

certain time.– When aluminum precipitation occurred, turbidity started increasing, and head loss increase was also

observed in some cases.4. MB LOCA vs. LB LOCA : T1 vs. T2

– With NEI-processed bed condition, the head loss increase and turbidity trend for both MB, LB LOCA condition looks similar. No big difference observed.


1. Prototypical temperature & aluminum condition (LOCA) vs. non-prototypical LCOA temperature & aluminum (100times more than prototypical) condition: T125 vs T34

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Turbidity measurement to detect the precipitated particles in solution

T1 T2 T5

T4T3

In T1,2 and 5, turbidity never increased during the testing periods no particle formation but particle filtration or segmentation

In T3 and T4, turbidity decreased and after day 6-7 started increased Potential of aluminum precipitation due to supersaturation


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Head loss

0 1 2 3 4 5 6 7 8 90

20

40

60

80

100

120

140

Norm

alize

d He

ad lo

ss a

t 20o C

[''H2O

]

Time [Day]

Column_1(Blender) Column_2(Blender) Column_3(Blender)

T1 T2 T5

Head loss with NEI-bed (T12) was small but head loss (T5) with blender-bed was much higher.However, the head losses resulted from the initial release (zinc), no al precipitation effect

T4T3In T3, two increases in head loss were found, first increase was attributed to “zinc source effect” and second increase was “Al precipitation effect”. In T4 head loss increased as turbidity increased (Al precipitation effect)


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Metal concentrationsT1

T4

T3

Analyte (DL) T1 T2 T3 T4 T5

Aluminum (0.2 mg/L) 0.25 mg/L BDL 2.5 mg/L 5.1 mg/L BDL

Calcium (10 mg/L) BDL BDL BDL BDL BDL

Silicon (0.8 mg/L) 5.0 mg/L 2.0 mg/L 13 mg/L 15 mg/L 2.7 mg/L

Zinc (0.1 mg/L) N/A 0.7 mg/L 0.2 mg/L N/A 1.1 mg/L

*Back-up slice (page #34)


2. NEI-bed vs. blender-bed: T2 vs. T5 or T3

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Head loss (T2[NEI] vs. T5[blender], T3)T2: NEI

T5:blender

T3: NEI T3:blender


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SEM images for NEI-bed vs. blender-bed

NEI bedfrom T3

blender bed from T3

NEI bedfrom T2

blender bed from T5


3. Al precipitation effect vs. zinc source effect : T3 vs. T4

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Two types of head loss increase in T3 & T4


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Aluminum and zinc effects


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Particle size of T3 & T4


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Al precipitation map with CHLE tests data

20 30 40 50 60 70 80 90 1009.0

9.5

10.0

10.5

11.0

11.5

12.0

12.5

13.0

pH+p

[Al] T

Temperature (oC)

Solubility by VMINTEQ UNM, T5 test result UNM, T4 test result UNM, T3 test result UNM, T2 test result UNM, T1 test result

Non-precipitation region

Precipitation region

Day 7 in T3

Day 6 in T4

Precipitation line based on turbidity


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Add figure from Bahn article


4. SNC-001 Bench test result and proposed new Al release correlation (with passivation)

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Objectives• Current bench test is consisted of baseline Al release data

evaluating temp-effect, pH-effect with TSP in solution at different time(5h ~ 5day)

• The result clearly demonstrated passivation or inhibiting effect over time.

• Previous WCAP correlation is only function of Temp, and pH, but time variable was not incorporated in their model, which leads to not capture passivation effect on Al release

• In this study, new correlation is proposed and validated with SNC bench test data.

• In future, this proposed correlation will be further validated with other literature data and CHLE data


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Al release bench test with TSP in solution

Average test coupon surface = 0.00146 m2

Series pH Adjustment Target pH Temperature, °C

1100 TSP 7.34 85

1200 NaOH 7.34 85

1300 TSP 6.84 85

1400 TSP 7.84 85

1500 TSP 7.34 70

1600 TSP 7.34 55


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Al release [mg/m2] with time

0 1000 2000 3000 4000 5000 6000 7000 80000.0

2000.0

4000.0

6000.0

8000.0

10000.0

12000.0

14000.0

“Al release increased rapidly over the first 24 hours and stop release due to passivation (inhibiting effect on al release)”


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WCAP-16530 (Eq. 6-2)

“At intermediate times (i.e., less than 30 days), Equation 6-2 will underpredict the release rate. Hence, the cumulative 30-day integrated aluminum product release predicted by this equation should be used for screen testing, even if an intermediate time period is being simulated. If a cumulative value at an intermediate time is desired, individual plants must justify the derivation of that value.”

WCAP-16530 page 96

Release = f(Temp., pH)


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WCAP always overpredict even at intermediate time (i.e., less than 30 day)

0 1000 2000 3000 4000 5000 6000 7000 80000.0

10000.0

20000.0

30000.0

40000.0

50000.0

60000.0

70000.0

meausred release vs. WCAP release

1100 meausred al release [mg/m2] 1100 WCAP cal. Al release [mg/m2]

time [min]

Al re

leas

e [m

g/m

2]


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A proposed Al release equation with boric-TSP in solution

• Using multi-variable nonlinear regression scheme, following regression parameters were determined within the adjusted R-square value of 0.95.

• Matlab and Orgin were utilized for MVN regression.

A=-0.30694B=-715.3C=0.03044D=0.001584E=0.99T=temperature[K]pH=pH at the initial stageTime= corrosion testing time


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Test #Temperature[K] initial pH time[min] aluminum (mg)

aluminumrelease(mg/m2)

KIM's calculatedAl release(mg/m2) ratio

1101 358.15 7.34 300 2.70 1849.3 3016 1.631102 358.15 7.34 660 4.60 3150.7 3167 1.011103 358.15 7.34 1440 4.95 3390.4 3171 0.941104 358.15 7.34 3240 4.70 3219.2 3171 0.991105 358.15 7.34 7200 4.65 3184.9 3171 1.001301 358.15 6.84 300 1.00 684.9 955 1.391302 358.15 6.84 660 1.20 821.9 1002 1.221303 358.15 6.84 1440 1.40 958.9 1004 1.051304 358.15 6.84 3240 1.40 958.9 1004 1.051307 358.15 6.84 7200 1.35 924.7 1004 1.091401 358.15 7.84 300 9.50 6506.8 9867 1.521402 358.15 7.84 660 14.50 9931.5 10362 1.041403 358.15 7.84 1440 16.50 11301.4 10375 0.921404 358.15 7.84 3240 17.00 11643.8 10375 0.891407 358.15 7.84 7200 16.50 11301.4 10375 0.921501 343.15 7.34 300 2.90 1986.3 1651 0.831502 343.15 7.34 660 3.05 2089.0 1733 0.831503 343.15 7.34 1440 3.10 2123.3 1736 0.821504 343.15 7.34 3240 3.05 2089.0 1736 0.831507 343.15 7.34 7200 3.20 2191.8 1736 0.791601 328.15 7.34 300 0.45 308.2 887 2.881602 328.15 7.34 660 0.75 513.7 931 1.811603 328.15 7.34 1440 0.80 547.9 933 1.701604 328.15 7.34 3240 0.85 582.2 933 1.601605 328.15 7.34 7200 0.85 582.2 933 1.60


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0 1000 2000 3000 4000 5000 6000 7000 80000.0

2000.0

4000.0

6000.0

8000.0

10000.0

12000.0

14000.0

Measured release vs. UNM's release calculation

1100 measured al release [mg/m2] 1100 UNM prediction al release [mg/m2]1300-measured 1300 UNM-predictio1400-measured 1400-UNM-predictio1500-measured 1500-UNM-prediction1600-measured 1600-UNM-predictio

Time[min]

Al re

leas

e [m

h/m

2]


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T4 CHLE test• Water volume in CHLE tank is 300 gallon (1135 liter)• ICP results are given• Total Al area = 2.787 m2

• Al release is calculated below

Day 0 1 2 3 4 5

Al (mg/L) 0.2 4 5.1 5 4.9 4.9

Al (mg) 227 4540 5788.5 5675 5561.5 5561.5Al release[mg/m2] 81 1629 2077 2036 1995 1995


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Al release prediction with proposed correlation for CHLE-T4

0 1000 2000 3000 4000 5000 6000 7000 80000

500

1000

1500

2000

2500

Measured Al release vs. predicted al release over the first 5 days of T4 at Temp=80 C, pH=7.22

T4 Measured al release(mg/m2) proposed correlation's predictio for T4 al release (mg/m2)

Time [Min]

Al re

leas

e [m

g/m

2]


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24 hours, Al release


BACK-UP SLIDES…

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Aluminum oxide layer thickness from XPS

T3 aluminum oxide layer ~ 15 nmT4 aluminum oxide layer ~ 2.3 nmMaybe zinc effect …


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Al release rate vs. Al release• Al Release rate : mg/m2-min• Al Release per unit area : mg/m2

• In long-term corrosion, release rate might be accurate and misleading user.

• Release per unit area is more clear method to describe how much Al corroded or release into solution

• In this study, all data and comparison will be made based on the Al release [mg/m2] as a reference unit.


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pH effect on Al release [mg/m2]


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Temperature effect on Al release [mg/m2]


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Flow sweep test with NEI vs. blender

0 20 40 60 80 100 120 1400.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4

1.6

Supe

rficia

l velo

city (

ft/s)

Head Loss in NEI Bed("H2O) Superficial Velocity (ft/s)

Time (Minutes)

Head

Los

s ("H

2O)

0 20 40 60 80 100 120 1400.00

0.02

0.04

0.06

0 20 40 60 80 100 120 140 160 1800

10

20

30

40

Head Loss in Blender Bed ("H2O) Superficial Velocity (ft/s)

Time (Mins)He

ad L

oss (

"H2O

)

0.00

0.02

0.04

0.06

0.08

0.10

0.12

Supe

rficia

l velo

city (

ft/s)


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Al concentration and Turbidity

0 1 2 3 4 5 6 7 8 9 10 11 120

1

2

3

4

5

6

Turb

idity

[NTU

]

Al Concentration [mg/L] Turbidity [NTU]

Time [Days]

Conc

entu

ratio

n of

Al [m

g/L]

0 1 2 3 4 5 6 7 8 9 10 11 120.0

0.2

0.4

0.6

0.8

Al

Scale [Al(OH)3,?,?, etc.,]

Al3+

Corrosion / Release (ICP result)

Rapid Al Release

Al Saturated (no release)

Al supersaturatedPossible precipitating


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Ergun Correlation

Based on a comprehensive set of experimental data for flow through granular porous media with porosities (e) between 0.4 and 0.85,

BUT,Later investigator found that for laminar flow through fibrous porous media, characterized by HIGH porosity, the functional relationship between pressure and PorosityExpress above was not valid (NUREG, CR-6224, Appendix B)

Later,Based on a large data base for flow through fibrous media, Davis(1962) proposed that for laminar flow through fibrous porous media,

Ergun Correlation (1952)- Kozeny-Carman equation(1956)- Valid in laminar flow


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NEI bed behavior with analytic model

Assume that inertial term become negligible when the flow are in laminar regionNEI Bed sweep test indicate good example of the relationship between U & HL

“a” value for analytic equation for NEI-bed can be determined from the experimental upward flow sweep test result.

0.00 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.080.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4

1.6

1.8 Average head Loss in NEI ("H2O)

Head

Los

s ("H

2O)

Superficial Velocity (ft/s)


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Over prediction in WCAP grows as time progresses

Temperature[K] pH

Time[min]

aluminum (mg)

Measured Alrelase(mg/m2)

WCAP calculated Al release(mg/m2) Ratio

358.15 7.34 300 2.70 1849.3 2750.403911 1.487255358.15 7.34 660 4.60 3150.7 6050.888604 1.920499358.15 7.34 1440 4.95 3390.4 13201.93877 3.893905358.15 7.34 3240 4.70 3219.2 29704.36224 9.227313358.15 7.34 7200 4.65 3184.9 66009.69386 20.72562358.15 6.84 300 1.00 684.9 2180.887208 3.184095358.15 6.84 660 1.20 821.9 4797.951857 5.837508358.15 6.84 1440 1.40 958.9 10468.2586 10.9169358.15 6.84 3240 1.40 958.9 23553.58184 24.56302358.15 6.84 7200 1.95 1335.6 52341.29299 39.18887358.15 7.84 300 9.50 6506.8 3651.209465 0.561133358.15 7.84 660 14.50 9931.5 8032.660824 0.808806358.15 7.84 1440 16.50 11301.4 17525.80543 1.550768358.15 7.84 3240 17.00 11643.8 39433.06223 3.386604358.15 7.84 7200 16.50 11301.4 87629.02717 7.753841343.15 7.34 300 2.90 1986.3 1010.8516 0.508911343.15 7.34 660 3.05 2089.0 2223.873521 1.064543343.15 7.34 1440 3.10 2123.3 4852.087681 2.285177343.15 7.34 3240 3.05 2089.0 10917.19728 5.225937343.15 7.34 7200 3.20 2191.8 24260.43841 11.06883328.15 7.34 300 0.45 308.2 329.7195656 1.069757328.15 7.34 660 0.75 513.7 725.3830443 1.412079328.15 7.34 1440 0.80 547.9 1582.653915 2.888343328.15 7.34 3240 0.85 582.2 3560.971309 6.116492328.15 7.34 7200 0.85 582.2 7913.269575 13.5922

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