ML20148M826
| ML20148M826 | |
| Person / Time | |
|---|---|
| Site: | Yellow Creek  |
| Issue date: | 10/17/1978 |
| From: | Mattson R Office of Nuclear Reactor Regulation |
| To: | Boyd R Office of Nuclear Reactor Regulation |
| Shared Package | |
| ML20148M821 | List: |
| References | |
| NUDOCS 7811220152 | |
| Download: ML20148M826 (4) | |
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October 17, 1978 g fib T 4 q C MEMORAtlDUM FOR: Ro" - S, Boyd, Director, Division of h ct / Management % 3
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FROM: Roger J. Mattson, Director, Division of Syst n. Safety
SUBJECT:
POST-LOCA HYDROGEN PRODUCTION FROM MATERIALS INSIDE CONTAINMENT . I
References:
(1) Memorandum to D. B. Vassallo from C. O. Thomas,
" Recommended Licensing Board Notification - Post-LOCA Hydrogen Generation from Materials Inside Containment dated August 24, 1978; (2) Memorandum for Robert L. Tedesco from W. R. Butler,
" Post-LOCA Hydrogen Generation from Zinc," dated September 20, 1978; and (3) Memorandum for W. R. Butler from F. Eltawila through J. Kudrick, " Hydrogen Generation in Mark II Containment Due to Zinc Corrosion," dated September 20, 1978 In Reference (1) Mr. Thomas indicated that the post-LOCA hydrogen produc- .
tion due to corrosion of materials inside the primary containment, (such as aluminum and zinc) and the thermal, chemical, and radiolytic decomposition of organic components in protective coating systems may not have been adequately considered in the evaluation of combustible gas control systems and recommended notification of appropriate hearing boards. The effects of the matters discussed in Reference (1) have been conservatively evaluated to assess the potential for significant hydro-gen generation due to the presence of the stated materials , i.e. , conservative values were used for the hydrogen generation rates from gal-vanized steel and zinc-based coatings [provided by MTEB in a post-LOCA environment and to evaluate the potential consequences o]n the design of hydrogen control systems in both BWR and PWR containments. A brief sum-mary of the effects of these aspects as potentially additional contribu-tors of hydrogen production follows: 7 8112 2 0 15v
Roger S. Boyd October 17,1978 DEC04 POSITION OF ORGANICS: A substantial amount of organic materials is used in protective coating systems, including those over zinc-based primer paints . ins.ide..PWR and .BWIL containmentsu V When exposed to the LOCA environment (high tenperature, chemical, and radiation fields), these organic materials undergo a process of decomposition to form hydrogen and hydrocarbons. The Accident Analysis Branch (DSE) has estimated the resultant hydrogen and hydrocarbon concentrations resulting from the radiolytic decomposition of organics and the thermal and chemical reaction of organic coatings on concrete surfaces. Assuming a conservatively integrated radiation exposure of 108 rads, the Accident Analysis Branch (AAB) estimates the hydrogen concentration due to radiolytic decomposition of organic coatings to be less than 0.4% for PWR's and less than 0.2% for BWR's. For hydrogen generation due to thermal and chemical reaction of organic coatings on painted concrete surfaces the AAB estimates the resultant hydrogen concentration to be less than 0.3% for PWR's and less than .2% for BWR's. If we sum these hydrogen contributions from organic materials which were heretofore not included in our analyses, the additional hydrogen represents rougnly a 10% increase in the hydrogen generated from all sources previously considered; i.e., zirconium water reaction, radiolysis of water, and oxidation of zinc with its organic topcoat during the post-LOCA period. Since there will be a large amount of water, relative to the amount of organic materials, it can be concluded that the hydrogen gas generated - from radiolysis of water should daninate that from decomposition of the organic materials. CORROSION OF ZINC IN PRESSURE SUPPRESSION CONTAIUMENTS: The hydrogen generation from galvanized steel and zinc-based primers is a strong function of the containment tamperature history following a LOCA. For ice pressure suppression containments the post-LOCA tenperature profiles have been found to be sufficiently low that the hydrogen generation from zinc-rich coatings does not jeopardize the capability of the hydrogen recanbiner systems. Furthermore, for BWR containments, where the hydro-gen concentration is predicted to peak within a few hours af ter accident initiation, there is not sufficient time for the hydrogen generation from the zinc-rich coatings to cause the hydrogen concentration to exceed the 4% flammable limit before recombiner actuation or shortly thereaf ter. CORROSION OF ZINC IN DRY CONTAINMENTS: Because of the uncertainty in the hydrogen genera tion rates, calculations were performed to determine the impact of the uncertainty on the recombiner systems for several PWR plants (seeEnclosure3). The h steel (provided by MTEB)was ydrogen increased generation rate curve by a factor of 2.0for to galvanized bound the available experimental data for galvanized steel. This increase in the
Rog'er S. Boyd October 17, 1978 corrosion rate would only result in a very slight increase in the hydrogen concentration but would yield a H for Yellow Creek. In most cases,2the concentration recombiner systems slightly inhad excess of 4% the capability of maintaining the hydrogen concentration below the 4% flammable limit by actuating earlier in the post-LOCA period. In the analysis performed for the Yellow Creek plant, the hydrogen concen-tration would reach a peak value of about 4.13%; however, giving credit to the diluting effect of the steam in the containment atmosphere following a LOCA shows that the hydrogen concentration would not exceed the 4% flammable limit. While it is our view that no safety concern is involved as a result of our using the updated hydrogen generation rates for zinc-rich coatin.gs, we find that there is sufficient justification to warrant further staff effort toward examining the generation of hydrogen from zinc-rich paints and organic materials. A more refined knowledge of the behavior of these materials would increase our confidence in this area of review. We plan to prepare a User's Request to have RSR undertake studies in such areas as: 1) the impact of uncertainties in the hydrogen generation rates on the analyses of hydrogen accumulation in PWR dry containments includi:,g an assessment of the inherent conservatisms in such analyses (see Enclosure 3); and 2) the relative importance of the decomposition of organic materials as a source of hydrogen in containments. In summary, we find that the effects evaluated regarding post-LOCA genera-tion of hydrogen in both BUR and PWR pressure suppression type containments do not lead to new significant safety concerns not already being considered in our current safety reviews. Since this matter was not explicitly considered in our reviews until recently, I agree that notification of appropriate licensing boards may be appropriate.
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l t- , (. ~1 N, g Roger J. Mattsoni Director Division of Systems Safety Office of Nuclear Reactor Regulation
Enclosures:
As Stated cc: See page 4
-+
1 Roger S. Boyd October 17, 1978 l l
-1 cc: H. Denton R. Mattson R. DeYoung V. Stello D. Eisenhut
- 8. Grimes J. Knight R. Tedesco J. Glynn /
D. Vassallo /- W. Butler C. Thomas J. Kudrick . i F. Eltawila S. Pawlicki W. Houston P 1 Y a
Enclosure 1
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4 UNITED STATES (Reference 2) v- , t NUCLEAR REGULATORY COMMisslON
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WASHINGTON, D. C. 20055
..... SEP 2 01978 MEMORANDUM FOR: Robert L. Tedesco, Assistant Director for Plant Systems. DSS FROM: W. R. Butler, Chief, Containment Systems Branch, DSS l
SUBJECT:
POST LOCA HYDROGEN GENERATION FROM ZINC 1 l
Reference:
Memo for R. Tedesco f rom S. Pawlicki, " Hydrogen Generation l Rates after LOCA," March 15, 1978 We have received from the MTEB updated data, included in Attachment 1, on hydrogen generation resulting from the corrosion of zinc and zinc-based coatings. These data are in the form of hydrogen generation rates as a function of temperature. The purpose of this memorandum is to report the results of a study to determine the impact of using these revised MTEB hydrogen generation rates in our hydrogen control analyses. Our hydrogen control analyses were performed using the COGAP 2 code for five selected plants to gauge the effect of the hydrogen generation rates. The plants selected and their pertinent input parameters are shown in Table 1. All of the plants included in the study are reported to have a substantial quantity of zinc inside containment. For example, San Onofre, which has the smallest reported mass of zinc, still has enough zinc to produce a 4% H2 concentration, assuming all of the zinc reacts instanta ~ neously to produce hydrogen. Therefore, it is important to accurately represent the rate at which the zinc reacts to produce hydrogen. Figure 1 presents the calculated hydrogen concentration transients for the three dry containment plants (PWR) included in the study. For these analyses the recombiner actuation times, shown on Figure i, were taken from the applicants' SAR, with the exception of the Yellow Creek plant, for which the recombiners were arbitrarily started one day after the postulated LOCA. As can be seen from Figure 1, all of the plants main-tain the' hydrogen concentration below the lower flammability limit.
Contact:
C. Tinkler, CSB 492-7711
~
so .. .sp
, Robert L. Tedesco SEP
'- 2- 0973-Figure 2 presents the calculated hydt ogen concentration transient for the Watts Bar ice condenser containment plant. Even though this plant contains a large mass of zinc, in the form of galvanized matal, the hydrogen concentration is maintained well below the flammability limit.
The effect of the large zinc mass is mitigated by the relatively low containment atmosphere temperature post-LOCA, which results in a slower hydrogen generation rate. This lower generation rate can be accomnodated by the recombiners. Figure 3 presents the calculated hydrogen concentration transient for the Hatch 2 plant (Mark I containment) using our estimates of zinc in-side the containment since this information was not supplied by the applicant. Figure 3 also presents a comparison with a calculated hydro-gen transient assuming no zine was present. Figure 4 shows the post-LOCA temperature transient used to determine the zinc corrosion rates. It is apparent from the analyses performed that the effect of zinc, at least in the manner considered, was minimal for the Hatch 2 plant. This is probably due to the small surface area of zinc assumed to exist in the drywell and the relatively low post-accident temperature transient throughout the containment. Attachment 2 provides the results of analyses perfonned for the Susquehanna plant (Mark II containment), which considered zinc corrosion and subsequent hydrogen production. In surrmary, the conservative analyses performed for Susquehanna demonstrate that the hydrogen concentration remains below the flamnability limit. An evaluation of the design parameters for Mark III containments leads us to conclude similarly on the effect of zinc corro-sion for these plants. As a result of our analyses, we conclude that the effect of using the MTEB hydrogen generation rates to model the corrosion of zinc does not produce hydrogen concentrations above the flammabili ty limit. In general, the ef-fcct of using the updated zinc corrosion rates on the plants considered would be limited to decreasing the required recombiner actuation time. However, there are uncertainties associated with these analyses, several of which are listed below:
- 1. The MTEB hydrogen generation rates for the corrosion of galvanized steel are portrayed as " realistic" (see Attachment 1) and as such do not represent conservative or bounding values.
- 2. There is little experimental evidence to determine the effect of the spray or sump water chemistry or pH upon zinc corrosion rates.
p *
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N Robert L. Tedesco 3. The actual quantities of zinc present in the BWR plants are not known.
- 4. The entire curve for hydrogen generation from zinc based paint is derived from one experimental data point with the slope of the line assumed to be equal i the slope of the curve for gal-vanized steel.
Although our findings with the updated corrosion rates for zinc do not - appear to represent a safety hazard, it is our view that there is suf-ficient justification to warrant the continuation of staff efforts toward examining the generation of hydrogen from the reaction of materials inside containment. 4 G' 7 . Walter R. Butler, Chief Containment Systems Branch Division of Systems Safety Attachments: As stated cc: J. Shapaker J. Kudrick S. Brown ' F. El tawila W. Milstead p-**@*
Table 1 -
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t i Plant NSSS Thermal Volume Zirconium Mass and Surface
~
Rating (ft 3) Mass Area of Zinc in Containment (Mwt) Reacted Zinc Paint Galvanized Metal Yellow Creek CE 4100. 3,580,000 3750 lb. 15,000 lb /360,000 ft 10,940 lb /140,000 ft 2 Erie B&W 3876. 2,400,000 2600 lb. 20,875 lb./187,000 ft 2 7,000 lb /56,000 ft 2 .j San Onofre CE 3560. 2,305,000 2500 lb. 850 lb /6,700 ft 2 15,600 lb /138,000 ft 2 j 2&3 Watts Bar 1 1 3565. 1,230,000 648 lb. None 59,200 lb /336,000 ft 2 Hatch - 2 GE Drywell 2537. 146,266 560 lb. 6,710 lb /18,048 ft 2 None Wetwell 109,712 22,980 lb /61,823 ft None l
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fTTkl/WENf [ MIE[ CROOKHAVEN NATIONAL LADORATORY MEMORANDUM DATE: 0/2/78 Tor 11.r. con rad TROMP D. van TDoywt
'GUDJECT: H y BeImaan Trom 2n Corruzion Eze dite umned todeof the questf o.ru of (1) amotra ts o f rt - realistic curves var.
2 comervative curves, nuca (2) th e e ffec t o f pII - ren tra l purn unter vs . pII eg saith cron prersent.
- 1. 171gure 11 of try reyxt unL-mmrc-24532 rdacn
* -1 3.3 x 10 Scr.f t lar for a 100 hour te st at r4t 9.3. rh erefor e, if I hai tn corts truct a curva for this tx>s t realis tic curvo, I votId ctraw it au lino A , rigura 1, attached. Th e curve lo ba uel o n avo r--
ago rutas at varioun teweernturwis in bocatal cpray at PIT 9.S, a rd ,in ouppcrrted by f7US c:s w,L1 aa tar ank1_in In a tituto d a t a , i.e. 1. t i. s feit to be runlic ti c n in ee i t con ta i n-> sneve rs I po i n ts o f a vn mqq v a l ue s over periods of one day or incre, and we have novu rrt i w ets o f d ata that fi.t ronronnbly well. 'this curve falis below tlw Zi tte t poin t for avercge H re 2 lea te oE pit 9. 3 fcr ga lvan t r i.nq in h in 100 hour
-te s t , no thnt It s>+ css dit fIcult drtw it nny 1 crwnr unlo yz sect ob-tain morir data.
- 2. ' In dixetranica the plI uffeet, I asse tha t tin prns enee of bocebe i . 1 M4eg
__-- -_____-._____._.__.____1__
;tocaorarx1rms to II.Y., Conread O/07/70 does not nah a cigniti::cmt clif fo ronce, ro titat the conclusion ulll apply to DWR rwutral water sprayt: at pH 7. In Figure 14 of OffL-NUP.EG-2 45 32 it is shtnin tM t tM rute of IT2 ""1"""' f**" Z" I" #"""""
by n f ac to r o f 1. 3 to 1. 4 f or o a ch pa tm i t be lov 9. Th re f ore , tro valuea for p?! 7 nre proposed an line H in Flyuru 1 attacimd, which to 3.5 timma lino A, arvJ parntlel tn it. I u c e 3. 5 bec au co -th e p h i n tim field will probably in a little talow 7. Tiv) tuo linen corrr2spond to equa tioner Reate H2 - 1.3 x 10 exp - 14500 Airw A (pH 9. 5) 5 1 g scr.rt. hr Lino D (ph 7) Ra te II2== 4 . 6 x 10 5 exp - 14500 g
-2 IICF Y t . hr
-I late that lines a is identio.tl to Figure 11 of Um,-Tnntm-24532.
-With morc ord bottor data we could conutruct mirvcan wi th ge r-n tm e confid-rc e ,
u tantioned in my resort qtoted chovo. tW t ta r k ncrw1.w1 gu of hw tre n2 #"1"'i " b ouss tairwx1 over longe r po rlod u at tM lino r temp e rn tnru n will a teo embla a mre roullstic cvalnation of U butIdup y over a cycle snv_h as vauld M o xp o rt e rv:od Arrirry a LOCA.
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'b BROOKHAVEN NATIONAL LABORATORY 1 MEMORANDUM DATE: 0/2/78
.I l
I TO: II.F. Conrad l FROM: D. van Rooyen i
SUBJECT:
H2 Release From Zn Corrosion ) We discussed today the questions of (1) amounts of 11 7
- realistic curves vs.
! conservative curves, and (2) the effect of pH - neutral pure water vs. pH 9 with -boron present.
- 1. Figure 11 of my report BHL-NtJREG-24532 shows the best conservative curve for H from Zn at various ternperatures, and the text of that 2
report gives the uncertainties associated with the evaluation of available data. The curve was arrived at by establishing the best slope for log 112vs.1/ temp (*K) plot, and drawing such a curve through the "Zittel" highest point for a zinc-rich paint. There is no other point quite as high as this Zittel result, and he also re- - ported that the rate fell of f to near zero af ter one day for the paint. However, he also reported an average value equivalent to
-3 1 Th eref or e, 3.3 x 10 SCF.ft. hr for a 100 hour test at pH 9.3.
if I had to construct a curve for the most realistic curve, I woul draw it as line A , Figure 1, attached. The curve is based on avr age rates at various temperatures in borated spray at pH 9.5, ary* ts supported by NUS as well as Franklin Institute data, i.e. it is femt to be realistic since it contains several points of average values over periods of one day or Taore, and we have several sets of data
.tha t fit reasonably well . This curve falls below the Zittel point ,
for average H2 release of pH 9.3 for galvanizing in his 100 hour test, so that it seems dif ficult to draw it any lower unless we ob-
' tain more data.
- 2. In discussion the pH cffect, I assume that the presence of borate 1
Memorandum to li.P. Conrad 8/02/78 e does not make a significant dif ference, so that the conclusion will
, apply to BWR neutral water sprays at pil 7. In Figure 14 of BNL-HUREG-24532 it is shown that the rate of !!2release f rom Zn increases
, by ,a factor of 1.3 to 1.4 for each pli unit below 9. The refore, the values for pli 7 are proposed as line B in Figure 1 attached, which is 3.5 times line A, and parallel to it. I use 3.5 because the ph in the field will probably be a little below 7. The two lines correspond to equations: 5 1450* -2 -1 Line A (pli 9.5) Rate 11 1.3 x 10 exp - RT 2 5 1450 1 Line B (ph 7) Rate 11 = 4.6 x 10 exp - g7, SCF.Ft. hr 2 ! Note that line B is identical to Figure 11 of DNL-NUREG-24532. Witit more and better data we could construct curves with greater confidence, as mentioned in my report quoted above. Better knowledge of how the H2 UV 1"DI " lis sustained over longer periods. at the lower tempera tures will also enable a more realistic evaluation of 11 buildup 2 over a cycle such as would be experienced
- during a LOCA.
DvR/bMc ' -enc. cc:
- S.S. Pawlicki B. Turovlin P.M. Almeter l W.Y. Kato J.R. Weeks l l
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' UNITED STAT ES
[8'; .' % NUCLEAR REGULATOnY COMMisslON WASHINGTON, D. C. 205$5
%, . .". . . #' SEP 2 0 B76 MEMORANDUM FOR: W. R. Butler, Chief, Containment Systems Branch, DSS FROM: F. Eltawila THRU: J. Kudrick, Section Leader, Section A Containment Systems Branch
SUBJECT:
HYOR0 GEN GENERATION IN MARK II CONTAINMENT DUE TO ZINC CORROSION
Reference:
Memorandum for W. R. Butler from S. Pawlicki dated August 9, 1978 Since the spray systems in BWR's use water without additives for the purpose of reducing pressure and temperature inside the containment, it was previously believed that the corrosion of zine will contribute a negligible amount of hydrogen to the BWR containment atmosphere, ilowever, during the course of our review of Susquehanna Steam Electric i Station (SSES), a BWR Mark Il containment, we noted that the applicant has considered zinc corrosion as a potential source of hydrogen follow-ing a postulated loss-of-coolant accident. In order to determine the contribution of zinc corrosion to the total hydrogen accumulation in Mark II containment, an analysis was performed by the staff based on the following:
- 1. The masses and exposed areas of zinc paint and galvanized steel as reported in SSES' FSAR; ,
- 2. The containment temperature response to LOCA as reported in SSES' FSAR; and
- 3. Corrosion rates based on rate values recomended by the Materials Engineering Branch (see referenced memorandum).
~
l
,c . s-1 W. R. Butler -
2- SEP 2 01978 The results of the analysis show that the 100 scfm flow rate provided by each of the two recombiners (Susquehanna utilizes two 100 percent redundant hydrogen recombiner systems, each system consisting of two hydrogen recombiners with one located in the drywell and one located in the wetwell) is sufficient to maintain the hydrogen concentration below 4 volume percent. { However, most Mark II containments utilize only one fully recundant i hydrogen recombiner system with each system consisting of one hydrogen recombiner located outside the containment with the suction point located in the drywell and the discharge point located above the water level in the suppression pool. Therefore, a similar analysis was per-formed for LaSalle County Station (LSCS) to determine the contribution , of zinc corrosion to the total hydrogen accumulation assuming that'only one hydrogen recombiner serves both tne drywell and the wetwell regions. The results of the analysis show that the 150 scfm flow rate provided by the recombiner to control the hydrogen concentration in both the drywell and wetwell is sufficient to maintain the hydrogen concentration below 4 volume percent if the recombiner is initiated when the hydrogen concentration reaches 3.5%. On this basis, it is recommended that no design modification be required for the hydrogen control systems of the Mark II type containments. However, we will require the applicants to consider zinc corrosion in their analyses. y ZZi-t. a. F. Eltawila Containment Systems Branch Division of Systems safety cc: R. Tedesco . S. Pawlicki G. Lainas J. Kudrick C. Grimes C. Anderson T. Su T. Huang C. Tinkler F. Eltawila J. Glynn s
Parameters Used For the Evaluation of Combustible ' Gases in the Containment After LOCA '
~
r Item Value SSES LSCS Drywell Wetwell Drywell Wetwell Mass of zinc as galvanized steel (ib.) 7493 2611 7498 2611 Area of zinc as galvanized steel (Sq. ft.) 64,200 23,150 64,200 23,150 Mass of zinc as paint (ib.) 2430 2480 Area of zinc as paint (Sq. Ft.) 44,000 44,000 Mass of Zircalloy cladding surrounding the fuel (lb.) 78,700 75,324 Zir-water Reaction Percent Volume (Cu. Ft. ) 1. 1.* Reactor Power MWT 3439 3434 Fission Product Distribution and Radiation Energy R.G. l.7 R.G. 1.7 H2 &02 Yield Rate R.G. 1.7 R.G. 1.7 Metal water reaction for LSCS is .77%, the 1% netal water reaction used in this analysis is chosen to bound all Mark II Containments. i
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- umTEO STATES Enclosure 2 4 NUCLEAR REGULATORY COMMISSION (Reference 3)
WASHINGTON. D. C. 20055
%, V # SEP 2 0197B
**..+
MEMORANDUM FOR: W. R. Butler, Chief, Containment Systems Branch, DSS FROM: F. Eltawila THRU: J. Kudrick, Section Leader, Section A Containment Systems Branch
SUBJECT:
HYDR 0GEli GENERATION IN l'. ARK II CONTAINMENT DUE TO ZINC CORROSION
Reference:
Memorandum for W. R. Butler from S. Pawlicki dated. .- e August'9, 1978 Since the spray systems in BWR's use water without additives for the purpose of reducing pressure and temperature inside the containment, it was previously believed that the corrosion of zinc will contribute a negligible amount of hydrogen to the BWR containment atmosphere. However, during the course of our review of Susquehanna Steam Electric Station (SSES), a SWR Mark II containment, we noted that the applicant - has considered zinc corrosion as a potential source of hydrogen follow-ing a postulated loss-of-coolant accident. In order to determine the contribution of zinc corrosion to the total hydrogen accumulation in Mark II containment, an analysis was performed by the staff based on the following:
- 1. The masses and exposed areas of zinc paint and galvanized steel as reported in SSES' FSAR;
- 2. The containment temperature response to LOCA as reported in SSES' FSAR; and
- 3. Corrosion rates based on rate values roccmended by the Materials Engineering Branch (see referenced memorandum).
~
s*-- 'V
W. R. Butler SEP 2 019/8 The results of the analysis show that the 100 scfm flow rate provided by each of the two reccmbiners (Susquehanna utilizes two 100 percent redundant hydrogen recombiner systems, each system consisting of two hydrogen recombiners with one located in the drywell and one located in the wetwell) is sufficient to maintain the hydrogen concentration below 4 volume percent. However, most Mark II containmen'ts u;ilize only one fully redundant hydrogen recombiner system with each systen consisting of one hydrogen , recombiner located outside the containment with the suction point l located in the drywell and the discharge point located above the water level in the suppression pool. Therefore, a similar analysis was per-i formed for LaSalle County Station (LSCS) to determine the contribution of zinc corrosion to the total hydrogen accumulation assuming that only one hydrogen recombiner serves both the drywell and the wetwell regions. The results of the analysis show that the 150 scfm flow rate provided by the recombiner to control the hydrogen conccntration in both the l drywell and wetwell is sufficient to maintain the hydrogen concentration l below 4 volume percent if the recombiner is initiated when the hydrogen concentration reaches 3.5%. On this basis, it is recommended that no design modification be required for the hydrogen control systems of the Mark II type containments. However, we will require the applicants to consider zinc corrosion in their analyses.
~M (r . . c F. Eltawila Containment Systems Branch Division of Systems Safety cc: R. Tedesco S. Pawlicki G. Lainas J. Kudrick C. Grimes C. Anderson T. Su T. Huang C. Tinkler F. Eltawila J. Glynn s
-4
Parameters Used For the Evaluation of Combustible Gases in the Containment After LOCA - Item ' Value SSES LSCS Drywell Wetwell Drywell Wetwell bss of zinc as galvanized steel (15.) 7493 2611 7493 2611 trea of zinc as galvanized steel (Sq. Ft. ) 64,200 23,150 64,200 23.150 hss of zinc as paint (ib.) 2480 2480
.rea of zinc as paint (Sq. Ft.) 44,000 44,000 ! ass of Zircalloy cladding surrounding the fuel (lb.) 78,700 75,324 ir-water Reaction Percent Volume (Cu. Ft.) 1. 1.*
eactor Power MWT 3439 3434 ission Product Distribution and Radiation , Energy R.G. l.7 R.G. l.7 2 &02 Yield Rate R.G. 1.7 R.G. 1.7 Metal water reaction for LSCS is .77%, the 1% metal water reaction used in this analysis is chosen to bound all Mark II Containments.
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Enclosure 3 _D_ISCUSSI0il 0F UNCERTAlflTJ ES Afl0 CONSERVATISMS IN THE POST-LUCA flVDROGEli ACCUMULATION ANALYSIS
References:
- 1) Memorandum for Robert L. Tedesco from Walter R. Butler, " Post-LOCA Hydrogen Generation From Zinc," dated September 20, 1978.
- 2) liemorandum .
- W. R. Butler from F. El tawila thru J. Kudrick,
" Hydrogen Ct oration in a Mark II Containment Due to Ziac Corrosion," .ted September 20, 1978.
The above referenced memorenda discuss the impact of using the MTEB hydrogen generation rates for galvanized steel and zinc-based paints on analyses of the post-LOCA accumulation of hydrogen in various containments. The containment types selected for the study include several PWR dry containments, a PWR ice condenser containment, a BWR Mark I containment and a BWR ilark 11 containmcnt. The results of the study indicate that there is no apparent safety concern. However, because of uncertainties in the hydrogen generation rates for zinc-rich coatings, there is sufficient justification to warrant additional statf effort in obtaining more refined information regarding the behavior of materials inside cotainments following a LOCA. The uncertainties associated with the hydrogen generation rates for zinc-rich coatings, as sta ted in Reference 1, are as f ollows:
~
p ... m _ -~-
- 1. The MLB hydrogen generation rates for the corrosion of galvanized steel are portrayed as " realistic" and as such do not represent conservative or bounding values.
- 2. The entire curve for hydrogen generation f rom zinc-based paint is derived from Zittel's one experimental data point with the slope of the line assumed to be equal to the slope of the curve for galvanized steel.
Additional calculations have been made to assess the ef fects of these uncertainties on post-LOCA hydrogen accumulation analyses. With regard to Item 1, the analyses for the Yellow Creek, Erio and San Onotre plants were redone using the hydrogen generation rate for galvanized steel de-termined by li ttel . This essentially increases the hydrogen generation rate of galvanized steel by a factor of 2.0, whico represents an uoper bound of available data. For the Erie and San Onofre plants, the effect of increasing this rate was small. Both plants were reanalyzed assoning rocombiner actuation a', a hydrogen concentration of 3.5% decreased from 6 days to 5.5 days, and for the San Onofre plant, the time decreased from 21 days to 18 days. For both plants, when the recombiners were actuated the hydrogen concentrations leveled off and began to decrease. a c er-
The reevaluation of the post-LOCA hydrogen accumulation analysis for the Yellow Creek plant, using the higher hydrogen generation rates for galvanized steel, resulted in the hydrogen concentration exceeding 45, and reaching a maximum value of about 4.13%. Hydrogen recnmbiner opera-tion was assumed to be initiated one day after the accident. The results of the analysis are shown in Figure 1. Case A is the analysis that was presented in Reference 1; i.e. , the analysis based on different hydrogen generation rates for zinc-based paint and gaivanized steel. Case B is the analysis where the hydrogen generation rate for galvanized steel was taken from the same reference as the hydrogen generation rate for zinc-based paint. As mentioned previcusly, this represents an increase in the hydrogen generation rate for galvanized steel by a tactor of 2.0, which bounds the known experimental data. The lower curve on Figure 1 shows the results of Case B with the ef fect of steam dilution. Hydrogen accumulation analyses conservatively neglect the effect of steam present in the containment atmosphere. The icwer curve is only an estimate of the effect of steam dilution but it does demonstrate that the presence of the steam maintains the hydrogen concentration < 4%. The analysis described above for the Yellow Creek plant based the calcula-tion of the hydrogen generation from zinc-rich coatings and the mass of steam present in the containment atmosphere on the temperature profile calculated for the accident.
_4 We have also performed a bounding calculation which takes minimal credit for the presence of s team in the atmospnere. The mass of steam was minimized by assuming the temperature of the containment atinosphere to be a constant 120'F throughout the transient, which is the assumed ini-tial containment temperature prior to the accident. Using this conservative assumption for the containment's steam inventory, we calculated a peak hydrogen cencentration of 3.7% using the higher corrosion rates. A plot of the hydrogen concentration transient including steam dilution at 120 F is also shown in Figure 1. The analysis for the Yellow Creek plant is considered to be a bounding analysis for PWR dry containments for the following reasons: a) The zirconium cladding mass is the larges t that has been specified for the f'SSS vendor reactor cores; b) A 55 core iactal-water reaction was assumed; i.e., no Appendix K evaluation was performed to determine the extent of the cladding reaction; c) The containment temperature profile is relatively high since the spray sys tem provided for containment depressuriza tion has a relatively low capability. Since the hydrogen generation rates from zinc-rich coatings are a strong function of tempera ture, the high containment temperature profile will enhance the impact of the coatings as a source
~
of hydrogen on the overall hydrogen production analysis. w w _ _ _ - - - - - - - - - - - - ~ ' - - - - - - ---
The hydrogen accumulation analyses f or the BWR Mark I and Mark II containments and the PWR ice condenser containment were not re-evaluated since the hydrogen generation rates for galvanized steel and zinc-based paint were based on the conservative MTEB curve. Also, since tne hydrogen concentration for BWRs peaks within a few hours after the accident, there will not be sufficient time for the l zinc-rich coatings to contribute enough hydrogen to cause the concen-tration to exceed 4% before the time for recombiner actuation or shortly thereaf ter. Later in the accident, the recombiners are capable of controlling the hydrogen from this source. For the PWR ice condenser containment, the hydrogen concentration remains so low that increasing the hydrogen generation rate of the galvanized steel in the manner described above would not significantly atfect the results. In general, the low temperature profiles in pressure suppression containnents prevent the zinc-rich coatings from dominating the hydrogen production analysis. There are other considerations which suggest that the post-LOCA hydrogen accumulation analyses over-predict the hydrogen concentration in PWR and BWR containments. For example, a factor of 5 is applied to the core zirconium-water reaction; and all zinc rich coatings within the contain-ment are assumed to contribute equally to the generation of hydrogen. Although it is not possible to quantify the conservatism of this latter assumption, it is reasonable to assume that not all surfaces within a
<ontainment would behave in a unifonn manner.
__ _______,_-__---__a-------- - - - - - ^~
t Iten) 2 identifies-a concern about the hydrogen generation rate for paint since the curve is drawn through one data point. Ilowever, the data point chosen represents the highest generation rate obtained from the testing of several samples by Zittel at the Oak Ridge flational Laboratory. Te our knowledge, there are no data which suggest higher hydrogen generation rates for zinc-based paint. lherefore, although more data regarding the hydrogen generation rates for zinc-based paint would be desirable, the f4TEB curve is considered to conservatively. predict the hydrogen generation ra tes . W I s l l
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EllCLOSURE 1
/ % UNGEo A ES E /1 ' NUCLEAR HEGULAlORY COMMISSloN i :yN.k a: E wasmnaron o.c. 20sss t %g%, Wv [/ p,@ g 4 DTD
.o OlEMORANDUM FOR: D. B. Vassallo, Assistant Director for Light Water Reactors, DPM THRU: Steven A. Varga, Chief, LWR-4, DPN ,
FROM: Cecil 0. Thomas , J r . , Project Manager, LNR-1, DPM , SUDJECT: RECOMMENDED LICENSING BOARD NOTIFICATION - POST-LOCA HYDROGEN GENERATION FROM MATERIALS INSIDE CONTAINMENT In accordance with the provisions of NRR Cifice Letter No. 19,
" Procedures for Notification of Licensing Boards of Relevant and Material New Information," I recommend that the appro-priate Licensing Boards be notified of the following information which has been brought to my attention concerning post-LOCA ,
hydrogen generation from uatorials inside containment. I believe that this information is relevant to and constitutes j material new information concerning all boiling and pressurized water reactor nuclear power plants. Following a LOCA in a light water reactor nuclear power plant, hydrogen may accumulate inside the primary containment as a , result of (1) metal-water reaction involving the fuel rod cladding; (2) radiolytic decomposition of the water jn the reactor core and containment sump; (3) corrosion of materials inside the primary containment, such as aluminum and rinc (in the form of galvanized steel and metal-rich paints); and (4) thermal, chemical, and radiolytic decomposition of organic components o f protective coating systems. Although. hydrogen sources (1), (2), and, to some extent (4) above are considered routinely by applicants in their determination of the required capacities of post-LOCA hydrogen control syster s , such as hydrogen recombiners, and by us in our evalua-tion of the adequacy of such sy,tems, there is reason to believe that hydrogen sources (3) and, to some extent,(4) above may not have been adequately considered. Although this may ' - prove to be insignificant in that. considerable margin is already provided in the capacities of post-LOCA hydrogen control systems, it may prove to be significant if it turns out that the capacities of the post-LOCA hydrogen control L. systems are such that the post-LOCA hydrogen concentrati6ns , cannot be maintained below their combustible limits.
~
o W**M~
D. B. Vassallo (djG t 4 IIT3 It is evident from the enclosed memoranda that the staff has solicited further information concerning this matter from external sources. The re fore , in accordance with the provisions of MRR Of fice Letter No. 19, I am providing for your consideration thi.s recommanlation that the appropriate Licensing Boards be notified of this matter. _ g' f;(/;0t ,f'.V), .-
f Cecil 0. Thomas , J r.
Project Manager, LKR-1 Division of Project Mar.agement ccs: J. Stolz yr map
d
- 4) UNtT F D STATES
'/g- g .g t flUCLE An Hr.GU LATORY CO.'.iMissI0ff, .
- j WAsFWJG TON, D. C. 20555 ,
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f - i MEMORANDUM FOR: R. Tedesco, Assistant Director for Plant Systems 8 Division of Systems Safety
\
THRU: J. P. Ynight, Assistant Director for Engineering FROM: S. S. Pawlicki, Chief . Materials Engineering Branch
.. I Z'l
SUBJECT:
HYDROGEN GEliERATION RATES AFTER LOCA. .
- '" >REFEREliCES: 1. Wachtell, G. P., The Franklin Institute Research Laboratories, F-C2697, September 1970 8 Proprietary
- 2. Wachtell, G. P. , The Franklin Institute Research Laboratories, F-C2928, January 1971 - Proprietary t
- 3. Turner, S. E., HUS Internal Me orandum to W. Mitchell, III, March 7,1977 CD-SET-il2
- 4. 'Zittel, H. F., Nuclear Technology, 17 February 1973 pgs. 143-146 ,
By memora'ndum of February 10, 197.8, we proposed to perforn a short tem
' " " 'rev'i'ew'of the available data on zinc corrosion re tes and to provide you-with a prelininary recomenda tion for suitable values to be used in
" -"J'icalcula ting hydrogen genera tion. We have found that there are little -
data- reported in the litera ture with sufficient experimental detail to-
. allow an appraisal of. its validity.
For exanple, we attempted to determine the experimental basis for the
- " - Zinc hydrogen ceneration ra tes reported in the ANSI WG56.1, ANS N-275 draf t standard, t,ut were unsuccessful. We contacted various members 'of the working grcup who indicated that the data were based primarily on Franklin Institute work (1, 2). Our own deriva tion of a hydrogen generation curve f rom the Franklin Institute data provided the lewer curve'in Attach :ent 1 covering only the tc..perature range fron 150 F to 200 F. This curve was corroborated by an' independent set of measurer.ents
- reported by S. E. Turner (3) to the ANS 56.1 Working Group. Zittel at ORNL (4) has reported hydrogen generation rates due to the corrosion of zinc and zinc-bne coatings (Points A and B respectively) at 265 F.
f R. Tedesco n . .2 - ' - 2-
^!
' Since there is a theoretical basis for expecting a straight line semi-log'
~
relation between rate and temperature, to the first approximation, we have drawn a line through the uopermost Zittel point parallel to the data of References 1, 2 and 3. We thereby define an upper limit that encom-passes all the limited data that we now have en hand. We, reccmmend tha t this curve be used for calculating hydrogen generation rates in the interim, until we develop additional data.
'In o'rd'er to resolve the situation we are pursuing a three pronged -
approach: (1) our consultants at BNL will continue to search the literature and make personal contact with workers in the field, (2) applicants with plants in the CP and OL stages of licensing are being requested to79i ve us the experimental basis for their hydrogen generation. rates, and (3) we are evaluating the need and extent of an experimental
. program to supplement available data.
If info'rmation is developed that would significantly change the recom- 2 mendations contained in this memorandum, we will irmediately notify you. In any case we expect to furnish you with an updated report by the end of July. t
' S. S. Pawlicki, Chief ,
Materials Engineering Branch - Division of Systems Safety Office of Nuclear Reactor Regulation s
Enclosure:
As stated cc: R. J. Mattson, DSS 1 J. P. Knight, DSS J. Shapaker, DSS J. Kudrick, DSS ' G. Laimas, DSS ' C. Tinkler, DSS A. Wang, D0R U. Potapov, DSS S. S. Pawlicki, DSS J. Halapatz, DSS H. F. Conrad, DSS B. Turovlin, DSS , , e 9
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k /;l! > '. q '. ' l . ' AUG S 1978 ..; I MEMORANDUM FOR: W. R. Butler, Chief Containment Systems Branch h I Division of Systcas Safety l \ FROM: S. S. Pawlicki, Chief Materials Engineering Branch lTr. L .'. .
SUBJECT:
HYDROSEN GENERATION FROM ZINC CORROSION IN BWR
~
i CONTAINMENT POST-LOCA Y e I
' ' ~ '
; -.: = m REFERENCESr 1. Memorandum S. S. Pawlicki' to R;- Tedesco, Hydrogen
'" ' ~
Generation Rates Af ter LOCA, March S',1978
- 2. BNL Memorandum, D. vanRooyen to H. F. Conrad, H2
, Release from.Zn Corrosion, August 2, 1978
- 3. BNL-NUREG-24532, Daniel vanRoeyen, Hydrogen Release
'~
Rates from Corrosion of Zinc and Aluminum, May 1978, Brookhaven National Laboratory. - Since we pro',ided CSB with' the " interim working rurve" of Reference 1, "
.. t
- . Attachment .1, we have been attempting to clarify the situation as regards the use of this cu.rve in regard to BWRs. We have searched for other
, experimental. data and have re-examined our existing data base.
. vInen"<'In Reference 2, Attachment 2, MTEB consultant D. vanRooyen recomends .
the use of Figure 11, BtR.-NUREG-24532 (Reference 3,. Attachment 3) for
. .c s.~..u..m. 41 u i d s ..o.f ..pH o f 7. The curve of Figure..ll is the same.as cur recommended.
I " interim. working curve." . .. We agree with his recomendation becaus.e of the uncertainty surrounding 'the
~
case of BWR water containment sprays indicates a ' conservative approach. We agree with the assumption that the change of pH is the.most important effect on the ~corrosiori rate. The addition of boric acid and sodium hydroxide 'will only affect the zir)c corrosion rate to the extent that they change the pH of solution.
. -..u..-._. We. concur with his further recommendation of a " realistic" curve. (Curve A of Reference 2) for the calculati.on of hydrogen generation from a borated 1
. . water spray of a pH of 9.5. In this case, test data from two independent !
studies are in agreement. l t
. l. . - ; -
i . l . i .
~
~ . .
AUG '
- 4 AUG 0 1978 1N.' R. Butler e
....c.- -
As your know, our trip to GE-San Jose yielded no, new da ta. GE reiterated
=
their position that hydrogen genera tion frem zinc is inconsequential . though they did not offer any documentation of experimental data to substantia te their position. g As the next step in the resolution of a experimentally valid hydrogen generation rate curve, we are preparing a " Users Request" for RES as agreed in the July 27, 1978 meeting. ' s llg / S. S. Pawlicki, Chief
. Materials Engineering Branch Division of Systems Safety
, Office of Nuclear Reactor Regulation
Enclosure:
As s,tated , cc w/ encl: J. Kudrick, DSS f J. Shapaker, DSS C. Tinkler, DSS A. Wang, DOR
.- F. Almeter, DOR J. Halapatz, DSS J. 7wolinski, DSS .
W. Paulson, NRP J. Wing, DSE W. Johnston, RES M. Picklesimer, RES S. Pawlicki, DSS R. Gamble, DSS H. Conrad, DSS B. Turovlin, DSS cc w/o enc 1:
- R. Tedesco, DS'S J. Knight, DSS R. Mattson, DSS i
. ...;. z . .
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7
._ . _ . .._. NDi )PRlDUli FOR:
S. Pawlicki Chief, Hatcrials Engineering Crench, DSS
- -=- FR04: -.. W. Bu tl er , Chi ef , Con ta i nmen t Sys tm s B ra nc h , DSS ., _ .:
SUBJECT:
CSD INPUT FOR RES USERS RECUEST REG'JDIN3 POST-LOCA h. AC iM L~.1,5 .K. d - HYDRO 3DI GEliERATION RATES FOR:MATEF.1/J S :INSIDE m. . .. t. . . C0 ffAIM4EUT . -
~
- - - - =.
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- ' ' ~ _ . . . . _ .
"~'As (result of a r:ecting among representatives of CSB, NTED, AAS cnd .
. ,.. RES , . . on . J u l y 27, 1978, we agreed..to provide por.tions of the. subject
.RES users request. Specifically, the CSS ms to provide a discussion.
n- -
-2 -
of the problem status and the licensing impact associated with the - ;. w-:- : - eva'.uction of hydrogen generation frcci certain construction r.ateriais ;-s,
"~-
(aluainua and zinc) inside contaircent. Our input for the subject . c.e. RES users request is enclosed. Note th!t we have addressed hydrogen . generation due to corrosion of aluminua and zinc. During our meeting of July 27,1978,-the issue of c : . n. . . . . . . c. .
... : hydrogen . generation from the radiolytic deccenposition of organic .
.--n--'caterf ah was raised by the AAD If the AAC finds that hydrogen . .~
':<- .. :.u;.*
generated froa organic caterials is significa/it, we would reco::x nd , . - , zu "
~ its inclusion in the proposed RES program.
- - .ec.r m a
. gi.2,.,V . .
~.
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. -* - If he can be of further assistance please contact us. . . ~ c ..n ,a.-
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......a.......
y .:
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. :.y ..
. , . . ~ . e. , ... . ;. .
Walter R. Cutler, Chief ' Contairment Systans Branch
.. Division o f Sys tems Sa fe ty . . .. ..... .
_ . . . . . . _ 2.
Enclosure:
'6 . .G ',<< . . . ' :
. .. As Stated cc: R. Tedesco -
r -
J ,. . . . J. Shapaker -
. .-F.-i J. Kudrick DISTRIBUTION: .,u,.,,,,,
C. Tinkler Central Files ~ HRR Reading a. Contact : CSB Reading C. Tinkler. CS3 ".'-..'. 492-7711
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Enclosure 258 IflPJT FOR Ri.5 USERS REQUEST Status of Problem Following a loss of coolant ac:ident in a light water'> reactor (Lb'R) plant, hydrogen may accumulate inside the primary reactor containment VFL > ~* assa result of:
~
(1) a metal-water reaction involving :the.f.uel rod -- cladding; (2-) the radiolytic cecomposition of,-water in the reactor core
~r - ~ . . , .
..-.'End' containment sump; and (3) the corrosion of certain construction -
materials by the spray solutien. This discussion is limited to the
. - - - - - - . . . ~ - - . . . ~ ._ .. ,
' - post-LOCA hydrogen produced from certain construction materials inside
' containment, most notably aluminum and zinc (in the form. of galvanized steel and zinc rich primer paints).
.>.4,,2 :v....-..
... The' staff has noted .in its review of ' applicant analyses of hydrogen _
c:1.',J.,' .N)' - pfoduction and-accumulation as presented.in safety. analysis :repotts
^ -'
. ._ that' there' are very lar*ge (order of magnitude) dif ferences in the _ , , . .-
' ass 0mptions for corrosion rates for certain materials. Since the' rate- '
of hydrogen production and accumulation ,within the containment is the
- '- controlling factor governing the functional design of -the pl. ants' - -
. , .ccabustible gas control sys'tems, it is important.that corrosion rates of various materials be known with better pre ~ cision.
The potential for hydrogen gelieration from aluminum under post-LOCAr monditions has led applicants to limit the use of aluminum in Ph'R
. .. .. "J. . : : .
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..:con ta '- inmen t s . ..
- e. .. e -- On the other ha'nd',"2inc based primers an. d.. galvanized .. .
- r ..
steel are used extensively.
' We have~ noted, however, tha t one app'1 fian o
galPt has limited the mass of zinc inside containment because of it t over the potential for post-LOCA hydrogen generation. k . y"
. .. Applicant analyses of post-LOCA hydrogen production and accumulation in BWR. plants do,not consider the corrosion of aluminum cr'zine as sources j
d ., ,, .m; . m of hydrogen.
' ^ ~ :u m . '
- The. reason for this is that the pH'for th'e primary coolan 4
! . ,, and suppression pool water is essentially neutral.
' Hcaever, one applice h e
- " - ~
.3 ~ -. as r. cently suggested that aluminum.
. . . . and zinc corrosica will occur..even with neutral pH xater. .
The staff at 'this time does not have recccinended values for hydrogen, generation rates for aluminum or zinc materials in neutral pH steam-water environments. w..-_..w--=--..
~- . ......: .. __._-._.,,___ .. ..
=--,,.----... L i cen s i ng Impa c t .
,q._....
~~'--~-'.-".17"-- -
1, .
.......c..
- ..[To c; properly evaluate the functional design of a LIh. plant's co gas control ~ systen following a postulated LOCAT it 'i,s' es,s. 7 ;; .f; .
.:: T;
- tit; c~ic..-=v
s ' - ' ' - en tia l' ~tha tT-
< meaningful data be available regarding the gorrosion of raterials such
, , as aluminum and zinc.
- . .. . - .u Therefore, the proposed program will study in T -
depth the paramete,rs which influence the corros~ ion of materials le
..710 hydrogen generation.
If the hydrogen genera tion rates for aluminum
.and zinc are found to be significant, the hydrogen produ: tion and ' -- ---
( '-
. accumulation analyses for LWR plants and in particular the BhR plants must be appropriately revised ar.d the impact on performnce requirements
.-: for combustible gas control systems evaluated.
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c._ M. .ID. . RAND,UM FOR ; Jacs P. Knight, Assi'stant Director for Engir,ecringj. DSS
.t... ...._...._
. T. HR.U: . . Richard H. Vollrcer, Assistant Director for Site dalysi DSE
... t FRO:l: Cordon L. Chipean, Jr., Acting Chief, .iccident Analysis Branch, DSE
'~
- r, gggy
SUBJECT:
POST D3A liYDEDGEN GESERATION RATES '
' 'O
The ccmrandun, Tedesco to L'aight, dated 1/30/78 identified the necd
' [ [,l .C,.
if.or realistically conservative zinc corrosion rates for use by CSS ' - >
~~
in ~ don'fi'mctory analyses of cc,bustible gascproduction in postJ ' ' ' '2 -
"Wl'" " .acc.i den t en v i r :rcr.s n t s . The cce.orandua. Pawlicki to Tedesco, dated -
i .- 1/10/78 cccnit ted ;ED to initiate a RES program to deveisp-the necess'ary
. data should* existing experi.?. ental data be found inadequate.
s A RES program designc.d to develop hydrogen ceneration rate data was discussed io a aceting en July '27, 1975 attended by MED, CSS, PSB, AAB and RSR. Cased on this. meeting and cur evaluation of gas pro-
~ ~ duction in. post-accident environm.Ents,' we believe 'that existing -
_. cxperimental data are ir. adequate.
. :- The AAS ha.s review responsibility for organic e aterials in-contairnent '.c,,.c~.f', 7 u,under SRP, 6.1.2, " Organic ?:aterials". Included in its scope of. review is the asses ment of hydrogen and hydrocarbon ~ gas ge cration under DBA m a : - n m. _ . c rcon$11tions from themalc chemical and radiolytic'ef f ects on'orgahi'c'
g- ' ~ ~ ~ ' component's of protective. coating systems. , At present, useful data o~n e . , . / , . . r.
.. . e. .. . ,.
r ..
.:these .cf.fects is lac'< ing, Ce 72 quest that the proposed RES prograa' ~
.., include.. consideration of all claterials in' nuclear' protect 1Ve coating
.T.7Z' ..E. J' systems 'and should be directed sta include' the 'de'velop=ent'of' data or, hydrogen and hydrocaroon gas generation under synergistic chemical, themal and radiolytic DEA envircrsental conditicns.. 'n'e can provide as ist ance as necessary.id drafting a specific research proposa'l.
,..,s... .
M Gordon L. Chipman, Jr., Acting Chief
- , Accident Analysis Branch
', Division of Site Safety and Envircraental Analysis cc: See attached sheet t
or..e e n . . QS~' . AD: Ab5$ g
~~f
,..rihden/be RHV 11mer
.,. .i . . - . _ - -
o ,' Q ~, AUG S 'JT; S. 5. Paalicki ! ( ~ 2' - 2'2 s-
. - cc: J. E. Knight Distribut100 R. Tedesco R. Vollmer Lentral File W. Paulson mm 1.cading W. Buuce Ar. -e r11e .
b,. Johnson DH Reading ' J. Wing K. Cripe 9 4 E . .. . 4 a em O be p m .- e ' g 8
. e me 9e S
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',"" fsVG 1 h IM3 gg 2 f h d. '" g '"J-:*r !.h;N g5A,b.ig M"f.3 E t@sC h q.p,\. f W 4 MU40,RAtiDUM FOR: 5, '.ev ine , Di rec tor r .
s.N V .. 1.44 I 2"H ' Office of Nuclear Regulatory 8esearch' .
. C , h Mt > I
-99 4 l 1
FROM: H. R. Denton, Direc tor .r - , l Office of Nuclear Reactor Regulation
SUBJECT:
POST-LOCA HYDROGEli GEtiERATION RA1ES FOR MATERIALS INSIDE CONTAINMENT A. Backcround and S tatus of Problem s Following a loss of coolant accident.in a light water reactor (LWR)
- r- . - ' plant, hydrogen may accumulate inside the primary reactor containment 2
'as a result of: (1) metal-water reaction involving the fuel rod e w ter "' cTaddins,t :(2) tr e radiolytic decomposition of the water in the reacter
~
"'~ core and containment sump, andi(3) the corros ion o,f Certa in cons truc. tion -
~
materials by the spray solution. The metal-water reaction involving 1 the fuel rod clcdding and the radiolytic decomposition of the water in
~
'the reactor core and cmttainment sump is discussed in Regulatory
.- - Guide 1. 7, " Control of Combus tible Gas Concentra tions in . Containments o . . u o n -- t uFotlowing a Loss-of-Coolant Accident," >The acceptable-rates for- the -
"~ *t W 'gc~nerat' ton rof. hydrogen from the corrosion of cons truction*.ma teria } s in -
~
a
'*"~ " containment, particularly aluminum and zinc-(in the f.orm of galvanized 6," * " 'sitee'l'and metal-rich paints) ~is not adequa tely' defined in the Guide, t
4 The staff has noted in its review of hpplicant anal ses3 of hydrogen
-production and accumulation, as presented in safety analys.is reports -
(SAR), that there are very 1arge (order of magnitude) dif fbrences in the assumptions for corrosion rates for certain materials. Since the
?l e %g % e. = n9 a
.. . . . - ..:...~. , . . . w :. x -- .u .- . , v . .-
. . -.x..:,
l $. 6%:... eb $$$5?$$$,$$$W".kh?'5?D'$Yh??ib.OI?.5.$?.b???b.?$?*?iY . l
Y .
.t * ;
i tt.in the caratecoffhydrogen production and> accumulation within the containment: J t' t' ~'t G"il 10: ? is the controlling factor governing the ftnctional design of-the plantsf ':- C' -- ' combustible gas control systems, it is important- that corrosion and. " hydrogen generation rate.s of various ma.terials be known wi.,th better precision. 1" um m:'"' The tpotential for hydrogen ~ genera tion froa aluminum under pos t-LOCA ~ - ." .-
- . - conditions has led applicants to limit the use of aluminum.in.PWR _
-s' - - t con'ainments. However, zinc based paints and galvanized steel is used extensively. We have noted, however, that one applicant has limited the mass of zinc insis a containment because of its concern g over potential for post-LOCA hyd'rogen generation.
Applicant analyset of post-LOCA hydrogen production and accumulation
- - , - ,. in BWR-plants do not consider the corrosion of alum.inum or zinc as . . .. .
.nu . c:4.v t . sources of hydrogen. The reason ~,for this is .tha t the pH forc.thes .
. . :s t-
- o t . m .. primary coolant and suppression -pool water is essentially ncot.ra.1. .
imn j :en:rrHowever, one applicant has recently suggested that aluminum.and zinc- ./ -
, . corrosion will occur even with. neutral pH water.
-- - To properly evaluate the funcMonal design of a LWR plant's combustible
'"' ' ' ' gas' control system following a LOCA, it is essential tha t meaningful -
" ' data be available, regarding the corrosion of materials such as aluminum and zine and the degradation, with subsequent hydrogen evolution, of metal-based paints.
n.:; ;.4 ' r ^ . ", I .
3- - l
.v . "
The staff (MTEB) and their consultants have reviewed the availab}c experimental data 'and have developed conservative curves depicting - bydroge'n genera tion rates due to the corrosion of zinc (galvanized in steel)3 pos t-LOCA environments. These curves were recommen,ded for
. calculating hydrogen generation.
B. Informational Deficiencies
'""Tn'"'
The'present data base for establishing hydrogen generation rates is - - very limited. flost of the information reported in the literature is not ammenable to the evaluation of the experimental basis or procedures, i In addition, there is little infonnation reported of the results of
. ee - neerp tests at lower temperature ( $5-4462f) or with a range of pH's.
cInformation is lacking on the effects of additives, such as boric. acid and sodium hydroxide versus neutral unadjusted water, upon the corrosion rates of zinc. I 1 l
-l' --- In evaluating the literature data prior to developing the recommended -
1 hydrogen generation curve, a number of unanswered questions were - apparent about some of the parameters of the corrosion rate. The l
-"-following questions should be answered by the research program:
l
. .. .l . For: metal coatings, aluminum or zine (galvanizing), what is the effect on hydrogen generation of,
- a. variations in metal coating
- b. composition of metal coating -
- c. method of application
.:J, . . .
~
.3,q , .
1 e wo.trate d., alloying of metal coa ting wi th ' steel subs tra te . .s'tC;
;ses :e N m2.niIs oxygen depletion of the atmosphere a factor in hydrogen e a 'h j 7 evolution?
- 3. Are there two slopes (activation energies) in the zinc hydrogen generation curve? One slope for metal-steem reaction above i
- c. :r.;i boiling and petal-liquid reaction below boil.ing? .
~ '
/
- 4. If the pH is controlled to a fixed value will a change of ppm w.treem ee 1 h(x?) of an additive have an ef fect on the hydrogen . evolution. -' "' i'-
i .e. . . is boron concentra tion a fa'c tor? '
.,.. . .. 5_..Is. there an induction period for the s tart of hydrogen evolution ..
from paint oc metal coatings? Does the temperature have an - effect? Does preconditioning, i.e. , sta tic exposure to humid ..'
.. _=m. . containment a tmosphere, effect the induction period, if any? -.
< ~ ' ~ " - 6. Does aging effect the performance of the coatings? '" '- -
"' ;r ~7.t po variations in the metal pigments (si.ze, shape, quantity,;
. . m.o ne e-4.e..., composition) have an effect on -the degradation of the coatings? -
-.. .s ( . .. ..q.,.. yj.11 varia tions in paint vehicle or topcoa t -have an effect on " ---'~
the evolution of the'. hydrogen? Will inhibitors have an. ef fect? 7C. Status of Known Programs Directly~ Related to the Requested Research - There are no known experimental programs, being sponsored by- the s
- _: . . fluclear Regula tory Commission that is directly related to the requested research. Various other organizations have done experimental research
. directly related to.this problem. ilone .of these organiza tions now l
. . . * }, :.
.
- 1 ,
- .5. .c ~e:: - thavesan: ongoing program. The.f.ranklin Ins ti tu te Re:earch L.Ocr !:ories - S-
-i,ng..tn . :rc(F.IRL').has inves tiga ted this problem by measuring .the hydrogen in a
. ;1J- 7 closed vessel while spraying a controlled water solution onto .
galvanized steel grid. Oak Ridge flational Laborato-ies di,d a similar experiment but measured the hydrogen content in the vessel only at c.. u' . . the end of the experiment rather than a t intervals during the ' experiment as did FIRL. Westinghouse Electric and others did cor-ouo ur qu .ue ros,ionj studies on small galvanized samples but measured only weight . . . . l os s .: Except for the results rcported by FIRL it is.difficuit to . evaldate the validity of the-results or the technique.
]
D. Desired Completion Da te l The research program should be done in at least two phases, short ..
.- -" ~
-' term and long term. The short term program to be completed by. the .end of -the calendar year should focus uppn .six experimental runs to -
- '"" "* corroborate the accuracy of the recommended caltIclation ~curms at .
" a r '"
_ 'mathe vlower tempera tures . The' hydrogen evolution a t -the ' lower temper - - ' -
.l 1
atures (130 -200 F) is important because during post-LOCA the ' containment environment is at these temperatures for very long periods. , i
-- , The experimental runs should also compare the hydrogen evolution -
1 from galvanized steel when sprayed with pli controlled water when 1 boron is added versus pure water. . 4
.' %A-
<2 ,
% g ,
- 4* .
'S , n. . . . . . , - - . -
g l
, b, .w tha l y uIhe..'long term program t hould bh-designed to answer the questions >
. ..previously s ta ted. With the many . variables to be investigat d the ' ' ~ '
long tenn program will take at least two years. ' " { E. Magnitude of the Resear ch Program *
.a, .... .. .;I.h,e, p,rogram will require a reasonably large closed vessel into which - -
l
- ti . ,,, .several mid-size samples can be , exposed. Auxiliary equipment will '
i
.. require provisions for neating 'the spray solution and controlling i
, the chemical compositien of the. spray. In addition the a tmosphere i must be sampled, at intervals; for hydrogen. It is estimated the short term program would cost about 40K-50K. The long term program would cost 150K to 200K.
F. Licensing Impact
,, a .
Jhe . hydrogen genera tion ra tes a t various tempera tures reccmmdnded ' ' ' f
.o .... ira m gga,1cula tion of hydrogen accumula tion in contairment are~very ; '- +
. , , . . . . . . . . .'.. cons e rva ti v e .
, , The evaluation,of...the applicants' assumptions in'th6.
- SARs is difficult if the applicants' assumptions differ 'from the '
recomended values by orders of magnitude. This is so because of the
;. c. . .: . . .: limited fi,rm da,ta available to the.staf f. . If,the hydrogen generation - -
.,.. ..;ratqs.for aluminum, zinc and coa tings are found to be signi'ficant,
. . , . . . . , 3he.hyctrogen production ,and accumula tion analysis for LWR plants and -
BWR plants, in particular, must be appropriately revised and the , i
.. impact or performance requirements for combus tible gas contcol '
+
t e . l . . . e i C... .,TdJ - L a..
s e,w. -
~
. . sys tems re-evalua ted. There is some evidence t! it several plants will have to redesign when the present conservative values are used in the evaluation
\
H. R. Denton, Director Office of Nuclear Reactor Regulation cc: R. Boyd V. Stello R. Ma ttson F. Schroeder J. Knight D. Ross . Z. Rosztocry R. Tedesco W. Butler B. Grimes V. floonan S. Pawlicki L. Rubenstein H. Conrad R. Gamble A. Wing C. Tinkler F. Almeter B. Turovlin MA 23 SR 2 . 4
~
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Case Boards Black Fox 1&2. ..... . . . . . . .ASLB Cherokee 1-3 . . . . . . . . . . . .ASLB - ASLAB Diablo Canycr 152. . . . . . . . . .ASLB FNP. . . . . ... . . . . . . . . .ASLB - ASLAB 6PEdst? (cuw'ry, . , , . A7.S/B Hartsville . .ASLB - ASLAB Hope Creek 152 . . . . . . . . . . .ASLB - ASLAB Jamesport 1&2. ...... . . . . . .ASLB - ASLAB Marble Hill 1&2. . . . . . . . . '. . .ASLB - ASLAB McGuire 1&2. . . . . . . . . . . . . .ASLB Montague . . . . . . . . . . . . . . .ASLB North Anna 1 . . . . . . . . . . . . .ASLB - ASLAB Pebble Springs 1&2 . . . . . . . . . .ASLB Perkins 1-3. . . . . . . . . . . . . .ASLB Phipps Bend 1&2. . . . . . . . . . . .ASLB - ASLAB Pilgrim 2. . . . . . .}}