Text

Long-Term Test Program of Nuclear Steam Generator Tubing Samples from TMI-1, First Interim Rept
	ML20080A333
Person / Time
Site:	Three Mile Island
Issue date:	10/31/1983
From:	; WESTINGHOUSE ELECTRIC COMPANY, DIV OF CBS CORP.
To:	;
Shared Package
ML20080A318	List: ML20080A316; ML20080A333;
References
	PROC-831031, NUDOCS 8402030457
	Download: ML20080A333 (184)
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{{#Wiki_filter:--- Westinghouse Electric Corporation Water Reactor Divisions Steam Generator Prograns P.O. Box 855 Pittsburgh, PA 15230 LONG-TERM CORROSION TEST-PROGRAM of NUCLEAR STEAM GENERATOR TUBING SAMPLES from THREE MILE ISLAND UNIT 1 to GPU-NUCLEAR, Reading, PA I l FIRST INTERIM REPORT October 1983 8402030457 840131 PDR ADOCK 05000289 R PDR ( 0914c/0127c/010684:5 1

a-Table of Contents Section Title Pace

1.0 INTRODUCTION

10 1.1 The Present Program 10 1.2 Background Discussions 10 2.0 OBJECTIVES 13 13 2.1 Primary Objectives 2.2 Additional Objectives 13 3.0 PROGRAM

SUMMARY

/ PLAN 15 4.0 FACILITIES DESCRIPTION 17 17 4.1 Once-Through System 18 4.2 Recirculating Peroxide Loop 5.0 SPECIMENS AND ENVIRONMENTS 24 5.1 Materials 24 24 5.2 Sample Configurations 27 5.3 Test Solutions 45 6.0 OPERATING HISTORY 6.1 Test Parameter Precording and Control 45 6.2 Loop Cleaning and Preconditioning 46 47 6.3 Autoclave Loading 48 6.4 Long Term Corrosion Experiments 6.5 Autoclave Operational Variations 49 0914c/0127c/010684:52

Table of Contents (Cont) Section Title Pace 50 6.6 Chemistry Monitoring During the HFT, First and Second Operating Cycles of Lead Test 1 52 6.7 Chemistry Monitoring During the HFT, First and Second Operating Cycles of Lead' Test 2 53 6.8 Hydrogen Peroxide Experiment. 80 7.0 RESULT. 80 7.1 Visual Examination 80 7.2 Weight Changes 81 7.3 Metallographic Examination 81 7.4 Auger and X-ray Photoelectron Spectroscopy (XPS) Analyses for Sulfur Pickup by New Surfaces of OTSG Tubing. 83 ' 7. 5 Eddy Current Inspection' Results 115 8.0

SUMMARY

117 9.0 FUTURE WORK 118 10.0 APPENDICES 118 10.1 Procedure for Loop Operations During Lead f Test HFT Cycle. 120 l 10.2 Procedure for Loop Operations During the Lead l Test Operations Cycles. 124 10.3 Methods for Preparation of Stock and Makeup Tank Solutions 132 10.4 Procedures Used During Hydrogen Peroxide Test Oaerations. l 0914c/0127c/010684: 53

Table of Contents (Cont) Section Title Pace 142 10.5 Operating Conditions for Loop 1 and 2 Through Operations Cycle 2. 175 10.6 Auger and (-ray Photoelectron Spectroscopy (XPS) Studies of Sulfur Pick-up by Archive OTSG Surfaces. 181

11.0 REFERENCES

0914c/0127c/010684:54

LIST OF FIGURES Figure No. Figure Title Page 4-1

Autoclave and Refreshed Sample Stringer with 20 Axial Loading.

4-2 Refresned Autoclave System.used for Once-Through 21 Solution Flow Through the Sample Stringer. 4-3 H0 L p f r GPU-N OTSG Tube Corrosion Tests. 22 22 4-4 Hydrogen Peroxide Loop System Consisting of Two 23 Autoclaves Containing Specimens Assembled. for Series Flow. 5-1 Photographs of As-Received Material. 29 5-2 Lead Test Specimen Bellows Loading Assembly. 31 5-3 Repair Test Specimens Bellows Loading Assembly. 32 5-4 C-ring Specimen Configuration 33 34 i 5-5 Strain Gage Results 35 5-6 Zircaloy C-ring 36 5-7 Core Material Specimens 52 6-1 Typical Specimen Packages 58 6-2 Stylizeo HFT Curve. 59 6-3 Stylized Lead Test Cycle i 0914c/0127c/010684:5 5 l

0 LIST OF FIGURES Figure No. Figure Title Page 6-4 H0 Concentration Values 60 22 6-5 Estimated H 0 Consumption Rates 61 22 6-6 H0 Experiment pH Levels 62 22 85-96 7-1 thru Specimen Macrographs 7-12 7-13 Eddy Current Calibration Standard 400 Khz 97 Drilled Hole Signal. 7-14 thru Tube Sample Eddy Current Inspection Signals 98-108 7-24 10-1 Titration Curve 146 10-2 thru Monthly Autoclave Operating Conditions 147-160 10-15 10-16 Normalized Sulfur Peak-to-Peak Height 179 Versus Depth Below the Surface for Three Ion-Implanted Standards 10-17 Calibration Curve for Sulfur Analysis for 180 Inconel Alloy 600 by AES. .0914c/0127c/010684:S6

LIST OF TABLES . Table No. Table Title Pace 5-1 TMI-l Full Size Tube Identification 37 5-2 Inconel 600 C-ring Material Identification 38 40 5-3 Compositions of Alloys Used to Prepare Mini-U-bends 4 Alloy Supplier, Heat No., and Form 41 5-5 Alloy Heat Treatment and Mechanical Properties 42 43 5-6 Alloys and U-bend Coding. 44 5-7 Long Term Corrosion Test Specifications. 63 6-1 Autoclave Specimen Loading 65 6-2 Analytical Data for Autoclsv3 31 HFT Cycle [ 66 6-3 Analytical Data for Test 11st Operating Cycle 67 6-4 Analytical Data for Test 12nd Operating Cycle 68 6-5 Analytical Data for Test 2 HFT Cycle 69 6-6 Analytical Data for Test 21st i I Cycle l 0914c/0127c/010684:5 7

a LIST OF TABLES Table No. Table Title Page 6-7 Analytical Data for Test 2 2nd 70 Cycle 6-8 Analytical Chemistry Results for Loop 3 71 During Cleanup and Preconditioning 6-9 Analytical Chemistry Results for Loop 4 72 During Cleanup and Preconditioning 6-10 Apparatus Changes and Events: Peroxide 73 Cleaning Runs. 6-11 Average Daily Make-up Tank Peroxide Concentrations 74 an1 pH values. 76 6-12 Daily Peroxide Usage 77 6-13 Peroxide Loop Analytical Data 7-1 Results of Visual Examination of C-rings 109 Test No. 1 7-2 Results of Visual Exanination of C-rings 110 Test No. 2 7-3 Results of Visual Examination of Specimens 111 After Peroxide Experiment. 112 7-4 Weight changes of Exposed C-rings. 113 7-5 Summary of Tube Eddy Current Inspections 0914c/0127c/010684:58

~ LIST 0F TABLES Table No. Table Title Pace 161-173 10-1 thru Operating Parameters for Test Loop 1 and 2. 10-13 10-14 Fraction of Sulfur Atoms Stopped Within a 174 10 NM Slice of Material at Various Depths Below the Surf ace 0914c/0127c/010684:59

1.0 INTRODUCTION

1.1 The Present Program The GPU Nuclear Corporation (GPU-N) is engageo in a repair program for the nuclear steam generators at its Three Mile Island Unit 1 (TMI-1) generating plant. A part of that program incluoes the establishment of the long-term corrosion behavior of steam generator tube samples, from the TMI-l steam generators, under a programed exposure of representative reactor coolant chemistry and temperature variations. This long term corrosion test (LTCT) program is being conducted for GPU-N by the Westinghouse Electric Corporation through the Westinghouse Steam Generator Programs Activity which tponsors the testing operations at the Westinghouse Corporate R ano O Center. The purpose of this program, as stated in the GPU-N Short Form Specification SP1101-22-008, Revision 2, is to demonstrate that the processes of kinetic ~ expansion and sulfur oxidation during peroxide cleaning and plant operation will not result in propogation of existing IGSCC or initiation of new IGSCC. The GPU-N Specification SP1101-22-008 was transmitted to Westinghouse unoer a cover letter of July 13, 1982, by F. 5. Giacobbe, Manager, Materials Engineering and Failure Analysis, GPU-N. That cover letter requested that the contractor's program incluoe two interim reports and a final report. The present report is the first of the two interim reports which are structureo into the Westinghouse agreements with GPU. This report covers all program activities from inception into May 1983, as delineated in Section 3.0, Program Summary. l 1.2 Background Discussion l The 2 nuclear steam generators of the TMI-1 f acility are the once-through steam generator (OTSG) design furnished by the Babcock and Wilcox Company. As part of that supplier's manuf a, turing sequence, the entire finishec OTSG is given a stress relie. heat treatment, the time and temperature cycle of which f creates a grain boundary chromium depleted (GBCD) microstructure in the nickel-chromium-iron alloy (Inconel Alloy 600) which is the tubing material of 0914c/0127c/010583:5 10

4 the generator. Extensive testing of this microstructure in aqueous environments which can cause elevated temperature paustic stress corrosion cracking (SCC) has demonstrated that the GBCD condition is as least as resistant as, if not more resistant than, the " mill annealed" condition to the typically intergranular caustic SCC form of degradation (References 1-6). Other tests have demonstrated that the GBCD microstructure possesses high 4 resistance to the "Coriou" type of phenomenon, an intergranular cracking process requiring'high stress, or high strain, or a high strain gradient, coupled with a typically prolonged exposure at elevated temperatures (> 600*F) to high-purity water (Reference 7). The only extensively investigated conditions which demonstrate that the GBCD condition is selectively susceptible to intergranular forms of degradation are at low temperatures (at 'or near room temperature, for example) in aqueous species which are not representative of normal nuclear steam generator environments. Apart from boiling nitric acid solutions (the "Huey" and " modified Huey" tests), there exist certain sulfur-containing oxyanions which can be deleterious in low temperature aqueous solutions to iron-chromium-nickel alloys in general, if these alloys possess the GBCD structure. - In these potentially aggressive oxyanions, the oxidation state of sulfur is less than 6* (or VI), species such as tetrathionate (S 0f), thiosulf ate 4 2 r "polythionic acid" (H S 0 ) having received attention (S 023), 2xy in recent years (References 8 and 9). This form of intergranular attack (which is selective to and requires the GBCD structure) has not been identified for the very common sulf ate ion, SOf, however. Definitive observations of the relatively high resistance of the GBCD structure, comparea to the " mill annealea" condition, to intergranular attack in acid sulf ate solutions have recently been published under EPRI sponsorship. These tests, which used 80,000 ppm Na 50 at an initial room temperature pH of 3 2 4 (obtained with H 50 ), showed that the GBCD condition was at least as 2 4 resistant as the " mill annealed" condition of the same heat, in 5000 hour exposures at 630*F (Reference 10). The low-temperature reduced sulfur oxyanion attack of GBCD Inconel 600 remains one of the few cases to which the GBCD condition can be demonstrated to be selectively sensitive. A detailed, f ailure analysis of TMI-1 GTSG tubing 0914c/0127c/010583:5 11

which exhibited primary-sid:-initiated intergranular attack and intergranular cracking has led GPU-N to conclude that low-temperature sulfur-species attack was responsible (Reference 11). This conclusion is also supported by additional f ailure analysfs reports (Raferences 12,13,14,15). Both References 11 and 12 provide possible sources of an ingress of sulfur species into the reactor coolant system during the prolonged layup of TMI-1, and both documents address mechanistically plausible chemical scenarios for the production of an aggressive aqueous low-temperature sulfur-bearing species. It is the TMI-l OTSG tubing which has had the history outlinea above and detailed in Reference 11 which is the subject of the current LTCT program. [ 0914c/0127c/010583:5 12

2.0 OBJECTIVES ~ 2.1 ' Primary Objectives The two initial objectives of the LTCT program are responsive to the GPU-N Specification SP1101-08-022 and were (1) the determination of the long-term corrosion and stress corrosion performance of service-exposed TMI-1 OTSG tubing material from the generators and (2) the identification of any Tne potential in-plant corrosion issues and the conditions for such issues. tests are to be performed using reactor coolant chemistry composition representing the upper bound of specified limits for contaminants. GPU-N Specification SP-1101-08-022 provides the chemistry limits and time ano temperature cycles for the tests. f To meet program objectives four types of specimens were utilized in four separate test vessels. Specimens consisted of full section, axially loaoed " Lead Test" and. " Repair Test" specimens, C-ring, and U-bend specimens. " Lead Test" and " Repair Test" specimens were prepared from service exposed Unit 1 steam generator tubing which had been removed from the upper tubesheet i l region. " Lead Test" specimens consisted of open lengths of tubing white " Repair Tests" specimens consisted of tube /tubesheet mockups prepareo by explosively expanding tube sections into an outer collar following a procedure which duplicates repairs perfonned on Unit 1.- C-rings, which were loaded to place I.D. surf aces in tension, were prepared from both service exposed and archive (non-service exposed) tubing. U-bends were prepared from other The materials used in the f abrication of Unit 1 core structural components. test operational sequence and chenical compositions of the solutions usec for each test simulated conditions encountered in plant operations and were, with minor variations, identical in all tests. The only difference between test environments was that one contained thiosulf ate and the remaining three contained sulf ate additions. 2.2 Additiona.1 Objectives 1 t Additional secondary objectives, not originally incluceo in GPU-N SP1101-08-022 have been ioentified and met as the LTCT program and on-site f 0914c/0127c/010683:5 13

operations at TMI-1 have prcceeded. The chief of these secondary objectives became the development of equipment for and the achievement of the hydrogen peroxide cleanup of selected OTSG samples for the subsequent inclusion of such cleaned samples into the LTCT. Another secondary objective which is an outgrowth of the preceding cleanup activity became and is the verification of the performance of stressed alloys representative of in-core materials when such materials are (1) pre-exposed to a " conditioning" of reactor coolant (ctntaining approximately 100 ppb of 50 ), (2) exposed to the hydrogen peroxide cleanup cycle, and (3) 4 subsequently exposed for prolonged perioos to the " worst case", but normal, reactor coolant chemistry programmed by (and identical to) the main LTCT program. A third secondary objective was to determine, using Auger electron 2 spectroscopy ( AES), how much sulfur (in ug/cm ) is present within the first 100 nm of the inside (ID) surf aces of GPU-N steam generator tubes that were conditioned to simulated reactor coolant chemistry at elevated temperatures, using standards prepared by ion implantation to calibrate the AES technique, and X-ray photoelectron spectroscopy (XPS) to identify the sulfur compound (s) present. i i l l l 0914c/0127c/010683:5 14

3.0 PROGRAM SUtHARY/ PLAN The program. plan has undergone several' iterations, modifications and alterations of scope since its inception under the original GPU-N Specification SP1101-22-008. As presently structured, the program consists of three principal elements. 1. Two extended duration " Lead Tests" using " Lead Test Samples", as oefineo in GPU-N SP1101-22-008. These tests started in October, 1982, and are continuing. 2. A hydrogen peroxide cleanup run to simulate the treatment of the TMI-1 primary system. This test applied to two " Repair Test Samples" and one " Lead Test Sample", as defined in GPU-N SP1101-22-008,.and " Core Material Samples", as described in this report. It was completed in Maren 1983. Two add'.tional " Lead Test Type" extended-duration corrosion tests using 3. the " Repair, Lead, and Core Material Samples" of Item 2, preceding. These tests started in May 1983 and are continuing using the same,"Leaa Test" operational sequence as the Item 1 tests. The present report encompasses Item 1 through May,1983, and the entirety of Item 2. Item 1 remains in progress and Item 3, as noted, is underway. Item 1, the two long-term " Lead Tests", follows essentially the plan originally given in GPU-N SP1101-22-008 and has consisted of two tests which differ only in the make-up sulfur-dosing spe:1es to the otherwise normal reactor coolant simulated chemistry (Li, B, H, etc.). Test 1 uses 2 thiosulf ate and Test 2 uses sulf ate. Both sulfur anions are at trace levels (100 ppb, nominally). Both tests follow the same operational sequenccs which are: (1) Hot Functional Test (HFT) Stage (2) Cycle '. (3) Cyc1e 2 (4) Cycle 3 (5) Cycles 4-6. . 0914c/012 7c/010583:5 15 - ~ ~

1 (The cycles ciffer in the amount of B, as H 80, and Li, as LiOH, which 3 3 are present in the test' solutions and which are varied to simulate plant I ~ operations.) ( This report covers the 2 leac tests,' Item 1, from inception throu5h the HFT and further through Cycles 1 and 2. As noted, the report also covers the hydrogen peroxide cleanup testing, Item 2, and, as such, thereby delineates the test matrix (of samples) which constitutes item 3, the in-progress leaa test type program with the peroxide-cleaneo samples. ~ 0914c/0127c/010583:5 '16

4.0 FACILITIES DESCRIPTION 4.1 Once-through System The once-through system snown schematically in Figure 4-1 anc in the photograph of Figure 4-2 is the basic apparatus used for all long term corrosion testing of GPU-N OTSG Inconel tubing. The basic element of this apparatus is "a standard Autoclave Engineers 2-liter, bolted closure autoclave, which contains the. test specimens. These specimens, which are samples of axielly loaded GPU-N OTSG Inconel 600 tubing, and cans of C-ring or U-bend samples (depending on the individual test specifications), are plumbed for a serles flow of solution upward through the samples. Entry ports (feed-throughs) in the autoclave head provide the means of nitrogen gas pressurization of the bellows of the specimen loading fixture as well as entry and egress of the tubing which carries the test solution to and from the specimens. The first item in succession of the flow-through apparatus is a stainless steel makeup tank (MUT) with a nominal 701 capacity, which is filled with The MUT is equipped with a sight tube' to monitor 50 1 of the test solution. the liquid level of the test solutions, and ports to provide means of solution i exit, sparging, and pressurizing (gas overpressure). The second item in series, following the MUT is a Whitey Model LP10 feed pump which is adjusted to maintain a 100 ml/h (ideal) flow of the test solution through the system. The test solution flows through. check valve, into the autoclave, internally through the specimens, and exits the autoclave through a cooler composed of coiled stainless steel tubing. The cooler effluent discharges through a Controhnatic back pressure (BP) regulator, which provides the method of l regulating the solution pressure. Located down-stream from the BP regulator is a tap for effluent sampling and, piped in parallel, a flow meter (F/M) to measure system flow rate. Finally, the effluent is collected, monitored ano disposed of in accordance to Nuclear Regulatory Comission requirements. Ports on the autoclave body are used for filling, evacuation, sparging and for the attachment of the rupture disk (R/D) and BP regulator necessary for controlling'the autoclave pressure. Both the autoclave rupture disk and the 0914c/0127c/010583:5 17

BP regulatcr are ? umbed to the radiation monitorcd collection drum for safety l h in event of an overpressure release. The autoclave is heated by means of external clamp on resistance heaters. Nor&al saf ety and control equipment are used with each autoclave system. This basic system has been used to conduct both the HFT and Lead Test Operations Cycles 1 and 2 (CFDA-82-353 and CFDA-82-370 respectively) for Lead Tests 1 and 2. The detailed operating procedures fer HFT and operations cycles are presented in Appendix 10.1 and 10.2, respectively. 4.2 Recirculating Peroxide Loop It is planned to expose the primary system of TMI-l to a hydrogen peroxioe solution to ensure that any residual sulfur ' species will be oxidized to the sulf ate form prior to system heat up. GPU-N elected to have the test speciraens for Tests 3 and 4 of the existing program also exposed to this peroxide clean up operation. In order to accomplish this, the once-through systems of Tests 3 and 4 were modified to produce a series recirculatir.g system. Additional changes to the loop system during the peroxide cleaning cycle were made to improve operating efficiency or to meet contingencies. The peroxide (H 0 ) loop cleaning 22 system, in its final form, is delineated in Figure 4-3, and shown photographically in Figure 4-4 l In essence, the H 0 1 op c nsisted of two once-through systems in a 22 series loop feo.by a single make-up tank. As previously describec for the cleaning solution tnrough the once-through system, the flow of the H 022 GPU test specimens within the autoclaves was in a series configuration. The circuit flow from the MUT, through the autoclave and back to the MUT is l straight-forward. The test solution is pumped from the MUT by a circulation pump at the rate of -7 1/h. A rupture disk, plumbeo to return the test solution to the MUT in the event of over pressurization of the system is located downstream from the pump. It is followed by a stainless steel surge i - 0914c/0127c/010583:5 18

bottle half filled with inert gas, the function of which is to dampen pressure fluctuations resulting from pump operations. The test solution, which is pre-heated by flowing through a regenerative heat exchanger and heating tape covered tubing prior to entering the first autoclave, flows serially through the GPU-N specimens and exits the autoclave. The solution flow through the second autoclave and GPU-N specimens is similar to that of the first autoclave. Af ter leaving the second autoclave, the hot test solution again enters the regenerative heat exchanger, with the purpose of heating the solution about to enter the first autoclave. Following the regenerative heat exchanger in the loop in the order stated are a cooler, a BP regulator to~ control the test solution pressure, a flow meter, a 4-way valve,'a chemical addition system, and the MUT. The normal solution flow direction is upwaro through the stainless steel chemical addition pressure vessel to assure i complete addition of the chemicals. It is appropriate to note the valving arrangements at the autoclaves which permitted preconditioning of the loop tubing with the autoclaves and samples isolated. Also note-worthy is the tubing from Autoclave 4 to the MUT return line, necessitated by the leakage of a Repair Test sample tube weld. This circuit returned to the MUT the very small volume of solution oassing through the weld defect and,.thereby, maintained the AP across the tute constant. l One of the first revisions to the apparatus was the addition of an Jutomatic chemical injector which allowed continuous addition of hydrogen peroxide l I (H 0 ) to the loop and eliminated the need for discrete hourly manual 22 H0 adoitions. It was also necessary to add a recirculation pump to 22 assure rapid mixing of all chemical additions to the system. Other valving and port arrangements in the chemical addition and loop system permitted pressurization, evacuation, and chemical pressure vessel orainage when necessary. The final system was a product of continuous refinement and improvement throughout the 500 hour peroxide cleaning (exposure) operation. l l l 0914c/0127c/010583:5 19

owg.93'*5A85 P Bellows j, Manifold mmh ir N N Manifold Regulator l 2 P Sparge \\. System 'l MUT -100 cc/hr 50 2 ,e P ^ CV \\ Autoclave Pump ][ a ,1 y v ~ ////////////f/// ~% 4 N f$. u vg a . 'Q N V=y ! \\ Air v N A Sample y V V \\ Coolers ( \\ \\ y Evacuate \\ Back ( Pressure Fill

r Regulators s

N Bellows-l.oading Rigs p

\\

Y" TMITubes Effluent V \\s Sample s \\ . _,L. " ' s C-Rings pfy y

[

.Can r'

ECT Caps

{ N Sparge 2 V CV Monitor Drain Figure 4-1 Autoclave and Refreshed Sample Stringer with Axial Loading 0914c/0127c/100583 :5 20

5828 4 I J ]f" g i l' I j y o t . j. A ?. t -.,x k f j. l r-J

4 f

s I ,,, A it. .. '5' ' '~

4. >

L. Figure 4.2. Refreshed Autoctave System Used for Once-Through Solution Flow Through the Sample Stringer i - - - - - - - -. ~..,,. 93

..,4..i., udddb' , Pressure Vessel Drain out Out 2 X , Bypass Bypass f, Tube Weld Repair fest Vacuum M o it d lk Overflow Chemical in in Leakage 4, -n o 14'Jaton TC o TC o d Pressure + Vessfl 4-f- jg3n h I Tubing CD eralCal -M-ok ~i e T""h ! 'l o g gg, Addition g y .( m ~ 4-Way Valve I X Mut -- d Yb FWay Pressure X Sample Valve / Auto

Auto-Clave Clave K]

y 1 2 cy gg. Automatic Cnemscal e Heating Tape N up g , Addition Regenerative Tant { Surge Bottle IMUT ) 2 Ingector Heat Dchanger t' "O2 l.-.N 0P gju 2 I R'5V0 0 2. 7 GPN f,! h it S* a + . O as..a. Heating 130e Circulation Pump Back Pressure , Regulator Cooler Pumo p 7 Liters /hr system l Figure 4-3 H0 L op f r GPU-N OTSG Tube Corrosion Tests 22 0914c /0127c/100583 :5 22

1 R a f 's r / , F95 .J* \\,* p j. A h .. ~.. i i Figure 4.4. Hydrogen Peroxide Loop System Consisting of Two Autoclaves Containing Specimens Assembled for Suies Flow

5.0 SPECIMENS AND ENVIRONMENTS 5.1 Materials Test materials included Inconel 600 steam generator tubing and various reactor core materials. The steam generator tubing was supplied by GPU-N either as sections removed from THI-l or as archive OTSG tubing. Tubes from TMI-1 were supplied both with and without eddy current detected defects. The~ defects were ID-initiated, circumferential cracks, some of which were through-wall. Tubes for full size specimen testing were received with end pieces welded on. The archive tubing previously had been mill annealed plus stress relieved at ll50*F for 18 hrs. Photographs of the as-received tubes are shown in Figure 5-1. The identifications of the full size tubes are given in Table 5-1. Table 5-2 presents the identification of material used to make C-rings. The compositions of the reactor core materials used to prepare mini-U-benas are given in Table 5-3. The only material that could not be traced to a heat number and composition was wire which was labeled 308L. An analysis made on the scanning electron microscope with the energy dispersive X-ray spectrometer (EDS) was consistent with the wire being 308L. In Table 5-4 are given the alloy supplier, heat number or heat treatment code, and alloy form. The heat treatments used and the mechanical properties are tabulated in Table 5-5 ano the coding of the specimens in Table 5-6. All heat treatments by Westinghouse were in dry hydrogen. 5.2 Sample Configurations Specimens were configured as stressed, full size tubes, C-rings and U-bends. The full size tubes were supplied by GPU-N in either a "leao" or " repair" test configuration. 5.2.1 Full Size Tubes In the present LTCT, the " Lead" specimens correspond to the free standing tubes in the steam generator while the repair tests 0914c/0127c/010583:5 24

All simulate explosively expanded tubing within and just below the tubesheet. of the specimens were lead type except B94-27 (1/2 to 6-1/2). \\ Both types of specimens were tested 'under a 500 pound Had except during temperature cooldowns to ambient when the load was increased to 1100 lbs. These loads are representative of those which woulo exist on OTSG tubes during operation and normal coolaowns, respectively. Loads were obtained with a bellows actuated r'ig which allowed remote adjustment at any time. Photographs of the bellows assemblies for each specimen type are shown in Figures 5-2 and 5-3. By pressurizing the bellows, an axial tensile load can be placed on the tube. Each bellows assembly was calibrated prior to use by pressurizing to 3000 psi and measuring the resulting specimen deflection. Specimen load was then be calculated from the elastic aodulus and dimensions of the tube. 5.2.2 C-Rings Inconel C-rings were made from 3/4" lengths of tubing per the schedule shown in Table 5-2. After transversely cutting, each specimen was drilled to take a loading stud and then slotted. The loading method is illustrated in Figure 5-4. An Inconel 600 stud protruded from a hole in the tube at 90* to the desired stress location. The stud was held in place with a nut inside the tube and a locating depression diametrically opposite the stud hole. The C-ring was loaded by turning the stud while holding the nut stationary. Af ter loading the C-ring, a second Inconel 600 nut was used to lock the stud into place. Three archive and four service tube C-ring specimens were strain gaged to determine the relationship between specimen strain and opening displacement. Initially, a biaxial gage was applied to an archive spacimen with the following results:

0914c/0127c/_010583: 5 25

Deflection

circumferential Saxial (mils)

(v strain) (u strain) 0 0 0 286 8 3.3 573 10 1146 8 10.0 1718 4 2291 6 16.6 2864 4 t ./ This test indicated that the axial strain component was insignificant.- Only uniaxial gages in the circumferential direction were applied to the remainin'g specimens. An LVOT-based diameter measuring device was developeo and calibrated for determining specimen displacement. Using this device the strain vs. displacement curves shown in Figure 5-5 were determined. Displacement was limited to 7 mi'1s to avoid gross plastic deformation of the specimens. Subsequent tests verified that the strain vs. displacement relationship remained linear to at least twice this displacement value. Baseo on the minimal scatter shown in the strain gage data, all specimen's were This value loaded to a displacement of 13.7 mils prior to autoclave exposure. was extrapolated from Fig'ure 5-5 to meet the request of GPU-N to strain the-C-rings to 0.25 percent (2500 u strain). All C-rings were weighed to the nearest 10 ug and macrophotographs of the stressed ID area were taken. The test configuration for the OD loaded Zircaloy 4 C-ring is shown in Figure 5-6. The specimen deflection used was 0.08 inches which is about 25 percent above the yield strain of the material. Type 304 stainless steel bolts and nuts were used to load the Zircaloy 4 C-rings. 5.2.3 U-Bend Specimens Varicus reactor core materials were included in the experiment as miniature U-bend specimens. 0914c/0127c/010583:5 26

_--____--_____--_________________________________________g

The blanks for mini-U-bends were approximately 1.5" x 0.25" x 0.030". For specimens with welds, the filler metal was deposited by the TIG process at a A location corresponding to the eventual apex and element of the U-bend. U-bend was made by bending the blank around a 1/8-in. diameter mandrel and bolting the legs parallel with an austenitic stainless steel nut and bolt. Figure 5-7 is a photograph of all of the U-bend specimens. 5.3 Test Solutions 5.3.1 Lead Test Solutions The preparation of the Lead Test solutions A followed a systemized procedure which is briefly summarized here. comprehensive description of the Lead Test Solution preparation is given in the Appendix 10-3. 4 Stock solutions were prepared from the reagent grade salts of lithium hydroxide monohydrate (LiOH.H O), sodium fluoride (NaF), sodium chloride 2

5H 0) and sodium (Nacl) sodium thiosulf ate pentahydrate (Na 3 0223 2
10H O).

I sulf ate decahydrate (Na 504 2 2 The nominal concentrations of the stock solutions were 5000 ppm Li, 1000 ppm F,1000 ppm Cl,1000 ppm S 0"3, and 1000 ppm 50 2 4 In preparing an individual Lead Test solution, a weighed amount of United States Bor'ax and Chemical Company Special Quality boric acic was dissolved in deionized water in a polyethylene holding tank. Aliquot volumes of the Li, n the test solution) stock solutions were 4 (or S 0, cepending and 50 23 added and the solution in the holding tank was deaerated by sparging with Prior to transfer of the test solution from the holding tank to the nitrogen. MUT, and just prior to the test startup, a weighed amount of 65 percent aqueous solution of hydrazine (N H ) and an aliquot volumes of F and 24 Cl were added to an in-line addition vessel. During the transfer process, these species are mixed with solution from the holding tank and flushed into the MUT. This procecure was used to minimize the loss of hydrazine and to e avoid adsorption of F and Cl on the walls of the polyethylene holding tank. l l 0914c/0127c/010583:5 27

The nominal chemical compositions for the individual Lead Test solutions are given in Table 5-7. The sulfur species for " Solution 1" (GPU-N designation) is exclusively thiosulf ate as shown in Table 5-7; for " Solution 2" it is exclusively sulf ate. 5.3.2 Hydrogen Peroxide (H 0 ) S lutions The 500 hour pre-operational 22 exposure of the GPU-N specimens to hydrogen peroxide solution was performed in a recirculating loop system according to the detailed operating procedure delineated in Appendix 10-4. The initial composition of the 50 1 of solution in the MUT consisted of 2350 + 50 ppm boron (as H 80 ), 1.8 to 2.2 ppm lithium (as LiOH) and 0.100 3 3 + 0.05 ppm sulf ate (as Na250 ). The lithium and sulf ate (50 ) were 4 4 added as aliquots of the stock solutions described in Section 5.3.1. The pH of this solution was adjusted to 8.0 - 8.2 with concentrated (28 - 30 percent NH ) amm nium hydroxide (NH 0H). 3 4 Hydrogen peroxide (H 0 ) initially was added manually to the loop in 22 hourly increments. Subsequently an automatic, chemical addition system was stock solution. The used to make periodic additions of a 50,000 ppm H 022 peroxide stock solution was prepared by weighing 166.7 g of Perone *30 EG by weight) into a 1 liter volumetric hydrogen peroxide (30 percent H 022 flask and diluting to volume with water. All of the water used for solution preparation and dilution was high purity deaerated deionized water, with a conductivity of - 0.1 mho. Other procedures required for test operation during the peroxioe exposure are also found in Appendix 10-4.

E. I. DuPont de Nemours, Inc., Industrial Chemical Division, Wilmington, Del.

0914c/0127c/010583:5 28

5828-6 2,. .= - 2 t', c :t, - 3 2." - c '/2. ~ _3 w ~ ~.. ?_'u-4a 2 3 ' ', e - 2,' t. 5 A ;2. - c. 2 3 e '. - 9 2. ~. e o 't. 2 a'- A-EE 7 , - M. A e c-E o> g .o... -. -, r..- .s v. 1s-L.?: >; A .3 - 5 2 c n -2c. A - i s - c.s Tc zol 3*,u' P. - : - 2 2. e 5:.p.- o. c-u.-2z R 59 - c,s ' ~ Figure 5.1. Photographs of As-Received Material

5828 7 4 -W -N l w -w 6-h ame====ememme 84 M -. - A24-94 36-42 C B94-27 4-1/2-10-1/2 l-Figure 5.1. Photographs of As-Received Material (Continued)

_m. -m__m--_m.-. 9 4 g 5838-C i l b I .E 3 3 l ( f S e g g i .5 w i H a e i 1

5828-9 h, t i ~ 7; a [- - !: t { } 1 e. 7 5 .g t. [ -Q. 1 1 g i. i i[ }. E E (. c

l 6 32 STUD "C" RING SPECIMEN Q 6 32 /,~ i5 / --- T T 7 7 ---- 8 8 I' 8 / NUTS l I i i ii i ;i t 600 f 4 i i 8 30o Q i i i i _ _ _ _ _ t___; _ _ _ _ 90 +.375 -* = .75 Figure 5-4 C-ring Specimen Configuration 0914c /0127c/100583 :5 33

o TMl C RINGS 1500 A = 1E7 B = 1E8 1400 C = 1 A6 D = 104 1300 f[ E = 286 f 1200 ,/! 1100 0 1000 qlE e = G 900 E m h E 800 f _i s 3 700 z. 4 C 600 500 400 300 A 200 l 100 05 0 1 2 3 4 5 6 7 8 9 10 DISPLACEMENT (MILS) Figure 5-5 Strain Gage Results 0914c /0127c/100583:5 34

= .376 ---* +--- 3 /4" * +-0.331 --*' +.022 ' 4L,'2 .2 m i q.

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[r - *g--)- C /:\\ , _.p u p NO. 4 40 TYPICAL TYPICAL 60 IDENTIFICATION NUMBER l l l Figure 5-6 l Zircaloy C-ring 0914c /0127c/100583 :5 35

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Table 5-1 TMI-1 FULL SIZE TU8E IDE'dIFICATION Defect Location (1) II) -Heat No. -Tube Section A24-94 19-5/16" 7/16" M2409 None A13-63 11" 9/16" M2408 16" B16-22 52" - 59" M2800 None A88-7 2" 3/4" M2560 6" A16-69 6-1/2" to 12-1/4" M23.45 9" A24-94 36" - 42" M2409 None 894-27 4-1/2" 1/2" M2869 None (1) Dimensions from original top of tube in the OTSG. f I \\ l i l l l ( l f 0914c/0127c/010583:5 37

Table 5-2 INCONEL 600 C-RING MATERIAL IDENTIFICATION Slot (2) C-ring Location (l) Ancle Heat Number Tube 1A1 A 88 7 9-3/4" 1/4" 180* M2560 1A2 A 88-7 9-3/4" 1/4" 270* M2560 1A3 A 88-7 9-3/4" 1/4" 0* M2560 1A4 B111-62 237-5/8" -240-5/8" 90* M2560 1A5 B111-62 237-5/8" -240-5/8" 180* M2560 1A6 B111-62 237-5/8" ~240-5/8" 90* M2560 1B1 A 24-94 25-7/16"- 30-13/16" 180* M2409 182 A 24-94 25-7/16"- 30-13/16" 270* M2409 183 A 24-94 25-7/16"- 30-13/16" 0* M2409 184 A 24-94 25-7/16"- 30-13/16" 90* M2409 185 A 24-94 25-7/16"- 30-13/16" 180* M2409 101 B 94-27 18-1/2" 1/4" 180* M2869 2A1 A 13-63 20-9/16"- 23-9/16" 180* M2408 2A2 A 13-63 20-9/16"- 23-9/16" 270* M2408 2A4 A 13-63 38-1/8" 1/8" 0* ti2408 2A5 A 13-63 38-1/8" 1/8" 90* M24u8 2B1 B 16-22 59" - 64" 180* M2800 2B2 B 16-22 59" - 64" 270* .M2800 2B3 8 16-22 59" - 64" 0* M2800 2B4 B 16-22 59" - 64" 90* M2800 2B5 B 16-22 59" - 64" 180* M2800 286 B 16-22 59" - 64" 0* M2800 105 8 34-19 10-1/2" 1/2" 180* M2869 I 106 B 34-19 10-1/2" 1/2" 270* M2869 107 8 34-19 10-1/2" 1/2" 0* M2869 108 8 34-19 10-1/2" 1/2" 180* M2869 (1) Dimensions from original top of tube in the OTSG. (2) Location of C-ring cutout, per GPU-N reference angles. Looking down tube, the angle. increases clockwise with 0* at 6 o' clock, 90* at 9 o' clock, 180* at 12 o' clock, etc. The slot (cutout) occurs 180* from the resultant maximum stress on the C-ring. 091

Table 5-2 (Continued) slot (2) C-ring Location (1) Angle Heat Number Tube 201 A 16-69 2" 6-1/2" 180* M2345 6-1/2" 270* M2345 202 A 16-69 2" 6-1/2" 0* M2345 203 A 16-69 2" M2320 1El Archive Material 1E2 Archive Material M2320 M2320 1E3 Archive Material M2320 1E4 Archive Material M2320 1ES Archive Material M2320 1E6 Archive Materi'al M2320 1E7 Archive Material PIA 1(3) A62-8 5" - 11" 0* M2560 P1A2 A62-8 5" - 11" 90* M2560 PlA3 A62-8 5" - 11" 180* M2560 P1A4 A62-8 5" - 11" 270* M2560 P1A5 A62-8 5" - 11" 0* -M2560 4-1/2" 0* M2345 P2D1 A12-62 2" 4-1/2" 90* M2345 P202 A12-62 2" P2A1 A37-29 49 -1/2" 1/2" 0* M2408 P2A2 A37-29 49-1/2" 1/2" 90* M2408 P2A3 A37-29 49-1/2" 1/2" 180* M2408 P2A4 A37-29 49-1/2" 1/2" 270* M2408 I P2A5 A37-29 49-1/2" 1/2" 0* M2408 P1D1 B34-19 6-1/2" 1/2" 0* M2869 P1D'2 B34-19 6-1/2" 1/2" 90* M2669 P103 834-19 6-1/2" 1/2" 180* M2869 P1D4 B34-19 6-1/2" 1/2" 270* M26o9 P1DS B34-19 6-1/2" 1/2" 0* M2869 t a prec. oat (3) Specimens with a "P" prefix were received treated with M and exposed to debris from the explosive expansion. 0914c/0127c/010583:5 39

Tali t e 5. _t Compimi t lons of Al loys list'il t o Pre p. ire Hin t-U-Benda (valuea les weiglit I) Eltment Nb + Alloy C SI Hn _ S_ _N_ i___ Cr _li Tl At Ta P Cu Co other l Inconel X-750 0.04 0.03 <0.01 0.(H14 72.57 15.60 7.10 2.60 0.70 1.01 O.01 0.03 0.23 h 0.038 0.86 0.40 0.(Hl3 4.30 15.79 Bai. 0.01 0.02 0.32 0.31 3.29 0.08 0.025 N I l 17-4 pit t 0.017 0.24 No 410 0.11 0.30 0.44 0.IH19 0.40 12.48 Bal. 304 0.061 0.60 1.60

0. 0.'

9.20 18.45 Ba l.- 0.031 0.32 0.13 0.42 No 0.10 N 10.0 19.0 1 3081.* D.03 1.0 2.0 0.0) to to ll.i l. 0.045 12.0 21.0 0.15 Inconel 600 0.06 0.22 0.17 0.007 76.05 15.40 7.92 0.14 Inconel 82 0.02 0.16 3.17 0.004 72.32 19.04 2.25 0.35 2.51 l aapproximate composition

Table 5-4 ALLOY SUPPLIER, HEAT NO., AND FORM Heat No. or Heat Treatment Alloy Supplier Code Form In:enel 3:-750 Universal Cyclops Corp. Q902 Plug machineo from bar stock Pittsburgh, Pa. 17-4 pH JOSLYN Stainless Steel, Heat No. 80581 Bar stock Fort Wayne, Inc. (2.5" dia) 410 Carpenter Technology, Heat No. 829985 1" plate Reading Pa. 304 Jessop' Steel Co., Heat No. 30653 Plate Washington, Pa. Wire' 308L Inconel 600 Williams and Co., Heat No. NX9349 Plate Pittsburgh, Pa. Inconel.82 Huntington Alloys, Inc., Heat No. 72980 Wire Huntington, West Va. Zircaloy 4 Data Proprietary - Stress annealed similar to B+W tubing. i 0914c/0127c/010583:5 41

7 g n 6 5 o "2 6 4 l E n i h et l g i~ni 0 0 sea nrk 4 1 et 8 9 s TS h t d g 0 l ni 1 ees 1 7 s i rk e Yt 4 4 S l trep l s o 4 0 r l s P ee wn 8 0 kd 3 8 l a c r c oa C H i Rl Jna h 5 c 5 e h H 0 F e l 1 l a b n / 0 0 a a F 0 d T 1 e 9 l 0 1 t n 5 a o e e l l l t n i m n n a + l a a t o e t 9 r n h o 8 8 7 l T e c i m 8 h e 6 H 8 t t / e 3 6 l 3 l a a F 4 r e e / a o s l l l l r 0 F n r a a a l T 5 r y 3 0 u d e e e n n n l t 1 0 f o o n n n a l + c a a a l e + l l ( l A e e e l ) h + h d dd s s s 5 h 5 e ee u u u v vl o o o h ik h h h 0 0 i 1 / / / e ec g g g F F F c 7 ci n n n e / ep i i i t t t 0 0 0 R 0 R 0 0 0 5 d s s s 8 9 6 s 1 sn e e e A 1 A a W W W 1 1 1 a n *

0 5

0 7 0 2 6 8 y X o l l l l l l e p e e i n n A no 4 L o o c 0 4 8 c c 0 0 n n n 7 1 I 1 4 3 3 I I

Table 5-6 ALLOYS AND U-BEND CODING j Coding of Mini-U-Benos Alloy Inconel X-750 Q-11 Q-12 i A-1 17-4 pH A-2 B-1 410 8-2 C-1 304 C-2 (ll50*F/7 h) D-1 308L Filler Metal 0-2 on 304 (as required) E-1 Inconel 82 Filler Metal E-2 on Inconel 600 l 0914c/0127c/010583:5 43

Table 5 LONG TERM CORROSION TEST SPECIF ICATIONS Test Test No. 1 No. 2 Boron (H B0 ) 2350 - 100 ppm B 2350 - 100 ppm 8 3 3 2.5 - 0.7 ppm Li 2.5 - 0.7 ppm Li Lithium (LiOH) Thiosulf ate (Na 3 0 )* 0.5 -.15 ppm 50 223 4 Self ate (Na 50 ) .05 .15 ppm SO 2 4 4 Chloride (Nacl) 0.5 - .15 ppm Cl .05 .15 ppm C1 Fluoride (NaF) 0.5 -.15 ppm F .05 .15 ppm F pH 5.0 - 7.5 5.0 - 7.5 Hydrogen 15-40 cc/kg 15-40 cc/kg Hydrazine (N H ) 2-10 ppm 2-10 ppm 24 Oxygen < 10 ppb < 10 ppb

Specified as sulf ate equivalent BORON LITHIUM CYCLE (ppm)

(ppm) Preconditioning 2350 + 50 2.2 - 2.5 KFT 2350 + 50 2.2 - 2.5 First Cycle 1200 + 20 2.2 - 2.5 -Second Cycle 1000 2 20 1.7 - 2.0 500 + 10 1.0 - 1.3 Third Cycle 100 + 10 0.7 - 1.0 Fourth Cycle 100 + 10 0.7 - 1.0 Fifth Cycle Sixth Cycle (which ends the test) 100 + 10 0.7 - 1.0 0914c/0127c/010583:5 44

r 6.0 OPERATING HISTORY The operating parameters for the long term corrosion and peroxide cleaning experiments were specified by GPU-N to simulate expected operating parameters of the TMI-l steam gtnerators. The experiments consist of maintaining pressurized flow of solution through the specimens while varying temperature and the applied load on the full size specimens. Two autoclaves have been used for the LTCT progran. Autoclave 2 contained specimens exposed to sulf ate chemistry and Autoclave 1 contained specimens exposed to thiosulf ate chemistry. Autoclaves 3 and 4 were operated in series for the peroxide experiment and have been converted into once-through long term corrosion apparatus for exposure of specimens exposed to the 500 hour peroxide treatment. 6.1. Test Parameter Recording and Control 6.1.1 Temperature - Proportional type controllers regulatec current to autoclave heaters. The indicating thermocouple was placed in a well inserteo through the head into the autoclave water. The control thermocouple was in contact with the autoclave 00 within the space envelope generated by the band l heaters. Typical temperature variation was + 5*F. Temperatures were recorded daily. 6.1.2 Pressure - Specimen ID and 00 (autoclave) pressures were equal oue to leaks in the specimen package. The pressure was developed and maintained with The a high pressure diagram pump and a mechanical back pressure regulator. test system pressure was maintained ;20 psig. l l The bellows gas pressure used to maintain specimen load was controlled to Since [ within 120 psig which is equivalent to about +10 lb on the specimens. the response of both specimens in an autoclave was slightly different, oue to slack in the loading system, total specimen load may have variec 110 percent from specification. l l 0914c/0127c/010583:5 45 J

6.1.3 Flow Rate Solution flow rates were typically 100 + 50 cc/hr. Some deviations occurred during temperature cycling; these were compensated for by adjusting the pumping rates where possible. 6.1.4 Record of Test Parameters Monthly tabulations of ' recorded temperatures, prassures and flowrates for Tests 1 and 2 are presented in Appendix 10.5. This appendix also contains plots of the measured temperatures and pressures for these tests. 6.2 Loop Cleaning and Preconditioning upon the completion of construction of each autoclave loop system, a perico of cleaning and sulfur preconditioning was undertaken prior to LTCT operations. The pre-operational system flushing and cleanup was accomplished by pumping high purity demineralized water from the MUT through the system with the autoclave at 600*F. During the cleanup, test samples were not placed in the autoclave with the result that the flushing process also cleaned the internal autoclave su d aces. The effectiveness of the hot water flush was determined by evaluating the results of periodic conductivity and chloride ion analyses. The following values are typical of those found for the makeup water used during the flushing process: conductivity <0.5 umho, Cl < 1 ppb, F~ < 1 ppb, 504 = 1 ppb. Flushing was terminated on Loop No. 2 when a Cl-concentration of 0.2 ppm and conductivity of 6 umho was achieved. When flushing was terminated on Loop No 1 the following concentrations in the loop effluent were measured: F~ = 1 ppb, Cl = 4 ppb, SD = 9 ppb. During preconditioning, a length of stainless steel tubing was placeo in the autoclave and f astened to inlet and outlet ports on the autoclave head. Preconditioning solutior, therefore, flowed thrcugh this tubing and did not contact the autoclave internal surf aces. The " preconditioned" stainless tubing was subsequently used to prepare the sample train used in the respective LTCT exposures. 0914c/0127e/010583:5 46

Both autoclave loops were preconditioned at 600*F with solution identical to that used in the Test 2 HFT cycles. Flow of preconditioning solution was 2 maintained until an effluent 50 concentration > 90 percent of the influent value was achieved. Three to five days was required to precondition test systems. 6.3 Autoclave Loading Test specimen identification for. each autoclave is shown in Table 6-1. All C-rings and U-bends were placed in cans in series flow with the full. size tubes. A typical package of specimens is shown in Figure 6-1. The totak load applied to a tube specimen is the summation of the load applied by the bellows and the load resulting from the pressure differential across the tube wall. Since it was originally intended to operate each test system with a AP across the specimen walls,- procecures were written which requireo that the bellows pressure be adjusted to compensate for changes in pressure across the tubing wall curing thermal transients and, therefore, would, maintain the sample load constant. However, during heatup it was noted that the primary to secondary AP decreased more rapidly than anticipated and eventually became zero due to primary to secondary system leakage through defects in the test specimens. During heatup the next effect of through-wall leakage and thermal expansion of the secondary fluid was the graoual elimination of the AP and establishment of a single phase (solid) secondary Until the secondary system was solid, this required that the bellows f system. l pressure be increased to maintain a constant sample lor.d. But once the system f was solid, specimen load was controlled solely by bellows load. Controlling specimen load during cooldown became so experimentally difficult that it required almost continual monitoring and control. This resulted from the f act that the leak rate through the tube defect was variable and insufficient to compensate for the contraction of water during cooldown. I A modification was therefore made to each of the four test systems which simplified the control of specimen load. The modification consisted of installation of a bleed line from the primary system to the autoclave or I f 0914c/0127c/010583:5 47

l secondary side. This line permitted the primary solution to fill tha ' autoclave and maintain a solid secondary system at the same pressure as the primary system throughout the entire experiment. Elimination of the aP across the tube permitted the specimen load to be controlled by only the bellows loading system. 6.4 Long Term Corrosion Experiments The two autoclaves Wre operated as long term corrosion experiments 1 and 2. The experiments consist of a hot functional test (HFT) of about one month duration followed ' y a series of six two months operational cycles with b varying solution chemistry. During each phase the system temperature and full size specimen loads were varied to simulate actual steam generator operating. conditions. The detailed test sequences for the HFT and operating cycles are presented in Appendix 10.1 and in 10.2, respectively. During heat up and while at temperature the full size specimen loads were maintained at 500 lb. At the beginning of each cool down to ambient, the load was increased to 1100 lbs ana held there until the final temperature was reached. The ' load was then reduced to 500 lbs., except at the end of the cycle where it was reduced to 0. Figure 6-2 is a stylized curve of the temperature vs. time regime for the HFT cycle of the GPU-N lead tests, and as such is an idealized representation of the cycle for both autoclaves 1 (Lead Test 1) and 2 (Lead Test 2). Figure'6-3 l is a also a stylized curve depicting the ideal thermal profile for all of tne subsequent operating cycles of both GPU-N Lead Tests. The departure of the temperature from the ideal curve was minimal in the ramping, cycling, and steaoy state stages of the HFT and operating cycles. Computer generated curves and tables for the actual operating parameters of Tests 1 ano 2 through the HFT and first two operational cycles are presented in Appendix 10.5. l [ 0914c/0127c/010583:5 48

l Water samples were withdrawn from the make-up tank and autoclave effluent after each new batch of make-up water was added (-3 weeks) and two weeks thereafter. 6.5 - Autoclave Operational Variations Both autoclaves operated through the f.irst cycle with little deviation from specifications. One general variation was the adjustment of the test sequences to conform to a five day work week. For example, Step 6 of the operational sequence (see Appendix 10.2) ' equires 10 continuous days of r tenperature cycles. These cycles were interrupted during week ends. The test At temperature at the end of a work week was maintained through the weekend. the beginning of the next work week, cycling was reinitiated as prescribec in the. test sequence. Test 2 was started before a technique was developed for measuring specimen load from bellows pressure. During the HFT it is estimated that loads were actually 200 lbs low in the specimen. Also, for this autoclave one bellows f ailed during the-pressure increase proceeding the cooldown to ambient for both the HFT and Cycle 1. After each bellows f ailure, tne system was opened, the bellows replaced and the remainder of the test continued according to the test specification. The next effect of the bellows failure was loss of load during the cooldown from 600 to 140*F. The bellows f ailure did not occur until most of the load increase was achieved with the result that the tubes were subjected to most (but not all) of the high stress at 600*F. The effect of this deviation from the test specification on the tube integrity can not be assessed. Examination of the bellows indicated ID initiated stress corrosion cracking as the cause of the f ailure. Failure was, therefore, from the gas side and not a result of exposure to autoclave water. Residual moisture and chloride contamination were suspected in the f ailed bellows. All bellows internal surf aces were subsequently washed in high purity water and thoroughly dried before use. 0914c/0127c/010583:5 49

1; Minor deviations from specifications are recorded in daily recoro log books on permanent file in the Westinghouse Research Center Remote Metallographic Laboratory. 6.6 Chemistry Monitoring During the HFT, First and Second Ocerating Cycles of Lead Test 1 During the performance of the various test cycles, analyses of MUT solutions 4 and effluent solutions, which had passed through or over the test specimens, were routinely' performed. The intent was to control MUT chemical concentrations within specified limits and monitor effluent solution levels to determ'ine what changes may have resulted from exposure to the test specimens. The results of these analyses would provide documentation of the chemical composition of'the test solutions during each of the exposure periods. MUT solutions were prepared as described in Appendix 10.3 (Section 10.3.2) from concentrated stock' solutions which in turn were prepared as described in Appendix 10.3 (Section 10.3.1). MUT solutions were always prepared from stock solutions whose concentrations had been verified by chemical analyses. However, due to the time delay between sampling and analyses of MUT so.lutions, no adjustments were mace in make-up tank compositions based on the results of chemical analyses of MUT samples. In most cases, make-up tank solutions were completely consumed prior to receipt of the results of chemical analyses on samples withdrawn shortly after their preparation. The analytical chemistry results for samples collected from Lead Test 1 are 1 given in Tables 6-2, 6-3 and 6-4 for the HFT, first and second operating cycles, respectively. The data in these tables shown that no difficulty was encountered in maintaining either MUT pH or dissolved oxygen within control l limits. Minor deviations in lithium and boron target concentrations were observed during both cycle 1 and cycle 2. These variations may have arisen from operational considerations between and during cycles. Between each operational cycle, the MUTs were backflushed with deionized water l If the MUT and drained prior to filling with freshly prepared MUT solutions. had been incompletely drained following the flushing operation, the new MUT l 0914c/0127c/010683:5 50 1 _m.

changa would be diluted by any unremoved flush water. The location of the drain value on the MUT (in the side rather than the bottom of the tank) makes incomplete removal of flush water a propable event resulting in a decrease in both lithium and boron in some cases. Likewise there was at least one operational variation which could have After resulted in an increase in chemical concentrations of these species. preparation, each MUT solution is sparged with inert gas to remove oissolved If the sparging rate or length of sparging time varied between MUT oxygen. preparations, concentration of MUT nonvolatile species may have resulted by loss of water vapor, carried off with the sparging gas. Either of these two events or. Some combination of these events may have occurred and caused the observed variations in targeted MUT concentrations. Minor difficulties in control of boron concentrations became apparent as the The concentration and the corresponding control band for boron decreased. relatively narrow control band for boron established at the lower nominal baron concentrations appears to be an unreasonably tight control band in the small volume test systems employed in this program. Broadening of this band snould be considered in subsequent cycles. Fluoride, chloride and thiosulf ate were to be controlled at low ppb levels in Extreme difficulty was encountered with control of the MUT this test. fluoride concentrations. Experience in toth Lead Test 1 and 2 showed that, although required volumes of the analytically verified fluoride stock solution were added to the MUT, low resulting fluoride concentrations were observeo. This was attributed to adsorption of fluoride on the walls of the polyethlylene holding tank. The practice of adding F directly to the stainless steel MUT during transfer of soluton from the polyethlene holding tank was adopted to attempt to minimize adsorption, but this practice has proved inadequat'e in increasing MUT fluoride levels. Adsorption of fluorice on the stainless steel MUT walls is also thought to be occurring. Some difficulty was also encountered in controlling chloride at the oesired MUT levels. Although chloride levels in the MUT were within the targeteo control band duing the HFT cycle of Test 2, MUT chloride concentrations during the HFT and second operating cycle were f requently a f actor of two high. 0914c/0127c/010683:5 51

Although the targeted thiosulfate level'in this test (0.0585 ppm) was only slightly above the limit of detection of thiosulf ate by the ion chromatographic analysis methoo, no thiosulf ate was detacte"d in any MUT or - effluent samples. Although sulf ate was routinely detected in effluent samples, the level of sulf ate in these samples decreased with time dur-ing each cycle. It can not be determined whether the observed sulf ate was derived from thiosulf ate or was simply a result of specimen (or specimen train) sulf ate contamination. Initial effluent samples were extremely high in fluoride, chloride and sulfate in each test cycle. Values for these species did decrease with continued exposure to fresh MUT solutions and effluent concentrations gradually approached those of the MUT solutions. This is attributed to contamination of the specimens and specimen trains during post exposure visual examinations. This contamination occurred despite strict compliance with operational procedures and techniques designed to minimize contamination. The highest effluent levels were observed in the initial effluent sample taken during the HFT cycle. Since the full length tube specimens received no pre-test rinsing and since some specimens received M,==o=e treatment, this high initia1 4 effluent values are not unreasonable. 9 Overall deviations from targeted concentrations have not been great and are not expected to have a major impact on tube corrosion. l 6.7 Chemistry Monitoring During the HFT, First and Second Operating Cycles of Lead Test 2 Tables 6-5, 6-6 and 6-7 are tabulations of the analytical chemistry results for water samples withdrawn during HFT, first and second operating cycles respectively of Lead Test 2. As in Test 1 (Section 6.6) some difficulty was 2 encountered in maintaining Li, B, Cl, F and 50[ MUT concentrations within the targeted MUT range for each of these species. The discussion found in Section 6.6 is also pertinent for the results of'this 2 The high initial effluent values for F, Cl, and 50 - test. observed early in each cycle are attributed to wash-off of these species from specimen and specimen container surf aces. 0914c/0127c/010683:5 52

6.8 Hydrogen Peroxide Experiment l The hydrogen peroxide experiment was a 500 hour experiment designeo to simulate the proposed TMI-1 steam generator cleaning procedures. Solutions containing hydrogen peroxide were passed through a series of full size tube specimens and cans of U-bends and C-rings. The recirculating system was regularly replenished with H 0 to maintain the peroxide concentration in 22 the specified control range. Nominal operating parameter specifications for this experiment were: Temperature,130*F Pressure 10 psig (from make-up tank overpressure) Flow rate 2 gallons /hr pH 8.0 - 8.2 Boron 2350 ppm Lithium 1.5-2.2 ppm H0 level , 15 - 20 ppm 27 Full size specimen load, 500 lbs. yp Cleaning and Preconditioning - Cleanup and preconditioning of the 6.8.1 loops used in the peroxide cleaning procedure was accomplished as described in Section 6.2. Each autoclave assembly was flushed with high purity deionized water, with the plumbing in the once-through mode. Water flushing of the first peroxide loop autoclave (Loop 3) comenced January 28, 1983 and was completed on. February 3,1983; the flushing of the second peroxide loop. autoclave (Loop 4) began on February 7,1983 and was completed on February 9, 1983. The high purity water cleanup of the autoclave systems was followed by

a. sulf ate preconditioning with the autoclave plunbing remaining in the individual, once through configuration.

The. primary function of the sulf ate preconditioning was to attain a stable system " steady state", relative to the sulf ate, in which the sulf ate concentration of the effluent is at or near the sulf ate of the influent solution. This was accomplisned by exposing the tubing and system, exclusive The of the GPU-N specimens, to a sulf ate solution and analyzing the effluent.

sulf ate analytical results for Loops 3.and 4 in the cnce-through cleaning ano flushing operation are given in Tables 6-8 and 6-9, respectively. l Since there was interest in monitoring the loop sulfate level curing the hydrogen peroxide experiment, care was taken during the clean-up ano preconditioning of the loop systems to establish baseline sulfate values. Tables 6-8 and 6-9 present the results of sulf ate analyses obtained by ion chromotography for samples withdrawn from the loops during these operations. Sulf ate preconditioning of Loop 3 was completed on February 9. The preconditioning of Loop 4 were completed on February 17. 6.8.2 Loop Operation with Peroxide Additions - After preconditioning, Loads 3 and 4 wer'e combined as shown in Figure 4-3 to form the closed loop system useo during the perioxide cleaning. The specimens, as identified in Table 6-1, were placed in Autoclaves 3 and 4 and the MUT filled with 50 1 of a solution containing 2350 ppm B as boric acid and 2.1 ppm lithium as lithiun hyoroxide. 2 . After the MUT was sampled to determine the baseline 50 level (See Table 4 6-13), one liter of MUT solution was flushed through the system (specimens remained by-passea).and removed via the effluent sampling line. A sample of this initial flush solution was also retained for analysis (See Table 6-13). Adcitio1s of aninonium hydroxioe and sodium sulf ate solutions were made to adjust the MUT pH to 8.2 and increase the sulf ate concentration to a value comparable to that used curing loop preconditioning. These aaditions were also made with the test specimens by-passed. Because a " primary-to-secondary" leak at the tube collar weld was cetected during the leak checking.(which is part of the specimen assembly procedure) a crain line was connected from autoclave 3 to the MUT. This drain line prohibited the autoclave pressure from gradually increasing to that of the primary system and, thereby, significantly simplifieo operation of the specimen loading fixture by eliminating the need to frequently adjust gas pressure in the bellows. This drain line remainea open to the MUT throughout the entire peroxide cleaning procedure. 0914c/0127c/010684:5 54

^ - The H 0 injections into the circulating system were started by discrete 22 manual introduction at hourly intervals. Later, an automatic peroxide injector was added to the system to allow routine metered peroxide addition to the system. A summary of the changes made to the apparatus for increased efficiency or because of unforeseen circumstanges is given in Table 6-10. The average daily peroxide concentration of the solution in the make-up tank, as well as the pH of this solution, is reported in Table 6-11; the oaily peroxide usage is tabulated in Table 6-12. All of the pertinent peroxioe cata listed in Tables 6-11 and 6-12 are plotted in figures 6-4, 6-5 and 6-6. It should be noted that in order to maintain the peroxide concentration in the make-up tank (MUT) within the selected limits, the peroxide additions (or deletions) were both continuous and discrete; i.e., the addition of the peroxide was generally accomplished with the automatic injector system, with additional manual injections if the MUT peroxide concentration was too low. Conversely, if the MUT peroxide concentration began to increase over the target value, the injector.was turned off for a predetermined length of time. l Because of this distinction, the average rate of peroxide addition was determined by dividing the weight of peroxide added in a given period (in all but the first and last cases, one day) by the nunber of hours in that period. The scatter in the data for the weight of peroxide added (concentration) and the average weight of addition for the first 90 hours can be attributed to tne learning process of the operators. This learning process is graphically illustrated in Figure 6-4: as the skill of the operators increased, the range of values of the average daily MUT peroxide concentration decreased. After 150 hours of operation, there was a gradual decrease in the amount (and average rate) of peroxide addition needed to maintain a 15 ppm hydrogen peroxide concentration in the MUT (Figure 6-5). This decrease in the amount of H 0 which was adaed can most probably be attributed 'to the gradual 22 decrease in volume of solution in the loop caused by sampling. 6

6.8.3 Chemistry Monitoring During the Peroxide Experiment - During the entire 500 hour peroxide exposure control of chemistry was very good. Figure 6-6 shows-that the system pH remained essentially constant at pH 8.2. Boron and lithium concentrations showed some minor variation which is presumed to be oue to the normal fluxuation in values resulting from the analysis of these species and does not reflect any eff ect of peroxide additions. Perox'ide ' concentrations ~ initially showed some variation from the 15-20 ppm specification due to the inadequacy of manual additions to compensate for consumption rates. Following installation of the peroxide injection system, the observed spread in peroxide concentration values was narrowed significantly (See Figure 6-4). The analytical chemistry data obtained by analysis of the solutions withdrawn 1 from the loop during the peroxide exposures are presented in Table 6-13. During the first three days of exposure to peroxide containing solutions, the sulf ate concentration in the effluent solutions gradually increased. Although l the refilling of the MUT with fresh solution on the fourth day of testing (which was necessary due to solution loss resulting from the events documented in Table 6-10) caused a temporary reduction in the effluent sulf ate concentrations (simply by dilution) effluent sulf ate values continued to increase through the first eight days of testing before stabilizing at - 300 ppb after 200 hours of exposure. Although the observed increase in effluent sulfate may have been due to oxidation of lower oxidation state sulfur containing species on tube surface or to the release of sulf ate from the network of intergranular attack comprising the tube defects, the possibility that the observed increase in effluent sulf ate was due to contamination during j the preparation of C-rings and U-bends or during assembly of the full length tube specimens can not be discounted. The inaccuracies involved in estimating the volumes of solution lost during the unexpected system leaks of February 25 and 26 (See Table 6-10) make any attempt at a material balance for sulf ate, at best, crude. Nevertheless, l material balance calculations were made which show that approximately 17 mg of 50 , or approximately 7 mg of 5, in exce'ss of that intentionally adoed to the loop in MUT solutions, was movec from sample train assemblies during the peroxide exposures. 0914c/0127c/010683:5 56

,r I ii TEST 3 4 .3 M

r. :

~ TEST 4 FIGURE 6.1 - Typical Specimen Packages, Test 3 Contains Two " Repair" Type Specimens and Test 4 Contains One " Lead" Type Specimen and Cans of C. Rings and U-Bends.

l i C.erv6 74 jt 7 3-/= Temperature Cycle A 600 I t I l l i f f I 0 1 2 3 4 5 6 7 8 Cycle Time (H) 700 Temperature Cycle A 600 [500 - f Exam,ne Specimens i E# Evaluate Results 3 t.oad - Open to End of g I)0 Evacuate Atmosphere HFT Cycle & 200 Add NH NH 2 2 [ E Add H I 2 'l 100 d'=' 0 0 10 20 30 40 Time (days ) Figure 6-2 Stylized HFr Carve

6 1 4 4 m la I_ & he ..e 5 u, t. bauti Sa i n L;,c' tw m 4 se.t An 9, %.. 200 s,. t Did1%. gy(. I AE "? ~ a n g 20 Il 40 50 a0 70 C 10 lime scapi j - i Figure 6-3 Stylized Imad Test Cycle e-e-, e,. ,r-.- .,,.,--4e4-- -.,w ,.n,w i- -. -.--v,--,.--.,.m v. , - -.,,.., -,. + -..

ll 1 055 0 { ' {h 0 5 X TN X 0 E 5 U 4 L X TF UF ME 00 - X 4 x T X N X E 05 M 3 S I X lI. i l R I E AV P 0 X 0 N X = O 3 E E X I r T uM A l oI l' E h T N I D 0 !l 5 C I N 2 O X C O 2 R 02 X 0 E 1 1 0 P 2 4 X 6 U i P l t 0 li i G 5 G I 1 F X X 00 1 0 X 5 X M0 0 5 0 5 g 5 5 a 5 0 l 5 4 4 3 3 2 E[ $$40 O" O 1l 1 I 1 I

I1 lI 885 )C 8 EC 5 G 4 A 3 R8 E V5 A( 8 8 TE 4 SG EA TR E RV 8 s 5 UA T O 3 E_ N HT S i E S lT M 9E A 1 T ( I 8 f R 8 N 3 O E I r P W X e E L E t r 8 uM R s 5 oI 2 h T G ED 2 I 02 X 1 8 1 O 8 D R 2 i lT E A P M I T U S S i S l P I G 5 6 i l S t t S il I G I F 8 5 1-r_ S 5 4 3 2 1 8 9 7 a 5 4 3 2 1 g 1 1 1 1 1 1 [n. 3 dt 4o uu Ng.43oe s i NN1 4e Fn.l ou IlIil l ftl l'

t 055 00 5 85 4 00 4 TNE 8 M 5 I 3 S. R l i l E V I. P 0 1 X 0 l e p i ^ 3 E rE 'I uM N E o I l i t h T k D 0 i i t I 5 il' 2 i X iX l O 2 R 02 E 0 1 1 0 P 2 6 U 6 P i t t G 0 i l i 5 G i 1 I 00 1 0 5 B 5 4 3 2 1 O 9 8 7 6 5 8 8 0 8 S 7 7 7 7 7 L I( T l il I il,l 1i1 l i1 1!I:i j J l

Table 6-1 AUTOCLAVE.5PECIMEN LOADING Full-Size C-Ring Test No. Tube Original Replacement U-bends 1 A13-63 1A1 (11-18 15/16) 1A2 +285 After HFT A24-94 181 4184 After Cycle 1 (19 5/16-25 7/16) 182 101 102 2A1 2B1 2D1 1El 1E2 1E3 2 816-21 2A2 41A5 After HFT (52-59) 2A4 +284 After Cycle 1 A88-7 282 (2-9 3/4) 283 2D2 203 1A4 183 103 1E4 1ES 1E6 3 A24-94 (36-42) 894-27 (4 1/2-10~1/2)

Table 6.1 (Continued) Full-Size C-Ring Test No. Tube Original Replacerrent U-bends 4 A16-69 PlAl Removed after H 0 Run All 22 (6 1/2-12 1/4) P1A2 P1A3 P1A4 PlAS P201 P202 P2Al Removed after H 0 Run 22 P2A5 PlD1 PlD2 PlD3 PlD4 PIDS

~ s TABl.E 6-2 1 ANALYTICAL DATA FOR TEST I IIFT CYCLE S023 N II24 4 ftWD D.O. 1.i it I: C1 fu mlio) (PIN) (l'IN) (l'IN) (PIN) (plN) (l'IN) (plN) (plN) SOlRICli pil ' q an l 5.0 2.2 2300 0.05 0.05 2' ~~ T Y LEVELS 7.5 2.5 2400 0.15 0.15 10 m TAKlW /2/82 MlE 6.5 40 <0.005 2.16 2323 0.075 2.22 0.183 0.053 <0.05 NIM MlE /3/82 liFF 2.21 2332 0.972 58.45 0.908 0.040 <0.05 /8/82 I?FF 2.21 2358 0.06 0.436 0.202 0.086 <0.05 fl0/82 liFF 2.34 2359 0.06 0.282 0.181 0.086 <0.05 fl2/82 14 4 5.6 60 (Agg) 2.28 2352 0.06 0.292 0.178 2.00 <0.05 NIM 14E OPliN TO ABIOSPIRIRE l.81 2519

0.05 0.399 0.168 2.50

<0.05 f23/82 EFF Sog celuivalent = 0.05 to 0.15 PIN. f i e

TABLE 6-3 ANAI.YTICA1. DATA FOR' TEST 1 IST OPERATING CYCLE S023 N II24 4 C(Nil

11. 0.

l_. i 11 1: Cl (l'IN) (l'IM) (PlH) (PlH) (PIN) (PIN) (PIN) (PIN) (omlu SOllllCli pil cm 5.0 2.2 1180 0.05 0.05 2.0 0.0585(AsNa 8 0 [ en 223 jr.ET Milt to <0.010 to to to to (MISTRY I.FVFIq 7.5 2.5 1220 0.15 0.15 to Ili TAKlW D2/22/82 Mir 6.08 58 <0.002 2.65 1315 <0.05 0.198 0.173 0.698 <0.05 2.64 1249 <0.05 0.232 0.064 0.041 <0.05 B2/28/82 DT 2.72 1274 <0.05 0.195 0.129 0.046 <0.05 12/29/82 DT 1/04/83 MTP 6.13 50 <0.005 2.56 1217 <0.05 0.161 0.135 0.321 <0.05 1.83 1260 <0.050 0.236 0.158' 8.2 <0.05 1/13/83 DT 1.96 1258 <0.050 0.223 0.064 4.5 <0.05 1/25/83 DT 1/26/83 MlTP 6.13 52 <.005 1.85 1253 <0.050 0.236 0.064 9.8 <0.05 Refill t 2.20 1235 <0.050 0.141 0.028 <0.1 2/08/83 DT 0.031** 2/11/83 MtTP 6.03 53 <.005 2.11 1215 <0.050 0.132 0.050 10.6 Refill 0.053** 1.95 1203 <0.050 0.137 0.028 <0.1 2/23/83 DT O.031** 2.15 1243 0.088 3/02/83 DF 1246 0.120+

TADIE 6-4 ANAL.YTICAl. DA*fA FOR TEST I 2ND Ol'ERATING CYCf.E S023 N 3324 914

11. 0.

I.i 11 F c1 [trtlIl p'uho (l'itt) (l'ISI) (l'IN) (PIN) (PIN) (l'IN) (PIN) (PIN) SXiltCli pil ( cna 5.0 1.7 980 0.05 0.05 2 0.0585 to as <0.010 . to to to to to [ET Hilt 2.0 1020 0.15 0.15 10 0 Na 0'2 3 2 UlSTRY 1.EVEl.S 7.5 Ji T A Kl W '4/83 MLTI' 7.10 44.5 <0.005 1.71 1015 < 0.05 0.226 0.131 7.15 <0.05 0.108+ '4/83 EFF 1.60, 979 <0.05 0.933 0.319 0.82 < 0. 0'S 0.340 0.3668 19 / 8 3 EFF 1.75 1023 <0.05 0.223 0.061 <0.01 <0.05 0.092+ <0.005 1.70 1028 <0.05 0.227 0.114 8.30 <0.05 f21/83 MIII' 6.25 723/83 EFF 1.81 1040 <0.01 0.302 0.038 ~ <0.01 <0.05 1.52 1042 <0.01 0.296 0.033 0.02 <0.05 916/83 EFF 918/83 HUT 6.07 38 <0.005 1.71 1046 <0.01 0.274 0.056 16.5 <0.05 l.62 1030 <0.01 0.287 0.028 0.02 <0.05 f23/113 1.FF Duplicate Analysis Techeck h/l?/81 CI'U Designat ion

~ f TABIE 6-5 ANALYTICAL DATA FOR TEST 2 HFT CYCLE S023 N 1324 4 1:0 Nil

11. 0.

1.i ll 1: Cl SOUllCli pil [pmino (l'IN) (l'IN) (l'IN) (PIN) (l'IN) (l'IN) (PIN) (PIN) \\ M J ^ l 5.0 2.2 2300 0.05 0.05 0.05 2 fF.T H;IT to <0.010 to to to to to to TJISTRY I.EVFl.S 7.5 2.5 2400 0.15 0.15 0.15 10 Research Mrr 5.73 42 <0.005 2.2 2395 0.02 0.06 0.115 " evidence" Analysis fl9/82 NI *' 1 22/82 Mir 1.90 2341 0.08 0.08 0.08 2.75 Ana ysts SPIKID Mfr WI'lli l',Cl- /25/82 MTP 1.97 2296 0.06 0.118 0.388 5.27 DT 2.10 2303 2.38 1.23 0.511 0.15 f25/82 f28/82 Mir 2.01 2315 0.041 0.102 0.214 0.44 <0.05 /28/82 DT 1.98 2305 0.47 0.47 0.24 0.018 /2/82 HLfr 5.6 38 (Air) 2.00 2297 0.073 0.100 0.234 0.76 <0.05 yy Open to Air /11/82 Mtrr 2.07 2350 0.06 0.155 0.220 0.193 <0.05

11/82 DT 2.07 2348 0.05 0.248 0.236

,0.079 <0.05

TAlli.fi 6-6 ANALYTICAI. DATA FOR TEST 2 IST CYCLE S023 N 3324 4 CONil

11. 0.

1.i it 1: Cl. I u nho (PlH) (PiH) (PlH) (plH) (PlH) (lilH) (PlH) - (Ply) S0llitCli pil (. cm j 5.0 2.2 1180 0.05 0.05 0.05 2 b"ETMUT lSTRY LEVELS to <0.010 to to to to to to 7.5 2.5 1220 0.15 0.15 0.15 10 3 TAKEN 3/82 Mir 2.07 1310 <0.05 0.323 0.171 0.02 10/82 Mir 6.5 40 <0.005 1.94 1119 <0.05

0. 2%

0.140 3.24 / /82 1.95 1281 <0.05 1.60 0.245 0.05 10/82 liFF 1.88 1185 <0.05 0.538 0.200 <0.01 10/82 !!FF <0.005 '2.16 1205 <0.05 0.146 0.039 0.005 REFil.l. MIT 21/82 Mir 6.03 52 0.136+ 2.25 1196 <0.05 0.148 0.037 0.005 23/82 !!FF 0.150t 2.14 1209 <0.05 0.163 0.033 0.012 ./83 !!FF 1/83 Mff 6.00 67 <0.005 1.87 1205 <0.05 0.217 0.098 4.6 <0.05 REFil.l. 1.93 1187 <0.05 0.236 0.097 <l <0.05 96/83 I!I;F )/83 Hir 6.10 51 <0.005 2.15 1214 <0.050 0.138 0.160. '8.0 RiiFil.l. D.I79 1.95 1204 <0.0$0 0.147 0.1 15 <0.1 D/83 liFl: 0.152 2.30 1203 <0.050 0.151 0.206.. 0.11 16/83 til:1: 0.221 2.29 1203 <0.050 0.127 0.179 3.6 17/83 lil:F 8.I97

Concentrator Coltann.

TAatE 6-7 ANAL.YTICAl. DATA FOR TEST 2 2ND OPERATING CYCL.E N II24 S023 4 t:twil

11. 0,

l.i 11 1: C1 S0111H:11 pil p nJin (l'IN) (l'IN) (l'ISI) (tilN) (lalN) (l>lN) (l>iN) (tilN) I ( C8! s 5.0 1.7 980 0.05 0.05 0.05 0.05 to t to to to. to to ET Mitt 7.5 <0.010 2.0 1020 0.15 0.15 0.15 0.15 ISTRY 1.EVEl.S 3 TAKf14 p27/83 HUT 6.50 70 <0.005 1.48 998 <0.05 0.242 0.171 0.40 New f28/83 EFF 1,47 990 <0.05 0.236 0.283 0.28 f8/83 HLTP 6.17 33 . <0.005 1.76 1026 <0.05 0.236 t.0.135 0.22 J0.142 Refill '0.17558 ./9/83 EFF 1.70 1019 <0.05 0.227 0.164 0.02 O.16685 !/23/83 EFF 1.72 1060 <0.010 0.279 0.130 <0.01 /6/83 EFF 1.79 1024 <0.010 0.286 0.121 <0.01 1/14/83 MLTP 6.24 <0.005 1.72 1037 <0.010 'O.276 0.119 12.41 EFF l.74 1037 <0.010 0.282 0.111 0.02 >/20/83 ll Ion Chrmatography Icop

l Table 6-8 ANALYTICAL CHEMISTRY RESULTS FOR LOOP 3 0URING CLEANUP AND PRECONDITIONING 2 Sample 50 B Li Date Source (PPM) (PPM) (PPM 1 Remark s Final Water Flush 2/3/83 EFF 2.950 Preconditioni ng 2/4/83 MUT 0.148 Preconditioning 2/4/83 EFF 1.200 Preconditioning 2/7/83 MUT 0.150 Preconoitioning 2/7/83 EFF 0.154 Preconditioning 2/8/83 MUT 0.150 Preconditioning 2/8/83 EFF 0.152 2/9/83* MUT 0.142 2389 2.04 Preconditioning 2/9/83* EFF 0.154 2296 1.92 Preconoitioning

Analysis performed.at Waltz Mill; others done at Westinghouse Research and Development Center 1

0914c/0127c/010683:5 71

~ Table 6-9 ANALYTICAL CHEMISTRY RESULTS FOR LOOP 4 OURING CLEANUP AND PRECONDITIONING 2 Smple 50 B Li Date Source (PPM) - (PPM) (PPM 1 Remark s 2/8/83 MUT 0.007 H O Flush 2 2/9/83 EFF 0.225 Final Flush S eple Preconditioning 2/10/83 MUT' O.14 7 Preconditioning 2/10/83 EFF 0.810 Preconditioning ' 0.152 2/11/83 MUT Dreconditioning 2/11/83 EFF 0.373 ~ Preconditioning 2/14/83 MUT 0.155 Preconditioning 2/14/83 EFF 0.183 2/15/83 MUT 0.150 \\ Preconditioning Preconditioning 2/15/83 EFF O.340 2/16/83 'MUT 0 1504 g Preconditioning 2/16/83 EFF 0.175 Preconditioning j

2/17/83 MUT 0.135 2385 2.11 Preconditioning Preconditioning
2/17/83 EFF 0.147 2294 2.57
Analysis performed at W11tz Mill; others done at Westinghouse R+0.

4 \\ i .+.,.. s s h s 1, \\ 0914c/0127c/010683:5 72 )

C o Table 6-10 APPARATUS CHANGES AND EVENTS: PEROXIDE CLEANING RUNS Date Event Action Result 2/22/83 No mixing of chemical Attached peristaltic Better solution additions in MUT puna to MUT to func-homogeneity tion as a mixing loop 2/24/83 Hourly H 027 Added automatic Steady addition H022 injector of peroxide to addition to system the system (5 ml/h initially) 2/25/83 Plastic line on Replaced line 8 L of solution peristaltic pump lost before broke repair 2/25/83 Rupture disk broke. Replaced disk, 19 L of solution Solution pumped to replumbed so that lost before

drain, in event of a future rEpai r rupture the solution would'be returned to the MUT 2/26/83 Line on peristaltic Replaced line and 8 L of solution lost befor~e pump f ailed again peristaltic pump repair with a centrif ugal rotary pump 2/26/83 Low MUT Level Added 50 L of 54.85 L in MUT solution 2/28/83 Low flow (1.8 gph)

Checked and replaced No disk rupture; through samples rupture disk possible leakage 3/16/83 AC pressure gauge None Possibility there broken on auto-was a bulk AC clave 4 pressure throughout the entire test period l 0914c10127c/010683:5 73

I' Table 6-11 AVERAGE DAILY MAKE-UP TANK PEROXIDE CONCENTRATIONS AND pH VALUES Average H 022 Concentration Date (ppm) Average pH 2/22/83 15.0 + 0 (5)* 8.233 + 0.004 (3)* ~ 2/23/83 14.9 + 2.3 (28) 8.219 + 0.008 (24) 2/24/83 17.8 + 3.4'(28) 8.211 + 0.012 (9) 2/25/83 17.9 + 3.3 (24) 8.243 (1) 2/26/83 15.6 + 2.2 (24) 8.240 + 0.0 (2) 2/27/83 16.5 + 1.2 (22) 8.230 + 0.010 (2) 2/28/83 17.2 + 1.9 (24) 8.195 + 0.045 (2) 3/01/83 17.8 + 1.4 (24) 8.190 + 0.020 (2) 3/02/83 18.2 + 1.4 (24) 8.195 + 0.035 (2) 3/03/83 18.5 + 1.6 (24) 8.190 + 0.030 (2) 3/04/83

18. 7 + 0. 7 ( 24 )

8.180 + 0.010 (2) 3/05/83 18.4 + 0.7 (24) 8.170 + 0.020 (2) 3/06/83 18.5 + 0.8 (24) 8.210 + 0.000 (2) 3/07/83 17.6 + 0.6 (24) 8.200 + 0.000 (2) 3/08/83 17.5 + 1.4 (24) 8.180 + 0.020 (2) 3/09/83 18.3 + 1.1 (24) 8.195 + 0.005.(2) 3/10/83 17.4 + 1.1 (24) 8.175 + 0.005 (2) 3/11/83 17.6 + 1.4 (24) 8.190 + 0.030 (2) 3/12/83 19.4 + 1.0 (24) 8.16 (1) (continued) 0914c/0127c/010683:5 74

Tat.le 6-11 (Continued) Average H 022 Concentration Date (pom) Average pH 3/13183 18.4 + 1.3 (24) 8.180 + 0.020 (2) 3/14/83 18.7 + 0.9 (24) 8.150 + 0.000 (2) 3/15/83 18.3 + 0.9 (17) 8.160 + 0.010 (2) (up to shutdown initiation) ~

The number in ( ) is the number of readings over which the average is taken.

The peroxide concentrations wer s generally determined hourly (approximately), and the pH was usually read twice daily.

Table 6-12 DAILY PEROXIDE USAGE 5 lution) (50,000 ppm H 022 Total Weight Average Weight H02 2(per Hour H 0 / Day Total 22) mg/h) (g Date. Hours ml Used 2/22/83 3.55 27.2 1.360 383 2/23/83 24 135 6.750 281 2/24/83 24 198.3 9.915 413 2/25/93 24 120 6.000 250 2/26/83 24 192 9.600 400 2/27/83 24 19 2 9.600 400 2/28/83 24 192 9.600 400 3/01/93 24 202 10.100 421 3/02/83 24 192 9.600 400 3/03/83. 24 191 9.550 398 3/04/83 24 192 9.600 400 3/05/83 24 192 9.600 400 3/06/83 24 192 9.600 400 3/07/83 24 19 2 9.600 400 3/08/83 24 178 8.900 371 3/09/83 24 165 8.250 344 3/10/83 24 175 8.750 365 3/11/83 24 179 8.950 373 may be lower than reportec 3/12/83 24 154 7.700 321 3/13/83 24 1 54 7.700 321 3/14/83 24 143 7.150 298 3/15/83 16 101 5.050 316 .m

TABLE 6-13 PER10XIDE II)0P ANALYTICAL DATA TIME 24 SAMPLE CtM01ATIVE - So 2 B LI p ATH il0tlR Clf)CK SOllRCE RINNING H0lES (PIN) (PPM) (PPM) REMARKS 2/18/83 MIT 0.052 2534 2.05 No Recirculation 2/18/83 1400 EFF 0.273' 2573 2.14 System Flush t2/22/83 1850 AC EFF 0.400 2581 2.29 From AC Bleed Line 12/22/83 1900 EFF 0.863 2579 2.44 Initial Sol'n. 'Ihrough Specimens Start 00.00 62/22/83 2010 >2/23/83 0932 EFF 13:22 0.284 2579 2.53 16:20 0.305 2590 2.58 12/23/83 1230 EFF 12/24/83 0930 EFF 37:22 0.344 2584 2.54 )2/25/83 1130 EFF 63:20 0.388 2648 1.67

12/25/83 2100 EFF 71;50 0.388 2542 1.59

'12/26/83 1110 MIr 87:00 0.209 2407 1.59 4

12/27/83 2l00 EFF 120:50 0.243 2423 1.54 D2/28/83 1045 EFF 134:35 0.226 2420 1.56 02/28/83 2200 EFF 145.50 0.263 2392 1.85 13/01/83 1100 EFF 158:50 0.263 2373 1.88 33/01/83 2000 EFF 167:5G 0.305 2386 1.86 03/02/83 1110 EFF 183:00 0.243 2387 1.54

@3/02/83 2000 EFF 191:50 0.300 2375 1.89 03/03/83 1330 EFF 209:30 0.305 2390 1.86 03/03/83 2000 EFF 215:50 0.320 2368 1.87 !03/04/83 1340 EFF 233.30 0.308 2301 1.94

03/04/83 2000 EFF 239.50 0.313 2375 1.87 9

TABIJf6-13'(CONF'D) PEROXIDE IOOP NYFICAL DPXA. TIME 24 SAMPLE Q M AATIVE 4 B Li m.rE HOUR ODCK SOUNCE R M4ING HOURS (PEM) (PEN) (PEM) 3/5/83 1005 DT 253:50 0.316 2370 1.88 3/5/83 2000 DT 263:50 0.305 2351 1.85 ~ i 3/6/83 1100 DT 278:50 0.311 2370 1.97 3/6/83 2100 EFF 288:50 0.313 2362 1.82 3/7/83 1105 DT 303:00 0.315 2364 1.91 3/7/83 2200 EFF 313:50 0.306 2311 1.81 3/8/83 2100 EFF 336:50 0.290 2313 1.79 3/9/83 1115 DT 351:05 0.293 2331 1,79 { 3/9/83 2300 DT 361:50 0.322 2331 1.78 l 3/10/83 1130 DT 375:20 0.286 2335 1.74 3/10/83 2000 DT 383:50 0.318 2302 1.80 l 3/11/83 1115 DT 399:05 0.354 2322 1.76 i 3/11/83 2200 EFF 409:50 0.340 2318 1.82 3/12/83 1100 EFF 422:50 0.325 2285 1.78 l 3/12/83 2300 ET 434:50 C.345 2289 1.79 j 3/13/83 1115 EFF 447:05 0.325 2287 1.86 3/13/83 2300 EFF 458:50 0.332 2296 1.86 3/14/83 1105 EFF 470:55 0.309 2280 1.77 3/14/83 2300 EFF 482:50 0.317 2269 1.79

TABIE 6-13 (OONr'D) PEROKIDE IDOP ANALYTICAL DATA TIME 24 SAMPIE CtMRATIVE 4 B Li DATE Il00R CLOCK SOURCE IGNING 1100RS (PEH) (PPM) (PPM) i 3/15/83 1115 EET 495:05 0.324 2285 1.84 3/15/83 1600 EET 499:50 0.331 2285 1.80 3/15/83 1930 MJr 503:20 0.327 2287 1.79 3/16/83 0800 MJr 515:50 0.365 2289 1.71 3/16/83 0800 EET 515:50 0.370 2267 1.68 3/16/83 1930 EET 527:20 0.348 2236. 1.72 Inop EffIuent EFT = MLrr = Make-Up Tank e

l l 7.0 RESULTS At the end cf each cycle, the specimens were removed and the C-rings were stereomicroscopically examined. Full size tubes were then eddy current examined while one C-ring was removed for weighing and metallographic examination. Occasionally additional examination techniques such as SEM or ESCA were employed. 7.1 Visual Examination The results of the C-ring stereomocroscopic examinations to date are summarized in Tables 7-1, 7-2 and 7-3. The examinations are subjective in . nature and have been reducea to a tabular from for presentation. Interpretation is difficult since most of the tubes had significant surf ace abnormalities in the as-received condition. The primary observation following the peroxide exposure was that the material in the ID pits, which pits are typical of the ID surf aces of the as-received 0TSG tubing samples, exhibiteo a discoloration with respect to adjacent ID surface films. This usually darker discoloration differentiated the pits from the adjacent surf ace regions to an. extent that the pits appeared anomalous and possibly active. However, the number of pits, the randomness of distribution of the pits, and tne sizes of the pits were typical of other C-ring samples which were not exposed to the peroxide clean-up chemistry. Since later examinations of these peroxioe pre-exposed samples following subsequent exposure to normal reactor coolant chemistry and temperatures gave observations which were typical of all other samples, the anomalous appearance of the material in the pits following the peroxide run is-potentially interpretable in terms of differences in thc reactivity or response of the deposits as governed by solution accessibility and/or localized variations in the deposit topology. Since destructive examination of U-bend specimens was not performeo after the peroxide run, the effect of the peroxioe exposure on these materials was baseo on visual examination of the specimen surfaces. These examinations showed n'o surf ace abnormalities. The peroxide exposure therefora, had no visually detrimental effects on these materials. Following completion of the testing, destructive examination of these specimens will permit a more cetaileo 1029c/0150c/010684:5 80

evaluation of the comoined effects of th2 p roxide, HFT, and opsrational cycles. Most of the specimens that had been through the long term corrosion test cycles have significant mechanical markings (scratches and score marks) and pitting. However, these were generally associateo with the "as receiveo" surf ace features. Figu~res 7-1 through 7-6 show before and after photomacrographs of the specimens removed from the experiments for metallographic analysis. The view is looking through the C-ring cutout slot at the stresseo ID surf ace. 7.2 Weight Changes Weight changes of C-rings removed from test to date are shown in Table 7-4. The average change was a 0.02 percent weight loss. 7.3 Metallographic Examination A metallographic exanination was made of each C-ring removed from the test. Each specimen was transversely sectioned. One midplane and one end surface were mounted and polished. Etched surf aces were prepared by a 60 second exposure to concentrated hcl, methanol rinse, 5-10 second exposure to 2 percent bromine ir. methanol, and two additional methanol rinses. Typical micrographs of the strested region, ID surfaces of each specimen are shown in Figures 7-7 through 7-12. No unusual surf ace features were observeo in any of the specimens. Surf aces exanined to-date have shown intergranular attack to a maximum depth of one to two grains. 7.4 Auger and X-ray Photoelectron Spectroscopy (XPS) Analyses for Sulfur Pickup by New Surf aces of OTSG Tubing Appendix 10.6 describes the experimental methodology for preparation of ion-implanted sulfur standards and the microanalytical procedures. 1029c/0150c/010684: 5 81

Archive OTSG tubing samples, which had not been service-exposeo in the TMI-l plant, were exposed to a pre-conditioning in loop 3 at elevated temperature in simulated reactor coolant. Auger and XPS studies of these conditioneo samples and the standards gave the following three results. 1. The analysis of ion implanted standards showed that Auger electrun 2 spectroscopy can detect q'uantities of sulfur as low as 3 x 10-9 g/cm 2 If (3ug/f t ) if distributed within the first 10 nm below the surf ace. such an amount of sulfur were distributed uniformly through a 100 nm tnick region below the surf ace, the total detectable sulfur content would 2 be 0.03 ug/cm2 (30pg/ft ). Amounts lower than that could escape detection. 2. The conditioneo samples showed significant boron contamination, absent in the standards. The Auger signal for the boron compouno (unidentifiea) consistec of a major peak at 170 eV ano a minor peak at 152 eV. Tne latter may interfere with the tulfur peak at 148 eV and increase the sulfur levels that can go undetected by a f ac' tor of ten or more. No peak overlap occurred in XPS, however, and the XPS detection limit for. sulfur 2 was determined to be five times that of AES, or 0.15 ug/cm (150ug/f t ) within the first 100 nm. 3. No sulf ur was detected in any of six areas analyzed on conditionea specimens. It is concluoed that those specimens containea less than 0.15 2 ug/cm2 (150ug/ft ) of sulfur within the first 100 nm below the surf ace and less than 0.015 ug/cm2 (15 ug/ft ) within the first 10 nm.

6 7.5 Eddy Current Inspection Results In September,1982, the Fielo Data Analysis section of Westinghouse Nuclear Energy Systems undertook eddy current' testing of a number of long term corrosion test tube samples which hao been reraoved from the Three Mile Islano (TMI) Unit No. I steam generators. A baseline multiple frequency eddy current inspection was perf ormeo at test frequencies which were specifieo by GPU-N. A list of eighteen tubes which were inspected is contained in Table 7-5. All eighteen tubes were eddy current inspected using a differential bobbin probe ~ and test frequer.cies of 45 Khz, 200 Khz, 400 Khz, and 800 Khz. The calibration standard consisted of a section of archive tubing with a 0.052 inch diameter thru-wall drilled hole. The phase. angle of the dril-led hole was set at 40* for all frequencies. The 400 Khz drilled hole signal is shown in Figure 7-13. A section of OTSG tubing with machined partial ID inoications, which was to be used f or ' repair' tests, was not employeo in this phase of the program. Indicatiers were noteo on five tubes during the baseline inspection: Tube Section Indication A16-69 (Fig. 7-14) 2"-6-1/2" 95 percent I.D. A13-63 (Fig. 7-15) 20-9/16"-23-9/16" Small dent 'A88-7 (Fig. 7-16) 2"-9-3/4" 82 percent I.0. I A13-63 (Fig. 7-17) 11"-20-9/16" < 20 percent 0.D. 9b percent I.D. A24-94 19-5/16"-25-7/16" 30 percent 0.0. Adoitional eddy current testing was performed upon completion of each cycle of operation of each autoclave loop. A summary of these inspections is presentea in Table 7-5 with further explanation following. On November 15, 1982, tubes B16-22 and A88-7 were reinspected af ter their first cycle of autoclave testing (the "HFT" cycle). There appeared to be no change in the signal from the indication on A88-7 (Figure 7-18) and no indications were noteo on 816-22. I 1029c/0150c/010684:5 83

Tubes A24-94 and A13-63 were reinspectcd on November 30, 1982, following their first ("HFT") autoclave cycle. Tube A13-63 (Figure 7-19) exhibited a thru wall indication. Tube A24-94 (Figure 7-20) exhibitea the previously observeo 30 percent 0.D. indication. Three tubes were inspected on February 15, 1983. Tubes A24-94, 36" to 42", and B94-27, 4-1/2" to 10-1/2" showed no indications. Tube A16-69, 6-l/2" to 12-1/4" exhibiteo an I.D. indication the size of which was difficult to estimate due to a distortion of the signal (Figure 7-21). It is estimateo that this indication coulo be as much as 80 percent thru wall. Subsequent inspections of this tube showed this indication consistently in the range of 60 to 80 percent. Inspections of tubes A88-7 and B16-22, 52"-59", were performeo on February 22, 1983. As can be seen from Figure 7-22, there was no change in the signal for tube A88-7. No indications were observeo in tube 816-22. Tubes A13-63 and A24-94 were reinspected on March 2,1983. There was essentially no change in tne i~ndications previously observea on these tubes. A copy of the signal for tube A13-63 is provided in Figure 7-23. On March 23, 1983, Tubes A16-69, B94-27, ano A24-94, 36" to 42" were reinspected. The indication on A16-69 (Figure 7-24) remained the same and no indications were observed on B94-27 and A24-94. l 1029c /0150c/010684:5 84

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Table 7-4 WEIGHT CHANGES OF EXPOSED C-RINGS Sample Initial F inal-Weight Last Cycle Number Weight Weight Change Canoletea (gm) (gm) (mg) H022 P1A1 7.88915 7.88771 -1.44 P2A1 7.69279 7.69167 -1.12 Hgby 1A2 7.81927 7.81571 -2.56 HFT 1B1 7.58345 7.58255 -0.9 1st-2A2 7.61330 7.61205 -1.25 HFT 2B2 7.47326 7.47159 -1.6 1st L. .0150c/010684:5 112

TABLE 7-5 SLD9WW OF 'IUBE ITDY CURRfNT INSPECTIONS Change Fran Date of Indication ' Previous Inspection ID. OD. Yl'S NO Cosment Inspection Tube Section + 9/82 A24-94 25 7/16-30 13/16 Baseline B94-27 18-24\\ Inspection B16-22 59-64 A16-69 2-6h X B111-62 237 5/8-240 5/8 A13-63 38 1/8-41 1/8 l i A13-63 20 9/15-23 9/16 Dent A88-7 9 3/4-12 1/4 A13-63 11-20 9/16 X X B16-22 52-59 A37-29 35h-41 B27-47 58-64 A37-29 29 -35h B27-47 52-58 B113-62 31h-37 A24-94 19 5/6-25 7/16 X 11/15/82 B16-22 52-59 X Atter HPr A88-7 9 3/4-12 1/4 X X 11/30/02 A24-94 19 5/16-25 7/16 X-X After IIPP A13-63 11-20 9/16 X X X

4 TABLB7-5 (Cont'd) SLMRRY OF 'lUi'E ITOY CURRENP INSPIXT. IONS Charyje frun Indication Previous Inspection Inspection Tube Section ID. OD. YES NO Cdninent l Date of Baseline Inspection - l 2/15/83 A24-94 36-42 B94-27 45,-10h X A16-69 6hx12h X X Post Cycle 1 l A88-7 9 3/4-12 1/4 X X D16-22 52-59 3/2/83 A13-63 11-20 9/16 X X X Post Cycle 1 A24-94 19 5/16-25 7/16 X X Af ter 110 Run w X 3/23/03 A16-69 6h-12 X B94-27 4h-10h A24-94 36-42 9 b L

8.0 SUMARY Consistent with the objectives of the LTCT program, testing is in progress to monitor the long-term corrosion and stress corrosion performance of service-exposed TMI-1 OTSG tubing. Specimens in two "Leaa Tests" have completed approximately six months of exposure to lithiated boric acio solutions, with compositions comparable to that of PWR primary coolant, in a refreshed autoclave system. . In adoition to lithium hyoroxioe and boric acid, each test solution also contained low level contaminants consisting of Cl- (~ 0.1 ppm as Nacl), .F- (-0.1 ppm as NaF) and sulfur containing species. Test 2 containea - 0.1 b ppm 50 as Na 50 and Test 1 contained - 0.058 ppm S 023 as 4 2 4 is the molar equivalent of'O.1 ppm 2j3(0.058 ppm 50 Na b 0 23 SO ). 4 .The specimens in these tests have been subjected to operational sequences which parallel those encountered in normal plant operations. Each test has completed a HFT cycle and two Operations cycles. Although the lithium hydroxide and boric acid concentrations during successive cycles has been reduced to simulate plant practice due to core depletion, nominal contaminant levels have remained unchanged. Specimens in the two lead tests consist of axially loaded tubes and C-rings stresssed to place the ID surf ace in tension. Tube specimens were preparea from a TMI Ol3G tube material both with and without in-plant generatea.oefects i l C-rings were prepared from both service exposed and archieve (non-service exposed), tubing material. g Metallographic examination of C-rings removed at the end of each cycle has I shown no evidence of new defect formation attributable to the simulated plant [ exposure conditions. Likewise, periodic ecoy current examination of the tube specimens.has shown no indication of growth of defects existing prior to start of the test. i i 1029c/0150c/010684:5 115

A 500 hour hydrogen peroxide clean-up exposure of other specimens cas performed in a recirculating loop. Chemistry and operational conditions during the exposure paralleleo those expected to be.used during the peroxioe clean-up of the TMI-l primary system. Specimens in the H 022 exposure consisted of axially loaded TMI '0TSG tubes which had previously.been explosively expanded into a collar (simulating the repair process for defected tubes in the upper tubesheet), an axially loaoed tube, C-rings comparable to those in Tests 1 and 2, and U-bends prepared from materials useo in other TMI-l core components. Visual examination of all specimens following the peroxide exposure showeo the existance of shallow pits on the ID surf ace of some of the C-rings. These peroxide exposed specimens have been inserted in two additional once-through loops and will be subjected to chemical and operational conditions identical to those of " Lead Test No. 2". All four tests are currently in progress. 6 a 1029c/0150c/010684:5 116

9.0 FUTURE WORK l. . Consistent with the program-plan, Lead Tests 1 and 2 are continuing through four additional operations cycles. The test solution composition during these exposures will be established as outlinea in Table 5-7. ' Likewise, the u specimens which were exposed to the peroxide cleaning solution, have been placed in two additional tests which will follow the " Lead Test" format. 'These tests, Tests 3 and 4, have been started and will be subjected to a HFT and four Operations Cycles. Tests 1 and 2 will be placea on holo until the HFT cycle of Tests 3 and 4 are completed. All f our tests will then be restarted at the same time and be maintained on the same operations schedule. ~This will make the eddy current and visual inspection shutdowns for all tests coincide. Completion of each Operations Cycle, including eody current anc visual examination of samples, should require approximately two calendar months. Post-test metallography, as presently structurec, shall consist of 48 samples selected for examination from those specimens remaining after the final test exposure. The option for examination of additional specimens shall remain open. A second interim report will update the operations of Tests 1 and 2 and report on the initial exposures of Tests 3 and 4. Specifically, the second interim will contain data generated during Cycles 3 and 4 for Tests 1 and 2 and the HFT and Cycles 1 and 2 for Tests 3 and 4. 1029c/0150c/010684:5 117

q 10.0 APPENDICES t - 10.1. Procedure for Loco Operations During Lead Test HFT Cycle. The following procedure applies to operation during the HFT cycle of Leaa Tests 1 and 2. 1. Fill the autoclave with make-up tank wate.r for the appropriate test. (No.1 = thio-sulf ate-dosed RCS, No. 2. = sulf ate-dosed RCS). Leave some head space in the autoclave, after the sample train is loaded. through the autoclave bulk, venting the N2 (and whatever 2 Sparge N2 waer vapor it carried) out the top of the autoclave and into the raowaste drain line. 3. After sparging has proceeded for a standard interval, initiate pumping at 1120 psig. Note: 1120 psig is the system pressure for all of the HFT phase only. (It corresponds to a pressure above the saturation pressure for 550*F, the maximum temperature of the HFT phase). 4. The autoclave will fill from pumping through the leak'. When full, valve off sparge inlets and exits. The autoclave pressure will now rise to 1120 psig. 5. Apply 2260 psig total te the pressurization loading bellows. (This gives a AP between the bellows and the bulk of 1140 psi which, acting on the 2 0.44 in area of the bellows, applies 500 lb. axial load on the samples). 6. Follow temperature cycles per GPU procecures, maintaining all 3 pressures (bellows, autoclave, and system) at the values given. Specific steps for 1120 psig system.1120 psig autoclave, and 2260 psig bellows, with constant flow are: 1029c/0150c/010684:5 118

(6a) Heat to 150 + 50*F and hold 24 + 8 hr. (6b) Heat to 550 + 5'F at (100* + 50*)/hr. (6c) Hold at 550 + 5*F for 24 + 8.hr. (6d) Cycle (550 + 5*F) to 450 + 5'F) 4 times at (100 + 50*F)inr. (6e) Hold at 550 ; 5'F f or 1 week (minimum). 7. Initiate cooldown. (7a) Increase bellows pressure to 3620 + 250 psig; that is to a range between 3370 psig MINIMUM and 3870 MAXIMUM. The lower eno of the range is preferreo to precluoe overloading if the system pressure drops on cooling. Notei The required sample load of 1100 lb + 10 percent (990 to 1210 lb) is achieved by a differential pressure between the bellows and the autoclave of 2500 + 250 psi (2250 to 2750 psi). Ex ample: 1120 psig autoclave + 2250 psi differential - 3370 psig bellows. (7b) Maintain 1120 psig in system and autoclave while still at 550 + 5*F. (7c) Cool to 130 + 5*F at a rate of (100 + 50*F)/hr. (as f ar as practical). In practice this rate will prevail until about 225'F. Below 225*F, the maximum achievable rate should be instituteo to reach 130 + 5*F in 4 to 5 hours from 225*F. (7d) While cooling, close attention to the autoclave pressure is requireo and adjustments to the bellows pressure may be required must be compensate for rapidly by decreasing the bellows pressure so that the bellows pressure is always within tee range of 2250 - 2750 psig greater than the autoclave pressure. In fact, the autoclave contents could become 2-phase on cooling if the contraction of autoclave water is not overcome rapidly enough by the pump rate through the leak, and the autoclave pressure will drop. When this happens, simply lower the bellows pressure so that it is not above 2750 psig more than the autoclave nor below 2250 psig more than the autoclave, and log all changes: time, temperature and pressures. 1029c/0150c/010684:5 119

(7e) At 130 + 5'F, maintain or restore the 1120 psig autoclave and system pressures followed by decreasing the bellows pressure to 2260 psig, while maintaining continuous circulation. 8. Maintain parameters of (7e) and I (8a) Vent MUT H2 overpressure with continuous venting for a minimum (8b) Sparge MUT solution with N2 from the gas space of the MUT. of 15 minutes to purge H2 (8c) Sparge air at atmosphere ' ressure into MUT p (8d) Maintain aerated MUT at atmospheric pressure 9. Circulate under conditions of (8d) for a minimum of 2 weeks, 1120 psig aqueous pressure, 2260 psig bellows pressure. 10. Depressurize all systems, stop circulations, open autoclave while warm (130!F) and remove samples for inspection. 10.2 Procedure for Loop Operations During the Lead Test Operations Cycles The following proceoure applies to operation during Operations cycles for Tests 1 and 2 which follow the HFT cycle in series. 1. Fill the autoclave with make-up tank water for the appropriate test (No. 1 = thio-sulf ate-dosed RCS, No. 2 = sulf ate-dosed RCS). Leave some head space in the autoclave, after the sample train is loaded. 2. Sparge N through the autoclave bulk, venting the N2 (and whatever 2 water vapor it carries) out the top of the autoclave and into the radwaste drain line. 3. After sparging has proceeded for a standard interval, add 15 psig H2 overpressure to the MUT and initiate pumping at 1760 psig. 1029c/0150c/010684: 5 120

n Nota: 1760 psig is th2 system pressure for all of the Operations Cycles. (It corresponds to a pressure above the saturation pressure for 600*F, the maximum temperature of the Operations Cycles.) 4. The autoclave will fill from pumping through the leak. When full, valve off sparge inlets and exits. The autoclave pressure will now rise to 1760 psig. 5. Apply 2900~ psig total to the pressurization loading bellows. (This gives a AP between the bellows and the bulk of 1140 psi which, acting on the 2 0.44 in area of the bellows, applies 500 lb. axial load on the samples.) 6. Follow temperature cycles per GPU procedures, maintaining all 3 pressures (bellows, autoclave, and system) at the values given. Specific steps for 1760 psig system,1760 psig autoclave, and 2900 psig bellows, with constant flow are: .(6a) Heat to 150 + 50*F and hold 24 + 8 hr. (6b) Heat to 600 + 5*F at (100* + 50*)/hr. (6c) Hold at 600 + 5'F for 24 + 8 hr. (6d) Cycle (600 + 5'F) to (500 + 5*F) 5 times at (100 + 50*F)/hr. hola each endpoint temperature for 24 + 8 hrs. (6e) Hold at 600 + 5*F for 2 weeks (minimum). 7. Initiate cooldown. (7a) Increase bellows pressure to 4260 + 250 psig; that is to a range between 4010 psig MINIMUM and 4510 psig MAXIMUM. The lower end of the range is preferred to preclude overloading if the system pressure. drops on cooling. 1029c/0150c/010684: 5 121

Note: The required sample load of 1100 lb 110 percent (990 to 1210 lb) is achieved by a differential pressure between the bellows and the autoclave of 2500 + 250 psi (2250 to 2750 psi). Ex ample: 1760 psig autoclave + 2250 psi differential = 4010 psig bellows. (7b) Maintain 1760 psig in system and autoclave while still at 600 + 5'F. (7c) Cool to 130.; 5*F' at a rate of (100 + 50*F/hr (as f ar as practical). In practice this rate will prevail until about 225*F. Below 225*F, the maximum acnievable rate should be instituted to reach 130 1 5'F in 4 to 5 hours from 225*F. (7d) While cool'ing, close attention to the autoclave pressure is requirec and adjustments to'the bellows pressure may be required if the autoclave pressure drops. Drops in the autoclave pressure must be compensated for rapidly by decreasing the bellows pressure so that the bellows pressure is always within the range of 2250 - 2750 psig greater than the autoclave pressure. In f act, the autoclave contents could become 2-phase on cooling if the contraction of autoclave water is not overcome rapidly enough by the pump rate through the leak, and the autoclave pressure will drop. When this happens, simply lower the bellows pressure so that it is not above 2750 psig more than the autoclave nor below 2250 psig more than the autoclave, and log all, changes:

time, temperature and pressures.

(7e) At 130 + 5*F, maintain or restore the 1760 psig autoclave and system pressure followed by decreasing the bellows pressure to 2900 psig, while maintaining continuous circulation. (7f) Maintain parameters of (7e) for a minimum of 1 week. 1029c/0150c/010684:5 122

8. Reheat to (60015) *F and hold. (8a) Heat to (600 + 5) *F at (100 + 50) *F/hr maintaining 1760 psig autoclave pressure and the required differential pressure on the bellows for the 500 lb load (see Step 5). Specifically, the bellows total pressure should always be between 2790 and 3010 psig (2900 psig nominal) for the autoclave pressure of 1760 psig (this gives ~ the 1140 1 110 psig differential bellows pressure of Step 5. (8b) Hold at (60015) *F for 1 month minimum. 9. Initiate cooldown. (9a) Repeat Steps (7a) and (7b). (9b) Cool to ambient. Follow steps (7c) and (7d) except take temperature to ambient. l (9c) At ambient, repeat Step (7e), by restoring autoclave to 1760 psig if necessary and lowering bellows pressure to 2900 1 110 psi. Maintain circulation. l l

10. Maintain conditions of (9c) and (10a)

Vent MUT H overpressure. 2 with continuous venting for a (10b) Sparge MUT solution with N2 from the gas space of the minimum of 15 minutes to purge H2 MUT. (10c) Sparge air at atmospheric pressure into MUT. (10d) Maintain aerated MUT at atmospheric pressure. 11. Circulate under conditions of (10d) for a minimum of 2 oays,1760 psig aqueous pressures, 2900 psig bellows pressure. 1029c/0150c/010684:5 123

12. D: pressurize all systems, stop circulations, open autoclave and remove samples for inspection.

The above 12 steps cover the first Operations Cycle of GPU SP-1101-22-008, Rev.1, on Lead Tests, their Paragraph 4.5.3.8, Steps 14-26. GPU SP-1101-22-008, Rev.1, Paragraph 4.5.3.8', Steps 27-30 are repeat operations. Each GPU step requires all 12 of the above Westinghouse steps, except that their Step 30 requires 2 of our 12 steps. Note from GPU SP-1101-22-008, Rev.1, that the make up tank chemistry is the only variation from GPU step to step. 10.3 Methods for Preparation of Stock and Makeup Tank Solutions For preparation of all solutions, except boric acio solutions, reagent grace chemicals will be used. Special Quality Grade * (Nuclear Grade) H3 0' 3 with a maximum sulf ate concentration of 0.00016 percent (1.6 ppm) will be'used to prepare all boric acid solutions in the LTCT program. Weignings will be made on an analytical balance for all weights below 50g. Over 50 g, a top loading balance will be used. Deionized water with a conductivity of -0.1 u ho (when deaerated) will be used m for dilution. Graduates.and storage (holding) tanks will be of polyethylene. One liter stock solutions,1000 ppm in respect to the anion, will be volumetrically prepared for sodium fluoride, sodium chloride, sodium thiosulf ate and sodium sulf ate. The lithium hydroxide stock solution will be 5000 ppm in respect to lithium. Aliquot volumes will be pipetted from the stock solutions for individual make up tank solution preparations. The orothoboric acid will be weighed and dissolved in approximately 201 of demineralized water. This solution will be placed in a 50-1 polyethylene

U.S. Borax and Chemical Corp.

1029c/0150c/010684:5 124

holding tank, along with the required aliquot volum:s of the specified anion and cation stock solutions and diluted to 501 with additional water. Due to problems associated with the loss of fluoride and hydrazine in the holding tanks, F, hydrazine, and Cl will be added to the MUT ouring the transfer process just prior to test startup. The 501 test solution will be deaerated (and mixed) by sparging with nitrogen; the sparging tube (stainless steel or Inconel 600), of sufficient length to extend to the bottom of the tank, will be manually swirled several tinies to compliment the mixing by sparging. The 50 1 of solution will be stored under continuous nitrogen sparging in the holding tank until ready for A minimum of 4 hours of sparging is required to provide mixing and use. deaeration of the solution. ) 10.3.1 Preparation of Stock Solutions Lithium Hydroxide (LiOH) Dissolve 30.2262 g LiOH*H O in deionized water in a 1-1 polyethylene 2 volumetric flask, and add sufficient water to make 1.01. LiOH will be weighed on an analytical balance. Lithium concentration is 5000 ppm. Solution will be stored ~1n a polyethylene bottle. Sodium Fluoride (NaF) Dissolve 2.2102 g. NaF (weighed on an analytical balance) in a 1-1 polyethylene volumetric flask partially filled with deionized water; ada sufficient water to make 1.0 1. The solution will be stored in a polyethylene bottle. The fluoride concentre; ion is 100D ppm. Sodium Chloride (Nacl) Dissolve 1.6485 g Nacl (weighea on an analytical balance) in a 1-1 Aaa polyethylene volumetric flask, partially filled with deionized water. water to make 1.0 1. The solution will be stored in a polyethylene bottle. The chloride concentration is 1000 ppm. 1029c/0150c/010684:5 125

1 Sodium Thiosulf ate (Na 5 0 '5H 0) 2 3 2 'Dissolvs.1.2918 g Na 5 0 '5H 0.(weighed on an analytical balance) 223 2 'in a 1-1 polyethylene volumetric _ flask partially filled with deionized water. Add enough water to make 1.0 1. The solution will be stored in a polyethylene 2 bottle.. -The solution will contain an equivalent of 1000 ppm 50 Sodium Sulfate (Na 50 '10H 0) 2 4 2 Dissolve 3.3540 g Na 50 *10H O (weighed on an analytical balance) in 2 4 2 a 1-1 polyethylene volumetric flask partially filled with deionized water. Add enough water to make 1.01. The solution will be storea in a polyethylene 2 bottle. The S0 concentration is 1000 ppm. a k. s \\ 6 4 s. \\ r 1029c/0150c/010684:5 126

10.3.2 Lead Test Solutions HFT Solution 1 - Thiosulf ate dosed RCS. HFT Solution 2 - Sulf ate dosed RCS. Weigh 672.1 g orthoboric acid (2350 ppm B equivalent) for each Solution.

Dissolve in 201 deionized water and place in 50-1 polyetnylene storage tank for each Solution.

add 5 m1 stock (1000 ppm equivalent 50 ) Na2 2 3 solution 30 4 to Solution 1 only, add 5 ml stock (1000 ppm 50 ) Na2 2 4 solution to Solu' tion 2 50 4 only. add 23 mi stock (5000 ppm Li) LiOH solution to each Solution. Add sufficient deionized water (-301) to bring total volume up to 501 for each Solution. Add 0.7210 g of 65 percent aqueous hydrazine solution, 5 ml stock (1000 ppm F) NaF solution, and 5 m1 stock (1000 ppm Cl) Nacl solution to the in-line addition vessel prior to solution transfer from the storage tank to the MUT. Calculated solution concentration (ppm): l B = 2350 Li = 2.3 F = 0.1 C1

0.1 0.1 504

Hydrazine = 6 Sufficient water will be used initially to dissolve easily the orthoboric acid. Enough additional water 1 -301) will be added to attain the 501 desired volume. Target value. Permissible range = 2-10 ppm. 1029c/0150c/010684:5 127 t-r r-i -e-

s 10.3.3 Lead Test Operations Cycle Solutions Cycle 1 Weigh 343.2 g orthoboric acid for each Solution.

Dissolve in 201 deionized water and place in 50-1 polyethylene holding tank for each Solution.

add 5 mi stock (1000 ppm 50 ) Na2 2 3 solution to Solution 1 only, 30 4 solution to Solution 2 only, add 5 mi stock (1000 ppm 50 ) Na 504 4 2 add 23 mi stock (5000 ppm Li) LiOH solution to each Solution. ~

Add sufficient deionized water (-301) to bring total volume to 501 for each solution.

Add 0.7210 g of 65 percent aqueous hydrazine solution, 5 mi stock (1000 ppm F) NaF solution and 5 mi stock (1000 ppm Cl) Nacl solution to the in-line addition vessel prior to soluton transfer from the storage tank to the (tVT. Calculated solution concentration (ppm): B = 1200 Li - 2.3 F = 0.1 Cl = 0.1 504 = 0.1 Hydrazine - 6 Target value. Permissible range 10 ppm. 1029c/0150c/010684:5 128

Cycle 2 Weigh 286 g orthoboric acio for each Solution.

Dissolve in 201 deionized water and place in 50-1 polyethylene holding tank for Solution 1 and Solution 2.

add 5 mi stock (1000 ppm F) NaF solution to each Solution. add 5 mi stock (1000 pom Cl) Nacl solution to each Solution. solution to Solution 1 only. add 5 m1 stock (1000 ppm 50 ) Na 5 0223 4 add 5 m1 stock (1000 ppm S0 ) Na250 solution to Solution 2 only. 4 4 add 18.5 mi stock (5000 ppm Li) LiOH solution to eacn Solution.

Add sufficient deionized water (-301) to bring total volume to 501 for each Solution.

Add 0.7210 g of 65 percent aqueous hydrazine solution, 5 mi stock (1000 ppm F) NaF solution and 5 ml stock (1000 ppm Cl) Nacl solution to the in-line addition vessel prior to soluton transfer from the storage tank. to the MUT. Calculated solution concentration (ppm): 8 - 1000 Li = 1.85 F = 0.1 Cl - 0.1 504 =.0.1 Hydrazine = 6 Target value. Pemissible range = 2-10 ppm. 1029c/0150c/010684:5 129

Cycle 3 Weigh 143 g orthoboric acid for each Solution.

Dissolve in 201 deionized water and place in 50-1 polyethylene holding tank for each Solution.

add 5 mi stock (1000 ppm 50 ) Na2 2 3 solution to Solution 1 only. 30 4 add 5 al stock (1000 ppm 50 ) Na250 solution to Solution 2 only, 4 4 add 11.5 mi stock (5000 ppm Li) LiOH solution to each Solution.

Add sufficient deionized water (-301) to bring total volume to 501 for each Solution.

Add 0.7210 g of 65 percent aqueous hyorazine solution, 5 m1 stock (1000 ppm F) NaF solution and 5 mi stock (1000 ppm Cl) Nacl solution to the in-line addition vessel prior to soluton transfer from the storage tank to the MUT. Calculated solution concentration (ppm): B = 500 Li = 1.15 F = 0.1 C1 = 0.1 504 - 0.1 Hydrazine - 6 Target value. Permissible range = 2-10 ppm. 1029c/0150c/010684:5 130

Cycle 4, Cycle 5, Cycla 6 Weigh 28.598 g orthoboric acid for each Solution.

01ssolve in 201 deionized water and place in 50-1 polyethylene holding tank for each Solution.

ada 5 mi stock (1000 ppm 50 ) Na2 2 3 solution to Solution 1 cnly. 50 4 solution to Solution 2 only. add 5 mi stock (1000 ppm 50 ) Na 504 4 2 add 8.5 ml' stock (5000 ppm Li) LiOH solution to each Solution. j

Add sufficient deionized water (-301) to bring total volume to 501 for each Solution.

Ada 0.7210 g of 65 percent aqueous hydrazine solution, 5 m1 stock (1000 ppm F) NaF solution and 5 mi stock (1000 ppm Cl) Nacl solution to the in-line addition vessel prior to soluton transfer from the storage tank to the MUT. Calculated solution concentration (ppm): B = 100 Li = 0.85 F = 0.1 C1 = 0.1 504 = 0.1 Hydrazine = 6 Target value. Permissible range = 2-10 ppm. I' 1029c/0150c/010684:5 131

10.4 Procecures Usid During Hydrogen Paroxide Test Operations 10.4.1 Test Loop Operations 1. Prepare 50 L of a deoxygenateo solution with the nominal test composition 2 (2350 j; 50 ppm B, 2.0 j; 0.2 ppm LiGH,100 j; 50 ppb 50 and pH 8.1 j; 0.1 adjusted with ammonia) and transfer to the MUT using standard metnoos already established for these operations. Prepare an additional batch of 4 L (or more) for filling autoclaves (Step 6). NOTE: From this point on in the test procedure it is important to accurately measure 'and record the volume of all solutions either added to or removed from the loop. All residual analytical chemistry samples should be retained following the analysis, with an analytical chenistry proceoure record of how much (volume or weight) of the submitted sample was actually consumed by the analytical procedure. Any other effluent samples (for pH, etc.) shoulo also be retained. A record should be kept of the amoung uf solution adoeo to the MUT and the time of addition. 2. Sparge the MUT for the standard time interval to assure that the solution is oeoxygenated. 3. Initiate flow through the bypass leg (with specimens isolateo) at maximum flowrate. 4. Maintain maximum flow conditions and sample the MUT hourly until two successive samples show that the pH and conductivity are stable - pH within specified range and measur.ed conductivity remains j; 2 umho. Make additions of the ammoniun hydroxide stock solution, as required, to maintain pH in specified range, level by IC. 5. Sample the MUT for determination of baseline 504 1029c/0150c/010684:5 132

v 6.

Fill thn autoclavcs with tha additional makeup solution of Step 1 and pipe-in the sample stringers. Note that the sample stringers go in test with the' "as-is" inside surf ace condition (no' pre-test rinsing or flushing) Maintain sample inlet and outlet valves closed and bypass valves open at this step, leaving air in the sample stringers. 7. Prior to initiating flow through the specimens, set the back pressure regulator in the pressu're relief / drain line of each autoclave at 400 psig and heat autoclave to 130 + 5*F. 8. Initiate recirculation flow through the ' specimens at the maximum flow rate achievable. The entrapped air. in the specimens will be pushed out and on into the makeup tank. 9. Adjust and balance temperature-flow values using heating tapes, ano - if i necessary - flowrate adjustments. 10. For the autoclave containing the 2 repair test specimens, apply 1155 psig total pressure to the bellows. (This gives a AP between the bellows and the autoclave bulk, which is at atmospheric pressure of 1140 psi, which, ' acting on the 0.44 in area of the bellows, applies 500 lb axial load on the samples).. l 11. For the autoclave containing the full section le&d test specimen, the f autoclave may begin to fill with primar solution through a possible leak. If this occurs, autoclave pressure will rise to 320 psig. The bellows pressure should thew be increased to 1460 psig total bellows pressure (this gives a AP between the bellows and the autoclave bulk of l 1140 psi which produces a 500 lb axial load on the sample. If the 400 psig primary pressure is insufficient to cause a primary to secondary leak, the bellows pressure should be set at 1155 psig as in Step 10.

12. -Using the value of the solution volume in the loop (see Step 1), add the required volume of the hydrogen peroxide stock solution to the MUT by way of the addition bomb to produce a MUT concentration of 20 ppm.

1029c/0150c/010684:S 133

Ten minutes af ter the peroxide addition, sample the MUT to verify that the desired peroxide concentration has been achieved. If peroxide concentration is not correct, continue to cir:ulate and adjust peroxide'.

13. When stable peroxide concentration, flowrate, and temperature are achieved on both systems, the 500 hour cleaning cycle has begun.

Sample the MUT and autoclave effluent and determine pH and H 022 concentration. I 14. Until the H 0 consumption rate and the stability of the pH is 22 determined, sample the MUT and autoclave effluent hourly

and perform H0 concentration and pH measurements. Measure and record the data, 22 hour and volume of af flushing and sampling volumes and of all volumes of additions to the loop, and maintain a continuous current record of the volume of solution in the loop for the entire duration of the test.

15. After conditions have stabilized and/or consumption rates have been determined, institute the reduced frequency of analyses which insures is maintained in the MUT. Continue the that 15-20 ppm H 022 operations for the remainder of the 500 hour test. 10.4.2 Procedure for H 0 Analysis Using Peroxide Kit HP-50 2 -2 Test Method. The HP-50** kit employs the reagent ammonium thiocyanate plus ferrous iron in acid solution to give a red-orange color with hydrogen peroxide. The test is based on the oxidation of ferrous iron to ferric iron by peroxide with the formation of the intensely colored ferric thiocyante complex.

At the beginning of the test cycle, peroxide analyses of effluents shoud be conducted more frequently than hourly, until it is established that the hourly rate is sufficiently frequent to track peroxide consumption.
- CHEMetrics, Inc., Warrenton, Va.

s 1_Q2_9210_150@ /0__106_84 : 5 _338__ _______ ______ _ ____ __ f

( Sample Preparation. ( 1. Measure 5.0 m1 of loop water into the " snap-cup" using the precalibratec t sampling syringe. I 2. Add two drops of 20 weight percent sulf amic acid solutione 3. Oilute to 25 ml with distilled water. NOTE: Each sample to be analyzed with this kit must be diluted, as above, prior to analysis with the kit. Analysis Procedure. 1. Insert the ampoule tip into one of the four depressions at the bottom of This the snap-cup and squeeze the sm3oule toward the side of the cup. movement will break the ampoule tip. The simple fluid will fill the ampoule, mix with the reagent, and form a colored solution whose intensity corresponds to the concentration of peroxide. A small bubble will remain in the tube. 2. Remove the ampoule and cover the tip with a finger. Invert the CHEMET several times, allowing the bubble to travel from end to end each time. (A protective cot may be used to prevent skin puncture.) Use the appropriate comparator to determine the level of peroxide in the sample. Readings should be taken no longer than 30 seconds after the CHEMET has been fired. 10.4.3 Procedure for Preparation of 50,000 ppm H 0; Stock Solution. g 1. Measure out 150 cc of 30 percent H 0 * (0.334 g H 0 /ml) solution. 22 22

DuPont " Perone" 30 EG Hydrogen Peroxide.

~ '1029c/0150c/010664:5 135

2. Quantitatively transfer to a 1 liter polyethylene volumatric flask, and dilute to one liter. Stopper and invert several times to assure mixing is complete. 3. Using a micropiet transfer 50 ul of the solution prepared in step 2 to another polyethylene volumetric flask, and dilute to one liter. Stopper and mix. (The concentration of this solution sh'ould be 2.5 ppm H 0 )* 22 4. Analyze the solution prepared in Step 3 using the CHEMetrics hydrogen peroxide analysis kit, 5. Calculate the concentration of the stock solution prepared in Step 2 using the following expression: C,. 1000 Cs" G s where a the concentration of the H 0 stock solution in ppm, C 22 = s the H 0 concentration determined by use of the CHEMetrics C, = 22 H0 analysis kit (Step 4) 22 the volume of the stock solution used to prepare the solution V = 3 in Step 3. 6. Label the stock solution prepared in Step 2 with the date and the concentration calculated in Step 5. 1 7. At least once each week, redetermine tile concentration of the stock solution by the procedure described in Steps 3 through 6. NOTE: Since hydrogen peroxide will decompose in bright light, store the stock solution in a dark place when not being used. 1029c/0150c /010684: 5 136

10.4.4 Procedura for the M 'en of Amonium Hydroxiom to the Loop 1. Withdraw 500 ml of solution from the loc,p using the effluent sample tap. 2. Adjust loop flow so that the chemical addition bomb is isolated. 3. Pressurize the sampling bomb from the top within nitrogen. The pressure appliec must be greater than the pressure in the MUT. 4. Open the valve at the bottom of the bomb to allow any solution in the bomb to be forced into the MUT. The bomb will be empty when pressure in the MUT begins.to rise. At that point close the valve at the bottom of the bomb. 5. Bleed the MUT nitrogen pressure back to the amount maintainea during normal operations. 6. Shut the valve at the *.op of the addition bomb and disconnect the nitrogen supply. 7. Connect the vacuum source to the valve at the to of the addition bomb. Open the valve and.begin to evacuate the bomb. 8. Calculate the volume of concentrated ammor.ium nydroxide (14 M) requireo to increase the inop pH by using the titration curve (Figure 10-1) and the following formula: present pH) ~ *I A" L (* desired pH

where, The. volume of 14 M NH 0H (ml) to be added, V

4 A= The volume (liters) of solution in the loop, Vt-the reading derived from Figure 1 which corresponds ml desired' pH = to the desired pH, ~1029c/015Cc/010684:5 137

the reading derived from Figure 1 t:hich corresponds i ml = present pli to the.present pH. NOTE. To avoid adding excess NH 0H and producing a higher pH than,desireo, f 4 adjustments should initially be made to the bottom of the 8.0 to 8.2 pH control range. After experience with the system and the procedure is achieved, adjustment to the middle of the pH range should be attempteo. 9. To -250 ml of the solution removed from the loop in step 1), add the volume of the 14 M NH 0H solution calculated in step 8). 4 10. Shut the valve at the top of the chemical addition bomb, and suck the solution centaining the NH 0H into the bomb by opening the valve at the 4 bottom of the bomb.'

11. When all of the NH 0H containing solution has entered the bomb, rinse 4

the container with the remaining 250 ml of loop solution from step 1), and suck this solutien into the sampling bomb. 12." Make sure that addition valves at the top and bottom of the bomb are closed, then divert loop flow through the bomb and flush bomb contents into the MUT. 13. Allow 15 minutes to assure mixing and then sample the MUT. Determine pH to assure that the desired increase has been achieved. 10.4.5 Procedure for the Manual Addition of Hydrogen Peroxide to the Loop 1. Withdraw 500 ml of solution from the loop using the effluent sample tap. 2. Adjust loop flow so that the chemical addition bomb is isolated. 3. Pressurize the sampling bomb from the top with.o nitrogen. The pressure applied must be greater than the pressure in the MUT. 1029c/0150c/010684:5 138

4 Open the valve at th2 bottom of the bomb to allow any solution in the bomb to be forced into the MUT. The bomb will be empty when pressure in the MUT begins to rise. At that point close the valve at the bottom of. the bomb. 5. Bleed the MUT nitrogen pressure back to the amount maintainea curing normal operations. 6. Shut the valve at the top of the addition bomb and disconnect the nitrogen supply. 7. Connect the vacuum source to the valve at the top of the addition bomb. Open the valve and begin to evacuate the bomb. stock solution (nominally 50,000 8. Calculate the amount of the H 022 ppm) required to change the loop concentration to the desired amount using the following expression: AC. VL VA" G s

where, 4 = the volume of stock solution (liters) to be Ljded to the loop, V

concentration, in ppm, aC = the desired increase in loop H 022 L = the volume, in liters, of solution in the loop, V stock solution, in ppm. C = the concentration of the H 022 s 9. To -250 ml of the solution removed from the loop in step 1), add the lution calculated in step 8). volume of the H 0 L p2 10. Shut the valve at the top of the chemical addition bomb, and suck the into the bomb by opening the valve at solution Ontaining the H 022 the bottom of the bomb. 1029c/0150c/010684:5 139

~ 11. Knen all of the peroxide containing solution has entered the bomb, rinse the container with the remaining 250 ml of loop solution f rom step 1), ar.c suck this solution into the sampling bomb. 12. Make sure that addition valves at the top ano bottom of the botb are closed, then 01 vert loop flow through the bomb ano flusn bomb contents itito the MUT. 13. Allow 15 minutes to assure mixing and then sample the MUT. Analyze for concentration nas been h;0 to assure that the desired H 022 2 achieved. NOTE: Hyorogen peroxiae.adoitions to the loop should only be maoe when loop pH is >7.0 to avoid decomposition. l'J. 4. 6 Proceoure for Loop Shutoown 1. At the completion of the 500 hour peroxide exposure (4:20 p.m. on harcn . 15, 1983), sample the make-up tank (MUT) solution for (a) peroxiae analysis, and (b) ion chromatographic sulf ate analysis. 2. Terminate peroxide additions. 3. Retain 500 pound load on specimens and ae-energize all loop heaters. 4 While maintaining flow through the specimens at the specified test flowrate, sample the MUT solution. hourly and analyze for peroxioe for the initial 2-3 hours of the cooldown perioc. 5. Maintain flow through the specimens overnight. Twenty-four hour surveillance during the cooldown is not rcquired. However, prior to leaving the laboratory for the evening, sample the MUT for peroxiae and sulf ate analyses. j

On the following morring, again sample the MUT for peroxide and sulf ate e. analyses. Terminate flow and reauce pressure on both tne bellows and the remaincer 7. of the locp system. Drain the contents of each autoclave into separate labeled containers and S. retain for further analysis at a later time. Open the autoclaves, disconnect the sample train, and crain solution from 9. Set each sample train into separate, appropriately labelea containers. aside for further analysis at a later time. Transfer specimens to appropriate location for post-test examinations. 10. Retain for 11. Drain MUT anc remainder of loop into labelea containers. subsequent post-test analyses. l 1029tIQ150cLO10684: 5 141 1

10.5 Operating Conoitions f o'r Loop 1 and 2 Through Operations Cycle 2. Operating temperatures, ' pressures, and flowrates for lead Test i (Loop 1) as measurec during the HFT cycle and Operations cycles 1 ano 2 are presente: monthly tabulations in Tables 10-1 through 10-6. Plots of the correspor.cing temperature and pressure data for the months of Novemoer,1962 through f*ay, 1953 are presented in Figures 10-2 tnrough 10-8. The analogous cata f or Test 2 (Loop 2) are presented in Tables 10-7 through 10-13 anc Figures 10-9 throsgn 10-15, respectively. 1029c/0150c/010684:5 142

The horizontal scale represent a depth below the surf ace, baseo on a knowr. sputtering rate of 50 A/ min (Ref erence 14). For eatr. curve in Figure 10-16, the f ractional area cf a 10 nm slice was Tne total area uncer the curve compared with the total area under the curve. represents a known quantity of sulfur and the fractional areas are proportional to the f raction of sulf ur atoms stopped within each slice. Table 10-14 summarizes the results of the calculation. Tne concentration of 5 in eacn slice is calculated from the f ormula (10.4-2) s " 2#0t/II' + 2f6t) x where t = ion fluence-(ions /cm ) or total dose f = f raction of ions stoppec within the selectec slice (Table 1)

t. = number of non-sulf ur atoms witnin tne slice (estimatec at 16 9 x 10 atoms, based on pure nickel)

By plotting normalized peak-to-peak heights (Equation 10.4-1) vs. sulf ur concentrations (Equation 10.,4-2), a calibration curve for sulfur analysis is obtained (Figure 10-17). The calibration curve of Figure 10-17 is casec on 15 16 tne data obtained from tne standaros with 5 x 10 and 1 x 10 2 The data for the third standard need to be correctea for sulfur ions /cm. loss due to sputtering during ion implantation, an eff ect tnat can be i neglected f or the lower fluences. Determination of Detection Limits When the sulfur peak-to-peak height becomes less than twice the noise level in the derivative Auger spectrum, the apparent sulfur concentration may be 100 percent in error and that concentration constitutes the instrumental detection Lower concentrations will go undetected or will be determined with limit. The instrumental detection limit for tnis very low accuracy if detected. investigation is encountered at the last point of each of the curves in From Table 10-14, the corresponding number of s atoms is Figure 10-16. 15 13 calculated to be 0~.006. x 5 x 10 x 2 - 6 x 10 atoms in a 10 nm slice.

2 Tnis is converted to ug/cm by multiplying the number of atoms by tne mass -2 of a sulf ur at m (1.66 x 10 kg x 32). The result is a detection lit.it of 3 x 10-3, fc,2 in a 10 nm slice. Analysis of Concitioned Samoles Six areas were analyzec on Inconel 6CO samples cut from TMI-1 OTSG tuoes whicn had been subjected to elevated temperature conditioning in simulatec reactor coolant chemistry. ho sulfur was detected in any of tne specimens at any depth level, bat all areas showed significant boron levels. The baron signal in the Auger spectrum consisteo of two peaks, the main peak at 170 eV anc a secondary peak at 152 ev. The peak-to-oeak height of tne secoridary peak was about half that of the main peak. Normal boron signals consist of only one peak at 179 eV. The reason for the shift ar,d the appearance of a secono peas is not clear at this time. One possibility is that a baron-compound was f ormec, but the compound has not been identifiec. because of the proximity of the second boron peak and the sulfur signal, X-ray photoelectron spectroscopy (XPS) was used to differentiate between sulfur anc boron. The XPS boron signal consisted of a single line indicating a is binding energy of 190.9 eV. No sulfur was oetected by XPS. Inis limits tne 2 amount of sulfur that might have been present to 0.15 ug/cm in the first 100 nm below the surf ace and to one tenth of that amount within tne first 10 nm below the surf ace. i The Auger analyses are summarized in " composition tables" attacneo to the report. The compositions given are essential.ly normalized peak-to-peak heights (similar to Equation 10.4-1, for each element) and not calioratec. They give, however, some qualitative idea of how the composition changes with sputtering time. The sputter rate used was 5 nm/ min. Summary Calibration curves for AES analysis of sulfur in Inconel 600 are available. Unfortunately, the presence of an unidentified boron compound makes the use of AES on the GPU-N tubes undesirable, at least for sulfur analysis. XPS is less

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1 i AUTOCLAVE #31' NOVEMBER 1982 4999 1 i 3998 i Pb PRESSURE (PSD 2ses i Pe S. Pa PRESSURE (PSD I' 4 1998 ra 1 } AUTOCLAVE TEMPERATURE (F i B I 2 4 6 8 18 12 14 18 18 28 22 24 26 28 38 l DAY FIGURI! 10-2 NOVINBliR OFliRATING CONDITIONS FOR TliST I t

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AUTOCLAVE #31 MONTH OF FEBRUARY i 4000 mutuows e-R u m m u M a crer> \\ ~ -~ 3500 - ~~ 3000 - l 2500 '^"" """""""" """**

- - - "" * ^"'

l 2000 1 1500 1000 T mMf*mR ATUM E C fr > AUTOCLAVm 500 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 g DAY FIGURl! 10-5 FEllRllARY OPERATING CONDITIONS R)R TFST 1

AUTOCLAVE #31'M0' NTH OF MARCH =- 5000 I ti l 4ese 3 BELLOWS PRESSURE (PSI) i ~ l i. 3909 AUTOCLAVE & SYSTEM PRESSURE (PSI) 2988 .Z. 1998 AUTOCLAVE TEMPERATURE (F) i 1 l i l a g 2 4 8 8 18 12 14 18 18 29 22 24 28 29 39 DAY FIGURE 10-6 MARGl OPERATING CONDITIONS FOR TliST 1 s

AUTOCLAVE #31 MONTH OF APRIL sees i i j 4900 - Pb PRESSURE (PSI) I 3BBS 1 t i P & Pa PRESSURE (PSI) 2000 l 1960 AUTOCLAVE TEMPERATURE (F) f l g_ 2 4 6 9 19 12 14 16 19 29 22 24 26 28 3B DAY \\ FIGlJRE 10-7 APitII, OPlillATING CONDITIONS FOR Tl!ST 1

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AUTOCLAVE #29 MONTH OF FEBRUARY 4000 asee - g .. m _. ....m.. 3000 - I I 2500 I l

.: w:;r'^=

I l 2000 l I 1500 I j l i l 1000 Aurocueva rasranaruna <w> t l 500 I i H g 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 DAY FIGlRE 10-13 FEBRUARY OPERATING CONDITIONS FOR TEST 2

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TABLB N OPERATING PARAMETERS FOR TEST LOOP 1 JTOCLAVEt31 TMI LEAD TEST #1 JVEMBER 1982 iY TIME' Ps Pa Pb Pmut AC T MUT T MUT LEVEL EFFLUENT F PSI PSI PSI PSI F F INCHES ml/hr b53 905 O.' O O 12 69 69 21.4

I 1.

955 1120 1120 0 12 69 69 4 1003 .1120 1120 2260 12 69 69 1029 1120 1120 2260 12-155 70 21.3 ~53

5 740 1120 1120 2260 13 153 73 20.3 51 3

745-1120 1120 2260 13 153 73 <3 .1200-1120 1120 2260 13 545 73 3-1400 1120 1120 2260 13 545 73 4 744 1120 1120 2260 i3 549 74 19.0 85 r

4 846 1120 1120 2260 13 445 74
4-945 1120 1120 2260 13 550 74 4

1030 1120 1120 2260 13 448 74 4 1130 -1120 1120 2260 13 550 74

4 1230-1120 1120 2260 13 453 74 4

1330 1120 1120 2260 13 548 74 - 4 1430 1120 1220 2260 13 450 74 4 1525 1120 1120 2260 13 550 74 ' 5 727 1120 1120 2260 13 548 72 17 8 *. 93 3 734 1120 1120 2260 13 549 71 14.3 86 * ? 733 1120 1120 2260 13 550 72 13.1 96 3 734 1120 1120 2260 13 550 71 12 0 101

1 728 1120 1120 2260 13 550 72 10.8 94 1

800 1120 1120 3400 13 550 72 1 1300 1120 1120 3400 13 132 72 1 ~1305 1120 1120 2260 13 13 2 72 1 1515 1120^ 1120 2260 0 131 70 10.0 101 2 738 1120 1120 2260 0 132 70 9.1

105 5-725 1120 1120 2260 0

131 74 28.8 98 6 720 1120 1120 2260 0 130 73 27.5 102 6 -1420 1120 1120 2260 0 130 73 6 1420 500 500 2260 0 130 73 6 1421 1120 1120 2260 0 130 73 7-1120 1120 1120-2260 0 131 73 36 3 98 8 738 1120 1120 2260 0 132 72 24.9 99 9~ 735 1120-1120 2260 0 131 72 23.8 102 2 720 1120 1120 2260 0 130 72 19.8 98 3 735 1120 1120 2260 0 130 72 18.6 97

4 725 1120 1120 2260 0

130 72 17.3 98 4 950 -1120 1120 2260 0 130 72 4 955 0 'O O O O 72 OTE D** INDICATES MUT OR EFFLUENT SAMPLE TAKEN OMMENTSi AY MUT. SAMPLE'PH-5.6 CONDUCTIVITY 68 uGHM i MUT OPENED TO ATMOSPHERE 2' MUT REFILL-

TABUE 10-2 OPERATING PARAMETERS FOR TEST LOOP 1 TOCLAVE631 TMI LEAD TEST #1 CEMBER 1982 Y TIME Ps-Pa Pb Pmut AC T MUT T MUT LEVEL EFFLUENT F PSI PSI PSI PSI F F INCHES ml/hr v. 1125 01 0 0 15 66 66 20.5

c72 1330 1760.

1760 0 15 66 69 1332 1760 1760 3510 15

66 69 a

1335 1760 1760 3510 15 o8 69 1422 1760 1760 3510 15 148 69 745 1760 1760 3510 15 149 73 19.8 62 750 1760 1760 3510 15 149 73 1258 1760 1760 3510 15 600 73 840 1760 1760 3510 15 603 75 15.3 77 905 1760 1760 3510 15 603 75 1005 1760 1760 3510 15 499 75 820 1760 1760 3400 15 500 72 14.1 64 835 1760 1760 3400 15 500 72 1020 1760 1760 3400 15 600 72 1515 1760 1760 3400 15 600 72 800 1760 1760 3600 15 602 82 13.0 64 830 1760 1760 3600 15 602 82 1000 1760 1760 3600 15 502 82 820 1760 1760 3300 15 495 84 11.9 98~ 835 1760 1760 3300 15 495 84 1020 1760 1760 3300 15 ~ 596 84 TE *** INDICATES MUT OR EFFLUENT SAMPLE TAKEN

' OPERATING PARAMETERS FOR TEST LOOP 1 'CLAVLt31' TMI. LEAD TEST-#1 ~ 4ARY 1Y83-1Ihf P5 -Pa Pb Pmut AC T riUT T MUT LEVEL EFFLUEN1 Fi-PSJ PSI PS.I PS1 F F INCHES ml/hr 735 .17o0 17eO 3600 15 o01 82 8.8 T20 v. h-746 1760 - 1760 36no 15 601 82 ~925 17eo 1760 3600 15 503 82 '92 '1014' r/co. 1?60 3000 15 502 81 7.5 1016-17eo 176v 3500 15 502 81 1150 lico 17'60 3600 15 597 81 31 0

92 740 1/oc 1/60 3500 15 602 80

'1020 1>oO 1760 3500 15 602 80 1220 1760 1/60 3500 15 501 80 78 725 1760 17o0' 3500 15-500 81 20.8 1010 1760 1760 3500 15 500 81 1140 1760 1760 3500' 15 599 81 720 1/60 1760 3500 15 SY7 78 27.5 62 735 1/ob 1760 3500 15 597 78 .100b 11oo '1760 3500 15 505 78 735 1760 1750 3475 15 501 79 24.0 110 74a 2}no 1750 3475 15 5'01 79 .900 17bo 1750 3475 15 600 79 73b-1/60 1/60 3400 15 597 79 22.9 89 745 leoO 176u 3350 lb 600 79 21.6 96 7a5 17n0 )}so 3150 15 598 79 ' 20.5 115 742-1290' 1760 2V50 15 600 79 19 5 120 Iv4e 1760 1760 3350 15 600 79 74d 17o0 17eo 2825 15 600 79 15.8 97 4 810 1760 1760 2925 15 o00 79 /4v 17eO 17o0 2700 15 596 77 15.o 99 ?40 1760 -1760 2b25 15 602 79 13.5 Y4 Vib 1760' 1760-3510 15 602 79 '750 1760. 1760 3510 15 SF9 76 12 3 116 755 1760 3260 3510 15 598-78 11.3 115 7.8 86 745 17o0 1/60 3510 15 599 78 th o 17eo 3760 3510 lb 599 , 78 810 1760 ivoc 4/Y5 15 599 78 '1430 i ~e 6 e 1/co 4)v5 15 131 78 ~6 1510 17eO 1/co 4/Yb 15 131 7E i 1510 1/ou 1760 3510 15 131 78 s-1545 17oo' 1760 3510 15 131 73 70 79 732 1760 17eo 3510 15 131 71 6.5 91

2 -

740 1760 1760 3500 15 131 70 5.0

95 7-73b-1/ou 1760 3510 lb 133 70 3o.3 90 i

-745 3720 1760 3500 15 133 72 2b.3 90 -1 730 1760 1760 3500 15 131 73 22.0 91 740 1760 17eo 3500 15 131-73 1 1400 1760 1760 3500 15 596 73 r OTE '** INDICATES MUT OR EFFLUENT SAMPLE TAKEN OnMEN1Si .AY MUT REF1LL (50L) ' BELLOWS N21kDGEN SUPPLY LOW .1 N MUPPLY RESTORED

-OPERATING PAkWrERS FOR TEST IDOP 1 AUTOCLAVE #31 THI: LEAD TEST #1 FEBRUARY 1983 EFFLUE T'7 LOW DAY TIME Ps Pa Pb Pmut AC T HUT T NUT LEVEL PSI PSI PSI PSI F F INC'HES ml/hr 1 735 1760 1760 3510 15 S90 77 21.0 104

2 800 1760 1760 3510 15 605 78 17.9 101 3

745 1760 1760 3500 15 597 80 18.5 79 4 808 1760 1760 3510 15 599 78 17.5 117 7 745 1760 1760 3500 15 600 79 14.5 100 8 735 1760 1760 3510 15 601 84 13.5 128

9 745 1760 1760 3510 15 604 84 12.3 134
10 735 1760 1760 3510 15 596 84 11.3 99 11 805 1760 1760 3510 15 604 84 10.1
75 l

14 747 1760 1760 3500 15 603 81 27.3 88 l 15 734 1760 1760 3510 15 603 82 26.3' 92 16 805 1760 1760 3510 15 605 80 25.1 93 17. 745 1760 1760 3500 15 602 78 24.0 92 l 18 730 1760 1760 3500 15 597 77 23.0 80 21 740 1760 1760 3500 15 602 76 19.6 106 22 735 1760 1760 3500 15 601 73 18.b 100 23 1107 1760 1760 3500 15 595 77 17.4 94

24 753 1760 1760 3500 15 604 81 16.5 87 25 015 1760 1760 3500 15 602 78 15.6 92 26 745 1760 1760 3500 15 601 79 14.3 88 28 740 1760 1760 3500 15 604 80 12.0 80 NOTE "*" INDICATES MUT OR EFFLUENT SAMPLE TAKEN CONNENTSi DAY 11 REFILL HUT (11 10) 02< 5 PPD. COND.= 53 uGHH PH=6.03 2' -: h

OPERATING PARAMETERS FOR TEST LOOP 1 eTOCuAVE431 TM1 LLMi TEST 41 iRCH 1YS3 W TIME Ps Pe Pb Pmut AC T MUT T MUT LEVEL EFFLUENT F P6I PSI PSI PSI F F INCHES ml/hr 1005 1760 1760 3500 8 72 73 9.5 65 740 ~1760.. 1760 3500 8 72 71 8.1 ,m 6 8 x 1030 0, 0 0 0 0 0 0.0 O 1400 0. 0 0 0 0 0 1430 1750 1760 3500 15 152 73 23 8

2 15
640 1760 1760 3500 15 151 76 23 0 65 1900 1760 1760 3500 15 150 76 2400 1760 1760 3500 15 596 76 e30 1760 1760 3500 15 599 77 22 0 85 1910 1760 1760 3500 15 600 77 2110 1760 1760 3500 15 504 77 735 1760 1760 3500 15 497 79 21.0 72 2110 1760 1760 3500 25 495 79 2310 1760 1760 3500 15 596 79 1850 1760 1760 3500 15 611 78 19.5 127 2100 1760 1760 3500 15 602 78 2230 1760 1760 3500 15 505 78 915 1760 17e0 3500 15 500 78 18 8

. 9 <6 2000 1760 1760 3500 15 49b 78 2100 1760 1760 3500 15 604 78 740 1760 1760 3500 15 606 81 17.3 97 1940 1760 1760 3500 15 610 81 2155 3760 1760 3500 15 503 81 830 1760 1760 3500 15 498 79 17.0 96 1930 1-760 1760 3500 15 498 79 2030 1760 1760 3500 15 598 79 2330 1760 1760 3500 15 604 79 135 1760 1760 ~3500 15 505 79 ,2310 1760 1760 3500 15 497 79 25 1760 1760 3500 15 601 79 1300 1760 1760 3500 15 596 79 13.5 84 2115 1760 1760 3500 15 600 79 2315 1760 1760 3500 15 504 79 1150 1760 1760 3500 15 499 78 11.8 87 1545 1760 1760 3500 15 500 78 1715 1760 1760 3500 15 595 78

1320 1760 1760 3500 15 603 78 10.5 70 810 1760 1760 3500 15 604 79 9.8 74 810 1760 1760 3500 15 603 84 8.8 72 745 1760 1760 3500 15 603 80 5.5
125 740 1760 1760 3500 15 610 81 27.9 125 750 1760 1760 3500 15 605 83 26.8 116
800 1760 1760 3500 15 609 80 25.5 91 810 1760 1760 3500 15 602 82 24.5 150 800 1760 1760 3500 15 604 84 22.0 40 750 1760 1760 3500 15 598 81 21.5 41 814 1760 1760

3500, 15 598 81 815 1760 1760 4795 15 598 81 1435.

1760 1760 4795 15 135 81 1440 1760 1760 3500 15 135 81 800 1760 1760 3500 15 136 77 19.5 108 810 1760 1760 3500 15 134 76 18.5 108 TE *** INDICATES MUT OR EFFLUENT SAMPLE TAKEN l l

OPERATING PAAHETERS FOR TEST LOOP 1 JTOCLAVE431' TMI LEAD TEST #1

R.IL 1983

!;Y-TIr.E~ Ps Pa Pb Pmut A: 1 MU T LEVEL EFFLUENT F PSI ebi PSI Pb1 F 4CHES ml/hr 750 1760[ 1760 3500 15 135 7; 3.0 fil2 i 17'0, 17c0 3500 15 135 76 11.5 2.10 3 e00 1/o9-20 '500 15 134 78 'M avy 78 5 1150 -1/60 lies 6 1o00 17oO 2/oD 3bov Ro9 // 10.3 120 *

7 905 1760 1760 3S30 15 594

/ "- 9.<. 102 ' o

107

3 815 1760 1760 3500 15 597 73 1

805 1760 1760 3500 15 595 7e 27.A '^e 2-745 1760 1760 3500 15 599 75 2,.e 1 : (, 4 800 1760 1760 3500 15 588 76 2*.9 12c 5 850 17ec 1760 3500 15 589 23.5 IL4 9 755 1760 1760 3500 15 593 is 19.8 94 9 1120 1760 1760 3500 15 593 73 18.3 105 0 805 1760 1760 3500 15 597 - 71 17.3 101

1 1005 1760 1760 3500 15 599 71 16.0 95 2

1525 1760 1760 3500 15 597 76 14.5 97 5 827 1760 1760 3500 lb 602 77 11.3 192 5 805 1760 1760 3500 15 603 76 9.8 180 7 750 1760 1760 3500 15 596 80 8.4 191 '3 755 1760 1760 3500 15 604 88 7.5 93 2 9 800 1760 1760 3500 15 591 77 6.5 136 OTE 'O' IND,1 CATES MUT OR EFFLUENT SAMPLE TAKEN OMMENTS7 AY REFILLED MUT AY 1983 AY TIME Ps Pa Pb Pmut AC T MUT T MUT LEVEL EFFLUENT F PSI PSI PSI PSI F F INCHES ml/hr 2 740 1760 1760 3500 15 607 77 6.0 75 2 750 1760 1760 4795 15 607 77 2 1500 17o0 1760 4795 6 100 77 2 1500 1760 1760 3500 15 100 77 3 800 1760 1760 3500 10 78 74 4 755 1760 1760 3500 10 75 75 4 1300 1760 1760 3500 10 75 75 '4 1300 0 0 0 0 0 0 0.0 0 1 800 0 0 0 0 0 0 OTd *** INDICATES MUT OR EFFLUENT SAMPLE 1AKEN OMMENTS; -AY ~ MUT N2 SPARGE (15 MIN.)/ MUT 5 PSI AIR J

BBLE 10-7 OPERATING PAPAMETERS EUR TEST ICOP 2 ) CLAVE 429 TMI LEAD TEST #2 IBER 1982 TIME Ps Pa Pb Pmut AC T MUT T MUT LEVEL EFFLUENT FLO PSI PSI PSI PSI F F INCHES ml/hr

D 1119 0.#

0 0 19 71 69 23 4 d.00 D ,1115 2050 2050 0 12 71 69 1400 2050 2050 0 12 71 69 1400 0. 0 0 12 71 69 1330-0 0 0 12 73 70 22.9 100 1330 1120 1120 1140 12 73 70 1418 1120 1120 1140 12 73 70 1430 1120 1120 1140 12 150 70 1520 1120 1120 1140 12 155 70 721 1200 1100 1150 12 154 72 20.6 100 81G 1200 1100 1150 13 154 72 913 1200 1110 2260 13 335 72 1000 1200 1110 2260 13 400 72 1200 1200 1110 -2260 13 548 72 1340 1200 1110 2260 13 549 72 1525 1120 1120 2250 13 547 72 650 1120 1120 2250 13 548 72 742 1120 1120 2250 13 53 72 840 1120 1120 2250 13 545 72 923 11'20 1120 2250 13 450 72 1023 1120 1120 2250 13 550 72 1115 1r20 1120 2250 13 446 72 -1210 1120 1120 2250 13 552 72 1300 1120 1120 2250 13 448 72 1505 1120 1120 2250 13 545 72 1505 1120 1120 2260 12 545 73 20.3 108 740 1120 1120 2250 13 548 72 18.9 63 811 1100 1100 2250 13 548 72 18.8

102
830 1120 1120 2250 13 547 73 17.6 90 835 1130 1130 2250 13 547 73 16.5 120

.I 842 1125 1125 2260 13 548 73 15.5

93
728 1120 1120 2260 13 548 73 14.3 112 i

730 1120 1120 3400 13 548 73 820 450 450 3400 13 437 73 ) 820 700 700 3200 13 437 73 7 1055 700 700 3200 13 225 73 7 1235 700 700 3200 13 135 73 7 1120 1120 1120 2260 13 135 73 7 1530 1120 1120 2260 0 133 73 INDICATES MUT OR EFFLUENT SAMPLE TAKEN DTE o** OMMENTS; AY 15:0b ADDED 75cc 0F HALIDE TO MUT 2

TABLE 10 OPERATING PARAMETERS FOR TEST IOOD 2 T OL'Le: EVE 429 TM1 LEAD TEST 42 VLNHtER 1982 -i TLME Ps Ps Pb Pmut AC T MUT T MUT LEVEL EFFLUENT F; PSI PSI PSI PSI F F INCHES ml/hr 835 112O ' 1120 2260 0 132 67 10.3 ('91 I 838

1120, 1120 2260 0

132 68 9.0 * . 91 742 1120-1120 2260 0 131 70 31.1 '113 740 1120 1120 2200 0 131 70 30.6 ~110 732 1120 1120 2260 0 130 70 29.1

128

-730 1120 1120 2260' O 131 68 24.9 100 73d 1120 1120 2260 0 128 69 23.5 107 732 1120 1120 2260 0 130 69 22.1 94 810 J120 1120 2260 0 130 6Y 20.8

115
705 650 550 2260 0

130 69 19.5 0 728 0 0 0 0 0 69 TE *** 1NDICATES MUT OR EFFLUEN1 SAMPLE TAKEN MMENTS; Y REFILL MUT PUNF MALFUNTION G W

g.,,9 -- CE'f2UL"'ING PARADE 32SS FCEt Hlsr m 2 Ib t., ~. f n : J L :. i u ' I 1, t 4,' b,1. -( --h y,h. r, t'i2 Pmut AC T NUT 1 NUT LEVEL -EFFLUEsJ: Pt:1 Pb1 F F INCHES ml/i ii .-u= t-. t., .0 O 1;' 0 '72 24.0

1,,o 1760 0

12-72 72 v.

Ur ste

. 4.c 17o0

f860 12'

~72 72 -12 150 72 ) ) 95 - 1'9 1/nu Juou

) Sax i > ou~

' 17 /.,# .2860 lb 151 72 0 170n= e O-27:>0 12 lb-72 0.0 115 0 'O 'o l' 154 72 96 h 0-0 15 155 72 24.0 * .o 1,69 . 530 15 155 73 e v:" Yc o 2700 14 '148-73 23.0 I 'h 19 11030 .148 73 1 91 .E30-1ie 170 1'?10 207"i ,14

7. 0 '

1900 -1800 3040-15 .151 75 21.5

e30-1Mue 18u0 3040 it 151-75 1

v10 11-wr _1760 -31iv 1% 24b 7b -1019 ..i %U J ) d,' t 3150 15 600 /G 98 17.3 ?K 1 90

.." 0-

.4150 lb-59 ', 74 5Y9 74 J,. ~. 8 - O j '60 3 ] t.0 1. 4v5 ', 6 0 2 60 3150 13 4V7 74 83 1W0 .31;,0 .1b 501 75 lo.3 3150 15 501 75 /6v ) < :.o 17.w lab 31b0 15 601 75 1003 . /.0 ..i 1too~ 3160 15 698 75 69 30 J75 100 1/ O 3150 lb 600 75 15.b 1930 2 G:t 1) 3,/u 61 b' ' 15 600 75 630-1 <3 1 t /o J150 15 509 /3 116 a130 lb 500 74 13.5 /. 0 - 09 . t..t 3 i/cu -31b0 15 000 74 17 c.0 3150 16 598 74 112 e < _? O oO

1,00 3150 15 o00 75 12 0 Yae-e.

~b5 l 'e c o 17ciG ';> iso - 15 600 75 7 '. : 31b0 15 501 75 ' L :) /6t I n. p 3150 15 502 75 8.3 128 1, :c '. E.. 8 ):4 - 4.Gro 11o9 1 % e. 3150 15 502-75 . - M. G - 1 < <,0 - D mv 3150 15 598 75 O.'O 1/60, 1/dO1 31::0 15 601 75 70 10v-7.2 / 3MO .>6 3150 15 601 75 8/ ~ 1. c, a i/60 3150 15' 504 75 80 5.5 7be D'6 J 3150 15 501 74 1, v 130 3150 15 501 74 - v ? O -- )..- J 7. 0 albe 15 598 74 80 10vt. t,0 17e6 5150 15 SYS 74 29.3

9 d.

1,c c.:. 1/eo 174o 3150 lb 599 73 28 0 ".o 1769 3150 15 599 73 'O', 'J /co 1760 3100 15 512 73 224,3 3. D ':s 1 60 17w .3100 15 501 73 4 e. 1 7,.,.* 1760. 3100 15 500 74 26.3 109 T 7w

: < ^9 1760 3J00 15 500 74 2-51'O 1, 6:

1, 6v 3100 15 590 74 140e '69 .ic60 .-300 1G 598 74 ...y - tf/0 a100 15 .b98 73 19.3 ill 120 W ':: s f. '. ; k. -- ; ; 6.. 3100 15 599 70 17.9 ?, D1:. 96 'O' a #. it o-

4.a 3100 15 602 80 1 c,. o

' ~ Q 175U 3100 15 .602 81 15.5 yv

N OPERATING PAPM"S1ERS FOR TEST IOOP 2

. i t I...... :. 6
r. -

r_ L u ILbi 1; .m..,. 4 5 e i n.. . 's i _ c.. i; A Pb Pmut AC T MUT T MUT LEVEL EFFLULt>l t'5 J v 51 PSI DSI F F INCHES ml/hr

~

17o0 3300 15 601 80 12.0 Eva a . m 4 liev 1760 3100 15 600 78 10.6 .96 b 6v-1 ~/ o O ~ 17o0 3100 15 600 7y 9.8 91 1 6 lo" l 'io 0 1/o 3100 15 601 78 8.5 ~78 o Sib 1/oO 17o0 3100 15 col 78 6 7b5 1o00 1600 3600 15 ~ 01 78 6 6- -600 2300 2000 0 15 601 78 o 810 ~100u 1000 0 15 406 78 6 82a 22k 225 0 15 406 78 o bab Sov 300 0 15 367 78 6 Sba 7L 7b 0 15 308 78 6 910 25 25 0 lb 275 78-6 104v 2b 25 0 lb 187 78, 6 1130 0 0 0 15 105 78 6 1300 0 0 0 15 78 78 6 1300 0 0 0 0 0 0 0.0 0 '1 14bo 0 0 0 15 0 76 28 5

O

.1 1525 500 600 500 15 70 76 .2 720 500 500 500 15 70 76 2 725 1760 1760 2000 15 70 76 2 728 1760 1760 3100 15 70 76 2 730 17eo 1760 3100 15 70 76 2 815 1760 1760 3100 15 131 76 2 1025 1760 1760 3100 15 ~131 75 28.3 84 3 740 1760 1760 3100 15 131 78 27.8 4 742 1760 1760 2950 15 125 78 27.0 68 63 4 -1040 1760 1760 3100 15 125 78 7 745 1760 1730 2825 15 128 76 25.3 76 7 810 1760 1760 2925 15 128 76 8 750 1760 1760 2700 15 129 74 24.8 63 9 745 1760 1760 2520 15 74 24 23.3 79 9 805 1760 1760 2520 15 129 24 9 915 1760 1760 3100 15 255 74 9 1335 1760 1760 3100 15 598 74 ? 1400 1760 1760 3100 15 599 77 23.5 85 3 740 1760 1760 3100 15 598 74 22.5 112 1 750 17eo 1760 3100 15 598 76 21.3 110 4 740 1760 1760 3150 15 598 74 17.3 110 5 725 1760 1760 3150 15 597 73 16.0 120 5 732 1760 1760 3150 15 597 69 14.5 115

7 739 1760 1760 3150 15 597 70 13.0 112 1

745 1760 1760 3150 15 597 71 11.8 111 735 1760 1760 3150 15 604 72 7.5 106 TTE '3' INDICATES MUT OR EFFLUENT SAMPLE TAKEN IMMENTS; ~u BELLOWS FAILURE MUT REFILL (50L) BELLOWS NITROGEN SUPPLY LOW BELLOWS NITROGEN SUPPLY RESTORED

TAB 1E 10-11 OPERATING PARA!E'IERS EDR TEST ILOP 2 C Ti1I LEAII I~EST #2 AUTOCl.p< vet 29 FEBRUA.Y 19U3 DAY T1HE Ps Pa Pb Pmut. AC T NUT T HUT LEVEL EFFLilENT FLOW ^ -( PSI PSI PSI PSI F F INCHES ml/hr j 1 748 1760 1760 3150 15 603 75 6.3 102 l 1 1305 1760 1760 3150 15 599 71 28.4

120 2

755 1'760 1760 3150 15 600 76 27.4 92 3 750 1760 1760 3150 15 600 79 26.0 94 4 805 1760 1760 3150 15 600 78 24.8 102

l 7

735 1760 1760 3150 15 600 81 21.1 122 1 8 740 1760 1760 3150 15 599 83 19.3 98

9 740 1760 1760 31GO 15 600 84 18.5 til
10 743 1760 1760 3150 15 599 83 17.3 108 11 800 1760 1760 3150 15

~599 83 15.0 105 14 745 1760 1760 3150 15 597 81 11.5 133 15 730 1760 1760 3150 15 596 80 10.3 112 16 730 1760 1760 3150 15 597 80 8.8 115 16 1530 1760 1760 0 15 83 80 0.3 115 16 2030 1760 1760 0 5 83 80 0.0 115 17 /35 1760 1760 0 10 74 75 0.0 (19

18 728 1760 1760 0

to 78 76 0.0 77 18 740 0 0 0 0 0 0 '0.0

O 27 1000 0

0 0 0 0 0 0.0 0 27 2015 1/60 1760 3150 15 75 75 21.0

160
27 2035 1760 1760 3150 15 150 74 21.5 160 20 735 1760 1760 3150 15 150 74 21.0 112
28 1930 1760 1760 3150 15 595 74 20.5 112 NOTE "*" INDICAl'ES MUT OR EFFLUENI' SAliPLF TAKEN COMMENTSi liAY

? E *I.i 1 HUI' REFILLED (50 L.) 16 1ELLOWS FollllRE i ft SHUT liOWN CYCLE il 1:11HPl. E I E e: cr on tair va i o 4>

TABLE 10-12 urEidau.Nr.i FARAMr.;rr nb rw u ruwr-u- ---------- 'f I 'f 0CLAV6429' TMI LEAD TEST #2 3CH 1983 ( T1hE Pt Ps Pb Pmut AC T MUT T MUT LEVEL EFFLUENT Fi PSI PSI PSI PSI F F INCHES ml/hr 1000 1760 1760 3150 lb 599 73 19.1 78 1910 1760 1760 3150 15 599 73 E' 17ec 3150 15 503 73 $2 201c 1760, 1750 3100 15 500 74 17 3 112 750 1750 1900 1750 1750 3100 15 501 74 204D 1750-1750 3100 15 597 74 E22 1~/60 1760 3150 15 601 74 15 1 63 1900 1760 1760 3150 15 601 74 2000 1760 1760 3150 15 505 74 950 1760 1760 3150 15 503 76 13.3 72 1910 1760 1760 3150 15 500 76 2040 1760 1760 3150 15 597 76 640 1760 1760 3150 15 601 77 12 1 120 1900 1/60 1760 3150 ,15 600 77 2000 1760 17eo 3150 15 504 77 630 17en 1760 3150 15 500 75 10.5 109 1910 1760 1760 3150 15 499 75 2110 1760 1760 3150 15 595 75 730 1760 1760 3150 15 601 80 90 97 2150 1760 17eo 3150 lb 601 80 2250 17e0 1760 3150 15 505 80 2100 1760 1760 3150 15 501 77 28.9

120 2210 1760 1760 3150 15 595 77 910 1760 1760 3150 15 600 79 28.5 81
2000 1760

-4760 3150 15 601 79 2100 17oO 1760 3150 15 505 79 74S 1760 1760 3125 15 502 78 27.0 92 1940 1760 1760-3125 15 503 78 2005 1760 1760 3125 15 597 78 925 1760 1760 3150 15 598 80 25.9 95 1310 17eo 1760 3150 15 598 78 22.0 65 1155 1760 1760 3150 15 597 77 21.1 98 1315 1760 1760 3125 15 600 77 19.9 95 812 1760 1760 3125 15 599 77 19.0 94 805 17eo 1760 3125 15 600 81 17.9 90 815 1760 1760 3125 15 599 78 14.6 95 600 1760 1760 3125 15 599 79 13.5 94 -750 1760 1760 3125 15 599 81 12.3 76

800 1760 1760 3125 15 598 79 11.0 96 630 17eo 1760 4195 15 598 79 1500 1760 1760 4195 15 135 79 1510 1760 1760 3150 15 135 79 810 1750 1750 3325 15 132 77' 6.0
165 800 1760 1760 3125 15 131 79 30.0 117 800 1760 1760 3125 15 132 78 28.5 120 810 1760 1760 3125 15 131 73 26.8 120 830 1760 1760 3150 15 131 73 25.4 120 915 1760 1760 3150 15 132 73 1520 1760 1760 3150 15 595 73 TE **' INDICATES MUT OR EFFLUENT SAMPLE TAKEN MMENTSi Y

j

TABLE 10-13 OPERATING PARAMETERS EUR 'IEST IOOP 2 TOCLAVE.429 il LcAU lEST 42 RiL 1Yoo l.i 1 Ini Ps Fa Pb Pniut AC T nut T MUT LEVEL EFF LUE.iil F F51 PSI PSI PSI F F INCHES ne l / r. t h/ / } i.- 17 e0 E 1760 3150 15 596 73 1Y.6 } 4.;

os.

17eO 3150 15 600 77 15. t, g103 12, 1760 1760 3150 15 598 76 17.1 f.10:i

4-,

'w

oO 3150 15' o00 7*

lo.3 '9e 2 76 - 1.; c '. 376'; 31t0 15 601 74 15.3 72 000 1760 1760 3150 15 599 75 10.9 liJ M:

ec,

's / n o * ,$ ' 5 0 15 600 7.5 9.5 11L c.- 1/6 s 310,0 lb 600 77 6.0

124
t..

leoC _760 3150 lb 596 70 27.0 120 / b.1 1,te 1/c0 3 ' 1.C 15 597 /c 22.5 116 .?. / o s. 3

U SYi 72 20.e 121 19.5 l'e 2 x

60 315')

15 SW 72 c - c 'i. - i ~ U 1 c. ') 2C

(,

7. 16.. l a'3 //( 1 i /- ; /av .i. ;. i.: ir s9

12. ~.:

1ie .<o /.*,. 3 ' di, 1ti t, Y /6 l '.' 4 _ / 5 4, f, 2 '. O 1;;# t'- S EO i..: i' 1 / ;. . i t.;) 1. t,M F Bi- / 5.: 4.: * ; J c. 56i-Y(- ,L ' O ;: ; 8J 7 #i: 7( ;-

*' " G 3

e.'~ ' ' n i. ; tu '7 60 136 c;* I Ic., 51 t;;; b / C o O o u.o e o "X" INDICA 2ES M OR EETIMENT SAMPLE TAIGN MENISa REFIIIED M M N2 SPARGED - M 5 PSI AIR ITOCLAVE429 TMI LEAD TEST 42 iY 1983 iY TIME Ps Pa Pb Pmut AC T MUT T MUT LEVEL EFFLUENT F PSI PSI PS7 PSI F F INCHES ml/hr 800 0 0 0 0 0 0 00 0 800 0 0 0 0 0 0 iTE

C' INDICATES MUT OR EFFLUENT SAMPLE TAKEN

i ~ Table 10-14 FRACTION OF SULFUR ATOMS STOPPED WITHIN A 10 NM SLICE OF MATERIAL AT VARIOUS DEPTHS BELOW THE SURFACE 2 Depth of TotalDose(S{/cm) Center of Slice 15 16 1 (nm) 5 x 10 1 x 10 5 x 10 5 0.175 0.131 0.190 15 0.149 0.131 0.216 25 0.162 0.145 0.206 35 0.162

0. 154 0.165 45 0.129 0.142 0.110 55 0.088 0.115 0.056 65 O.058 0.072 0.029 75 0.032 0.047 0.014 85 0.019 0.034 0.007 95 0.013 0.020 0.003 105 0.006 0.007 0.001 115 0.006 0.003 0.001 Total 0.999 1.001 0.998 m -&_ 5LTA--__ _________ _ ___ _-. --- --- -

p f 10.6 Auger and X-Ray Photoelectron Spectroscopy (XPS) Studies of Sulfur Pick-up by Archive OTSG Surf aces. This Appendix section describes the detailed analytical methodology, including standards preparation, that was applied to OTSG surf ace analyses for sulfur pickup following Sposuie of archive tubing. samples to a preconditioning at elevated temperature in simulated reactor coolant with H B0, LiOH, ano 3 3 2 very dilute 50 anion. Preparation of Standards Six sections of unconditioned archive Inconel 600 OTSG tubing, approximately 1 cm x 1 cm on the sides, were ground and polished on the ID side to provice a flat surf ace for mounting on a heat sink. The standards were prepared by exposing the OD surf aces of the ground 15 specimens to 150 kev S -ions to various doses ranging from 5 x 10 2 2 1 5*/cm, Theoretical calculations S[-ion's/cmto 5 x 10 2 pr. edict a mean penetration depth of 320 A with a straggling of 130 A, so that 99 percent of the ions would be stopped 'within 710 A from the entry surf ace. Analysis of ' Standards 15 Figure 10-16 shows the AES analyses of three standards (5 x 10 2 16 + 16 2 S[/cm,1x10 j,2, 5 x 10 3*/cm ) to a depth 2 of -1200 A. The vertical scale represents normalized peak-to-peak heights of the sulfur signal (n ), calculated as follows: s (10.4-1) h /a$) = (h I" s) / ( n s s where h is the peak-to-peak height of the sulfur line in the aerivative s spectrum is the sensitivity f actor as defined in Reference 16. a 3 h, a$ are analogous quantities for element i and the summation 9 is over all elemeats detected (S, C, 0, Cr, Fe, Ni, Ti).

) Tha horizantal scale represint a drpth below the surf ace, based on a known sputtering rate of 50 A/ min (Reference 17). For each curve in Figure 10-16, the fractional area of a 10 nm slice was cor" pared with the total area under the curve. The total area under the curve represents a known quantity of sulfur and the fractional areas are proportional to the fraction of sulfur atoms stopped within each slice. Table 10-14 summarizes the results of the calculation. The concentration of 5 in each slice is calculated from the formula x = 2fet/(N + 2fft) (10.4-2) s where et = ion fluence (ions /cm ) or total dose f = fraction of ions stopped within the selected slice (Table 1) N = number of non-sulfur atoms within the slice (estimated at 16 9 x 10 atoms, based on pure nickel) By plotting normalized peak-to-peak heights (Equation 10.4-1) vs. sulfur concentrations (Equation 10.4-2), a calibration curve for sulfur analysis is obtained (Figure 10-17). The calibration curve of Figure 10-17 is based on 15 16 the data obtained from.the standards with 5 x 10 and 1 x 10 ions /cm. The data for the third standard need to be corrected for sulfur loss due to sputtering during ion implantation, an effect that can be neglected for the lower fluerices. Determination of Detection Limits When the sulfur peak-to-peak height becomes less than twice the noise level in the derivative Auger spectrum, the apparent sulfur concentration may be 100 percent in error and that concentration constitutes the instrumental detection limit. Lower concentrations will go undetected or will be determined with very low accuracy if detected. The instrumental detection limit' for this investigation is encountered at the last point of each of the curves in Figure 1C-16. From Table 10-14, the corresponding number of s atoms is 15 13 calculated to be 0.006 x 5 x 10 x 2 - 6 x 10 atoms in a 10 nm slice. 1029c/0150c/010684:5 176

2 This is converted to ug/cm by multiplying the number of atoms by the mass of a sulfur atom (1.66 x 10-27 kg x 32). The result is a detection limit of 2 3 x 10-3 ug/cm in a 10 nm slice. The detection limit for sulfur in the XPS technique was determined as the sulfur level at which the uncertainty in the sulfur peak minus background value was as great as the scatter of the points in the background. It was 2 found to be five times the Auger detection limit, or 15 x 10-3 ug/an in a 10 nm slice. Analysis of Conditioned Samples Six areas were analyzed on Inconel 600 samples cut from TMI-1 OTSG tubes which had been subjected to elevated temperature conditioning in simulated reactor ao sulfur was detected in any of the specimens at any ~ coolant chemistry. depth level, but all areas showed significant boron levels. The boron signal in the Auger spectrum consisted of two peaks, the main peak at 170 eV and a secondary peak at 152 eV. The peak-to-peak height of the secondary peak was about half that of the main peak. Normal boron signals consist of only one peak at 179 eV. The reason for the shift and the appearance of a second peak is not clear at this time. One possibility is that a baron-compound was formed, but the compound has not been identified. Because of the proximity of the second boron peak and the sulfur signal, X-ray photoelectron spectroscopy (XPS) was used to differentiate between sulfur anc boron. The XPS boron signal consisted of a single line indicating a is binding energy of 190.9 eV. No sulfur was detected by XPS. This limits the 2 amount of sulfur that might have been present to 0.15 ug/an in the first 100 nm below the surf ace and to one tenth of that amount within the first 10 nm below the surf ace. The Auger analyses are sumnarized in " composition tables" attached to the report. The compositions given are essentially normalized peak-to-peak heights (similar to Equation 10.4-1, for each element) and not calibrated. ) WWXmraAAMM AE

They give, however, some qualitative idea of how the composition changes with sputtering time. The sputter rate used was 5 nm/ min. Sumary Calibration curves for AES analysis of sulfur in Inconel 600 are available. Unfortunately, the presence of an unidentified boron ccenpound makes the use of AES on the GPU-N tubes undesirabie, at. least for sulfur analysis. XPS is less sensitive to sulfur, but can be used to iifferentiate between baron ano sulfur. The detection limit for sulfur (by XPS) has been determined. l Standards are available to calibrate the XPS technique for quantitative sulfur ~ analysis. (However, the calibration is costly and time consuming.) __10291L01504/010684:5 178

.40 O W 2 .35 Q 1x10 .30 O i E .25', M

s

.20 us E .] .15 8 .10%- .05 W a 10 20 30 40 50 60 70 80 "O 100 116 120 Depth (natuteters) Fig. 10-16 No S r om la. sta @ @ ~

l l l /

4. 0.-

I / / / f 3.0 / / / oo / o 2.0 / N i

s v3 1.0

'f I I I I I I i t L 1 2 3 4 5 6 7 8 9 10 Sulfur normalized peak height (%) Fig. 10-17 Calihmtion Curve for Sulfur Analysis in Incenel Alloy 600 by AES. l

l:-

11.0 REFERENCES

1. I. L. W. Wilson and R. G. Aspden, Discussion in " Caustic Stress Corrosion Cracking of Iron-Nickel-Chromium Alloys", Conference on Stress Corrosion Cracking and Hydrogen Embrittlement of Iron Base Alloys, Unieux-Firminy, France, June 12-16, 1973, International Corrosion Conference Series NACE-5, National Association of Corrosion Engineers, Houston, TX (1977), pp. 1189-1204. 2. I. L. W. Wilson and R. G. Aspden, "The Influence of Specimen Type and Heat Treatment on the Caustic Stress Corrosion of Some Stainless Alloys", 3_2., 193 (1976). 2 Corrosion 3. G. J. Theus, " Relationship Between Acid Intergranular Corrosion and Caustic Stress Corrosion Cracking of Alloy 600," Corrosion R, 20 (1977). 4. Ph. Berge, J. R. Donati, B. Prieux, and D. Villard, " Caustic Stress Corrosion of Fe-Cr-Ni Austenitic Alloys", Corrosion y, 425 (1977). SI R. S. Pathania, " Caustic Cracking of Steara Generator Tube Materials", Corrosion 34, 149 (1978). '6. R. S. Pathania and J. A. Chitty, " Stress Corrosion Cracking of Steam Generator Tube Materials in Sodium Hydroxide Soluticos", Corrosion 34, 369 (1978). 7. For Example, Y. S. Garus and T. L. Gerber (Principal Investigators), "Intergranular Stress Corrosion Cracking of Ni-Cr-Fe Alloy 600 Tubes in PWI Primary Water - Review and Assessment for Model Development", Electric Power Research Institute Final Report NP-3057, Research Project S138-8, A. R. McIlree, EPRI Project Manager, Palo Alto, May 1983 (S. Levy, Inc., EPRI Contractor), and references therein.

8. Ph. Berge and H. R. Dcnati, " Materials Requirements for Pressurized Water Reactor Steam Generator Tubing" Nuclear Technology 3,88(1981). 9. G. P. Airey and F. W. Pement, "A Comparison of Intergranular Attack in Inconel Alloy 600 Observed in the Laboratory and 'in Operating Steam Generators", Corrosion 39, 46 (1983). 10. G. P. Airey (Principal Investigator), " Optimization of Metallurgical Variables to Improve Corrosion Resistance of Inccnel Alloy 600", Electric Power Research Institute Final Report, Research Project RP-1708-1, C. E. Shoemaker, EPRI Project Manager, Palo Alto, in-press (June 1983) (Westinghouse Electric Corp., EPRI Contractor). 11. GPU Nuclear Technical Data Report, TDR No. 341, "TMI-1 OTSG Failure Analysis Report", distributed to the Owners Group by J. P. N. Paine, Electric Power Research Institute, Palo Alto, by letter of August ?7, 1982. 12. A. K. Agrawal, W. N. Stiegelmeyer and W. E. Berry, " Final Report on Failure Analysis of Inconel 600 Tubes from OTSG A and B of Three Mile Island Unit-1 to GPU-Nuclear", Battelle Columbus Laboratories, Columbus, OH, June 30, 1982. 13. M. A. Ridgon and E.B.S. Pardue, " Evaluation of Tube Samples from TMI-1," Babcock and Wilcox Co., Lynchburg, VA 1982. 14. W. N. Stiegelmeyer, A. K. Agrawal and W. E. Berry, " Final Report on Examination of Inconel 600 Tubes RemoveG in the Third Pulling Operation from OTSG's A and B of Three Mile Island-1," Battelle Columbus Laboratories, Colunbus, Ohio, March 1983. 15. S. C. Inman, " Examination of OTSG Tubes from TMI-l Third Pulling Sequence," Babcock and Wilcox Co., Lynchburg, VA, December 1982. i

i c s 16. Handbook of Auger Electron Spectroscopy, Physical Electronics fr,dustries, Eden Prairie, Minnesota 1976. 17. N. Pessall, M. Barcn, J. Schreurs and J. B. P. Williamson, "The Influence of Ion-implantation on the Corrosion Resistance of Inconel Alloy 600", in " Ion Implantation into Metals", V. Ashworth, W. A. Grant, R. P. M. Procter, Eds., Pergamon Press, Oxford,1982. l l t / 1029c /0150c /010684; 5 193}}

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1.0 INTRODUCTION

SUMMARY

SUMMARY

11.0 REFERENCES

1.0 INTRODUCTION

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11.0 REFERENCES

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