ML20070S441

Overview of Progress in TMI-1 Tube Cleaning Experiment

ML20070S441
Person / Time
Site:	Crane
Issue date:	01/31/1983
From:	Robin Barnes, Lathouse J, Wensky A Battelle Memorial Institute, COLUMBUS LABORATORIES
To:
Shared Package
ML20070S421	List: ML20070S418 ML20070S441
References
NUDOCS 8302040398
Download: ML20070S441 (75)

Text

-

t i

I OVERVIEW OF PROGRESS IN THE IMI-l TUBE CLEANING EXPERIMENT

[

1 l

to

(

l G.P.U. NUCLEAR I

January 31, 1983 l

1 by i

I, 4

R. H. Barnes, A. K. Wensky, and J. Lathouse j

i i

i l

BATTELLE Columbus Laboratories l

505 King Avenue Columbus, Ohio 43201 l

l Battelle is not engaged in research for advertising, sales promotion, or publicity purposes, and this report may not be reproduced in full or in part for such purposes.

22ggeaseagg P-

1 OVERVIEW OF PROGRESS IN THE TMI-l TUBE CLEANING EXPERIMENT to G.P.U. NUCLEAR from i

BATTELLE Columbus Laboratories January 31, 1983 INTRODUCTION This is an interim report that presents preliminary results from studies performed at Battelle-Columbus Laboratories for G.P.U. Nuclear to evaluate and optimize a hydrogen peroxide cleaning process. This cleaning process is aimed at removing sulfur from corrosion pits in the Inconel-600

)

OTSG tubing that underwent intergranular stress corrosion cracking at Three Mile Island-Unit 1 (TMI-1) nuclear power plant.

The work described here is limited to experimental cleaning studies performed with Inconel-600 tubes which were removed from the TMI-l steam i

Supportingstudiesonthekineticsofsulfateproductionkrom generator.

the reaction between hydrogen peroxide and nickel-sulfide particles, and additional tube cleaning experiments will be presented in the final report.

The presentation of the results and the experimental procedure is given in a brief outline format because the main purpose of this report is to present an interim overview of the program. A comprehensive draft final report will be issued at the completion of the experimental work of the tube cleaning experiments or sometime in mid December, 1982.

i 2

BACKGROUND The most popularly held opinion concerning the mechanism of f

intergranular stress corrosion cracking of the TMI-l once through steam generator (OTSG) tubes involves sulfur species attack on the Inconel-600 tubes. The sulfur, most likely in the form of polythionic acids and thiosultate resulting from a series of oxidation / reduction steps during and after the incident, is known to cause intergranular stress corrosion cracking in Inconel-600. Support for this assumption came from surface analysis data of tubes showing sulfur levels in the range of %30 pg/sq.in.

area of the corroded tubes.

In addition ta that, experimental evidence demonstrating the ability of thiosulfates to induce stress corrosion j

cracking in the tube materici prompted the investigation of a process to remove the sulfur species present in the affected areas of the tubes. The four major activities carried out during this investigation are summarized below.

t (1) Determining the levels and forms (if possible) of-the sulfur species in the corrosion areas using both total sulfur, surface analysis, and ion chromatography (IC).

j (2) Defining the conditions for an effective cleaning process for sulfur removal using hydrogen peroxide by carrying out a series of

" beaker tests".

(3) Developing a global-rate expression that can be used as the basis for predicting the efficient of the reaction during cleaning.

(4) Applying the developed cleaning process to actual

)

OTSG tubes provided by G.P.U. Nuclear and under the actual plant repair conditions of the tubes.

1 l

l l

l l

3 SCOPE OF WORK The scope of work aimed at ultimately defining the cleaning process under actual plant tube repair conditions was divided into two phases. The first phase involved carrying out oxidation, using hydrogen peroxide, of NiS which was assumed to be the predominant sulfur species present on the inside surface of the tubes. These reactions were carried 1

out in " beaker tests".

The second phase involved the adaptation of the

" beaker test" Nis oxidation conditions to actual Inconel-600 tubes.

Following is a summary of the main activities carried out during this program.

LITERATURE SURVEY The literature was surveyed for the known chemistry of nickel sulfide (s) oxidation reactions. The stoichiometry of the reaction, the f

effect of pH, and the nature of the pH adjusting reagents were empnasized.

The article by S. Ahmed, et al., in " Corrosion" and the EPRI report by D. MacDonald and G. Gragnolino were used as starting points.

DESIGN OF " BEAKER TESTS" A "bealer test" was designed such that the amount of nickel sulfide, particle size, and total volume was appropriate for the periodic sampling for sulfate monitoring by ion chromatography (IC). NiS obtained in the smallest particle size available will represent the extreme case

?

of reduced sulfur state. Each test involved the preparation of the solation and periodic sampling and analysis for sulfate by IC and the determination of the peroxide level at appropriate time intervals during the course of the reaction in order to establish the half-life of peroxide. This hopefully will define the optimum conditions for the oxidation reaction.

A series of four preliminary beaker tests were run to investigate (1) the difference between stabilized and unstabilized peroxide, (2) the effect of bright Inconel-600 surfaces on peroxide decomposition, (3) the I

4 t

approximate reaction rate of thiosulfate ion with peroxide, and (4) the combined effect of stabilized peroxide, bright I-600, and 130*F temperature on peroxide decomposition rates. These tests are needed to minimize testing using actual TMI-l tubing specimens.

CLEANING OF TUBES A series of " beaker tests" were run to contirm the cleaning effectiveness of peroxide on TMI-1 specimens containing sulfur. Duplicate beakers were run at pH 8 and 2300 ppm B to simulate operations with the core in place and the other two were run at pH 10 and zero boron to y

simulate conditions with the core removed. A second series of tests were run under the above conditions except that sodium thiosulfate or sulfide were introduced at the same rate that sulfur was released.

CORROSION EXPERIMENTS A series of " beaker tests" were run using U-bend specimens of 304SS (sens) and I-600 (sens) as well as C-rings made from TMI-I tubing with addition of sodit.m sulfide and hydrogen peroxide in order to test conditions inducing corrosion.

KINETICS STUDIES The kinetics mechanism for the oxidation reaction was investi-I gated. Experimental variables covered for the analysis included pH, H 022 i

concentration, boric acid concentration, temperature, stirring rate, and effect of air versus argon as a cover gas for the beaker tests.

l The experimental data will be analyzed using a heterogeneous reaction model to define the reaction mechanism and establish a global-I rate expression that can be used as the basis of an extended model for predicting the efficiency of H 0 xidation for removal of NiS from steam 22 generator tubes. The analysis of the experimental data will take into account dissolution of the NiS particles and mass transport effects.

i J

I l-L f

5 l

The main analytical techniques employed during this program were ion chromatography (IC), total sulfur, infrared (IR), X-ray

(

diffraction, scanning electron microscopy (SEM) coupled with energy dis-

[

persive X-ray (EDAX) analyses.

OVERVIEW OF PROGRAM The program is progressing on schedule and is %75% completed.

All the experiments included in the original work plan with the exception of the tube cleaning and corrosion runs under oxygen as cover gas have been carried out.

The deleted experiments were found to be unnecessary in view of the long reaction times experienced even in the presence of hydrogen peroxide. In addition to that, several " beaker tests" and new tube cleaning experiments were carried out.

The additional tube cleaning runs involved Immunol treated and expanded tubes made available to us from B & W.

Table 1 summarizes all the " beaker test" runs completed to date and the reaction conditions.

Wark is currently on going to determine the total sulfur content of the tubes before and af ter cleaning as well as surface analysis of 1

the tubes by SEH, EDAX, and IR techniques.

i l

i l

l l

l.

l l

l L

I 6

TABLE 1.

" BEAKER TEST" RUNS COMPLETED 51 0; (ppm)

B (ppm)

S Form Temperature j

D:scription pH 2

Bed.ar Run-1,2 8 (NH )

200 (stabilized) 2300 NiS Room Temperature 3

Betksr Run-3 8 (NH )

100 (stabilized) 2300 NiS Room Temperature 3

Beibr Run-4,5,6 8 (NH )

200 (stabilized) 2300 NiS Room Temperature 3

Berksr Run-7,8 8 (NH )

200 (stabilized) 2300 NiS 32-35'c Bedsr Run-9,10 9 (NH )

200 (stabilized) 2300 Nis Room Temperature Berkar Run-11,12 2.6 mg L10H 200 (stabilized) 2300 NiS Room Temperature Be ist Run-13,14 8 (NH.)

200 (stabilized) 2300 NiS Room Temperature

• Be<.xsr Run-15,16 8OH) 25 (maintained) 2300 NiS Room Temperature 3

Berksr Run-17,18 7 (NH )

25 (maintained) 2300 NiS Room Temperature 3

13ro Run-1 8 (NH )

200 (unstabilized) 2300 NiS (17 ppm)

Room Temperature I:ro Run-2 8 (NH )

200 (unstabilized) 2300 NiS + I-600 Room Temperature Zsro Run-3 8 (NH )

200 (unstabilized) 2300 Thiosulfate (20 ppm)

Room Tamperature Zsro Run-4 8 (NH )

, 200 (unstabilized) 2300 NiS + I-600 130*F 3

Tube Run-1 8 (NH )

20 (maintained)**

2300 Tubet (3"-7")

130'F Tube Run-2 8 (NH )

20 (maintained)**

2300 Tubes (3"-7")

130*F Tubs Run-3 10 (LiOH) 20 (maintained)**

O Tubes (3"-7")

130*F Tuto Run-4 10 (LiOH) 20 (maintained)**

O Tubes (3"-7")

130*F Corrosion Run-1 8 (NH )

20 (maintained)**

2300 U-tubes C-rings, 130'F (02 cover gas) 3 Corrosion Run-2 8 (NH )

20 (maintained)**

2300 and sodium sulfide 130*F (02 cover gas) 3 Corrosion Run-3 10 (LiOH) 20 (maintained)**

O (20 ppa) 130*F (02 cover gas)

Corrotion Run-4 10 (LiOH) 20 (maintained)**

0 130*F (02 cover gas)

Immunoi Run-1 8 (NH )

20 (maintained)**

2300 3-1, 3-2, 3-3 130*F 3

Imunol Run-2 8 (NH )

20 (maintained)**

2300 3-4, 3-5, 3-6 130*F 3

F Imunoi Run-3 8 (NH )

20 (maintained)**

2300 3-7. 3-8, 3-9 130*F 3

Immunoi Run-4 8 (NH )

20 (maintained)**

2300 4-1, 4-2, 4-3***

130*F 3

Im. Exp. Run-1 8 (NH )

20 (maintained)**

2300 A111-13-2 #2***

130'T 3

Im. Exp. Run-2 8 (NH )

20 (maintained)**

2300 A111-13-2 #10***

130'F i

Imm. Exp. Run-3 8 (NH )

20 (maintained)**

2300 A111-13-5 #2 130*F Imm. Exp. Run-4 8 (NH )

20 (maintained)**

2300 A111-13-5 #10 130*F Imm. Exp. Run-1 8 (NH )

20 (maintained)**** 2300 A111-13:

B-1, B-2, B-3 130*F 3

C-1. C-2, C-3 Imm. Exp. Run-2 8 (NH )

20 (maintained)**** 2300 A111-13:

1-1, 1-2, 1-3, 130*F 3

4-1, 4-2, 4-3 Imm. Exp. Run-3 8 (NH )

20 (maintained)**** 2300 A111-13:

2-1, 2-2, 2-3, 130*F 3

3-1, 3-2, 3-3 Imm. Exp. Run-4 8 (NH )

20 (maintained)**** 2300 Bright Inconel-600 130*F 3

Imm. Exp. Run-5 8 (NH )

20 (maintained)**** 2300 A111-13: 4-1 (from 130*F 3

1munoi Run-4) j lam. Exp. Run-6 8 (NH )

20 (maintained)**** 2300 Reagent Blank 130'F 3

• = Argon cover.

• • = Unstabilized H 0 '

22

• • • = These pieces were not immunol treated.

• • • • = DuPont Perone H 0 '

22

7 EXPERIMENTAL SECTION,

A brief description of the experimental procedures followed during this program are given below:

l BEAKER TEST A " beaker test" typically contains the following reagents in a one liter glass beaker equipped with a magnetic stirrer:

e 500 ml distilled (DI) water e 6.57 g H B03 (2300 ppm B) 3 Enough 5:100 and NH 0H:H O to bring pH to desired level e

4 2

e 8.5 mg NiS 319 pl 31.3 percent H 022 in one liter water for 100 ppm H 022 e

Where actual tubes were used, a 3-inch long tube was used instead of the NiS. The tube was either sliced longitudinally or cut into 3-inch seg.ents in order to maximize surface contact with the solution. In addition, only enough solution was used to cover the tubes most typically 150 ml with all constituents scaled down appropriately.

SURFACE ANALYSIS To characterize the sulfur attack on the inside surfaces of the Inconel-600 steam generator tubes, and' aid in assessing the cleaning efficiency of hydrogen peroxide, a series of tube surface examinations were conducted using scanning electron microscopy with energy dispersive x-ray analysis (SEM/EDAX), ESCA, and infrared spectroscopy.

The SEM/EDAX studies wer2 performed with an ISI-100 SEM equipped with a Tracor Northern Model TN-2000 energy dispersive system. Tube samples were sectioned and examined both on the ID surface and in cross-section before and after cleaning. The examinations included scanr.ing electron microscopy at different magnifications, energy dispersive x-ray measurements for semiquantitative elemental analysis, and x-ray mapping to show the spacial distribution of elements in the tube samples. Depth of the EDAX elemental analysis runs between 75 and 150 pm.

The sensitivity for sulfur

I k

8

(

detection is about 0.5 weight-percent (w/o) on the ID tube surface and 0.1 w/o for the tube cross section.

ESCA measurements were performed using a Leybolt-Heraeus Model LHS-10 Auger /ESCA surface analysis system. The ESCA analyses which were I

performed on the ID surfaces of the tube samples, cover an effective area of about 1.3 cm x 1 cm.

Combined with argon-ion sputtering at 4 kev,

[

profiles of the different elements, along with their oxidation states, can be determined as a function of surface film thickness or depth below the surface of the solid base. Analysis depth from the surface is appro.ti-mately 20 5. The detection limit for sulfur is in the range of 0.1 to 0.2 atomic percent.

Infrared analyses were performed using both diffuse reflectance i

and microabsorption techniques. A Digilab Model 10 FTTR (Fourier transform infrared spectrometer) with a Harrick DRA-PSD diffuse reflectance accessory was used for the surface reflectance measurements and a Digilab Model 14 with appropriate condensing optics was used for the microabsorption measure-ments.

ION CHROMAT0 GRAPHIC CONDITIONS Both the Model 16 and Model 10 Dionex ICS were used under the following conditons for sulfate analysis:

Eluent: 0.003 M NaHCO3 and 0.0024 M Na2CO3 30 percent flow rate Standard preclean and anion analytical column Sensitivity: x1 or x3.

TOTAL SULFUR ANALYSIS The standard Br2 H 0/HNO reagent was used to oxidize all sulfur 2

3 forms to SO " and the sulfate was then analyzed using IC.

4

i r

9 L

(

HYDROGEN PEROXIDE ANALYSIS j

The hydrogen peroxide levels were monitored using Chemetrics kit which 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 iron by peroxide and the formation of the intensely colored ferric thiocyanate complex. The intensity of the color increased with the amount of hydrogen peroxide present in the solution. It was found that the presence of nitrite ions will-also give a positive response with this reagent. Since nitrite ions were found to form during the cleaning process, most likely as a result of NH 0H 4

oxidation by hydrogen peroxide, a small amount of sulf amic acid was added prior to analysis in order to remove this interference.

In addition to monitoring,the peroxide levels using the Chemetrics kiet, the " Spectrophotometric Determination of Hydrogen Peroxide with 8-Quinolinol," Analytical Chemistry, Vol. 39, No.1 (1967) was used for preparing secondary standards.

CORROSION TEST The corrosion test was conducted by immersing 3 C-rings made directly from IN600 TMI tubes and 3 U-bend made from sensitized IN600 and Type 304 stainless steel in the form of 0.062 inch commercial sheet stock in the test solution. This solution contained 2300 ppm B as H B0 3 3 adjusted to pH 8 using ammonium hydroxide or pH 10 using lithium hydroxide and no boron.

In all test solutions, the level of hydrogen peroxide was maintained at 20 ppm and a sodium sulfide solution having a concentration of 7.95 ug/ml was continuously pumped at a rate of 2 ml/hr for a period of seven days of the 14-day test.

l 10 RESULTS Details on the IMI-l Inconel-600 tube samples used in the beaker cleaning experiments are presented in Table 2.

The OD of the tubes is 5/8-inch, with a wall thickness of 0.036 + 0.001 inch. Typical data for the Inconel-600 alloy are summarized in Table 3.

Results available at this time from the total sulfur analyses on various tube samples are given in Table 4.

The results of the total sulfur analyses and other work still in progress, along with the corrosion experiments that have already been completed, will be covered in the final report. Details on each of the beaker cleaning series experiments are described below.

CLEANING SERIES 1 This series of cleaning experiments were performed on samples from four different TMI-l tubes as identified in Table,2.

Prior to being received by Battelle, the tubes had been cleaned prior to shipment by B & W using techniques such as running a felt plug through them, and then eddy current tested for cracks, but had not been treated with Immunol.

The beaker cleaning tests were epnducted at 130*F with duplicate samples at pH 8 and pH 10, with a total solution volume of 150 mi in each beaker.

Each beaker contained a 2-1/2-inch length of tube that had been cut in i

half along its longitudinal axis. Samples of solution were removed periodically from each beaker for sulfate analysis by ion chromatography and hydrogen peroxide analysis by the colorimetric method. Hydrogen peroxide was added as required to maintain its concentration at 20 ppm, and make-up water with appropriate pH was added as needed to keep the

(

solution volume at 150 ml.

The results of the sulfate and peroxide measurements are shown as a function of reaction or cleaning time in Figures 1 through 4.

In general, the total sulfate removed from the tubes at the end of the runs 1

i

\\

~

l

..~._,-m

_,._,,,-__,-,,..y,.,,.

,.c..-

-.n,-..

e 2.-,.

TABLE 2.

DETAILS ON TMI-I TUBE SAMPLES USED FOR BEAKER CLEANING EXPERIMENTS Tube Sample Beaker Identification Tube Sample Weight, a Cleaning Beaker Tube Sample Sample Form of Tube Sample Before After Series Test No.

No.

No.

Treatment Tube Sample Length, in.

Cleaning Cleaning 1

Tube Run-1 A 71-126 None 2 split halves 2-1/2, 2-1/2 Tube Run-2 A 78-32-2 None 2 split halves 2-1/2, 2-17/32 Tube Run-3 A 88-11 None 2 split halves 2-23/32, 2-25/32 Tube Run-4 8 8-25 None 2 split halves 2-17/32, 2-9/16 2

Ismunol Run-1 A 111-13 3-1,3-2,3-3 (a) 3 whole tubes 1-1/4 Immunol Run-2 A 111-13 3-4,3-5,3-6 (a) 3 whole tubes 1-1/4 Immunol Run-3 A 111-13 3-7,3-8,3-9 (a) 3 whole tubes 1-1/4 Immunol Run-4 A 111-13 4-1,4-2,413 (b) 3 whole tubes 1-1/4 3

Imm. 2xp. Run-1 A 111-13 2-2 (c) 2 split halves 3

13.897 13.897 3

13.479 13.479 Imm. Exp. Run-2 A 111-13 2-10 (d) 4 split halves 3-1/32 14.779 14.779 3-1/32 12.685 12.685 Imm. Exp. Run-3 A 111-13 5-2 (e) 2 split halves 3-1/32 13.458 13.456 3-1/32 13.967 13.965 Imm. Exp. Run-4 A 111-13 5-10 (f) 2 split halves 3-1/32 12.949 12.948 3-1/32 14.349 14.348 (a) Immunol treated tube section exposed to explosion debris from explosive expansion tgsts.

(b) No Immunol treatment. Untreated tube section exposed to exp*..aion debris from explosive expansion tests.

(c) Untreated tube sample exposed to explosion debris from explosive expansion of tube.

(d) Untreated tube sample in explosively expanded transition region.

(e) Immunol treated tube sample exposed to explosion debris from explosive expansion of tube.

(f) Immunot treated tube sample in explosively expanded transition region.

e

F k

4

{

12

[

TABLE 3.

PROPERTIES OF INCONEL-600*

w Density 8.43 g/cm3 Melting Range 2470 - 2575*F Specific Heat 0.106 BTU /lb

• F (32-212 F)

Thermal Expansion Coefficient 7.4 x 10-6 in./in./F Thermal Conductivity 8.6 Btu /f t.-hr.

• F (32-212*F)

Tensile Modulus of Elasticity 31 x 106 psi Torsional Modulus of Elasticity 11 x 106 psi Poisson's Ratio 0.29 e

Nominal Composition, Percent Nickel 76.0 Chromium 15.5 Iron 8.00 Manganese 0.5 Silicon 0.25 i

Carbon 0.08 Copper 0.25 Sulfur 0.008 (Max. 0.015)

• From Huntington Alloys Handbook, Fourth Edition, The International Nickel Company (1968).

I

TA8LE 4.

SIMIARY OF TOTAL SULFUR ANALYSES 04 TUBE SAMPLES Weight loss Total Sulfur Density of Sample Tube Sample Sample Tube Length Tute Sample after 8r /HNO3 Analyssl Area.In.g 10 Surfac Sulfur per unt 10 Area pe/te.)

Identtftcation Treatment Condition Form Analvred. In.

Weight. e Onpl & _on,1 b

9e 504 Tube No.A 71 126 Top i In.

None As received m ole tube 1-3/64 33.0 1.822 18.11 Tube No. A 78-126 Sottom I in.

None As received Whole tube 1 7/64 75.5 1.9,1 39.12 ide No. A 78-32-2 None As received Whole tube 1-5/16 42.0. 62.0 2.284 18.39.27.15 Tube No. A 88-18 None As received Whole tube 1 1/32 69.0 1.194 38.46 Tube No. 8 8-25 Top None As received Spilt tube halves 1 1/16.1-3/32 100.0 1.775 56.34 Tube No. 8 8-25 Sotton None As received Split tube halves 29/32.1-3/32 84.0 1.646 51.03 lube No. B-Ill-62-IA Top None As received Whole tube 1-3/64 52.0 1.822 28.54 Tube N3. 146-6 None As received Split tube halves 1-32.15/16 76.0 1.621 46.89 Tube No. A 11-126 None After cleaning Whole tube 11.5930 0.76 18.0 2.190 8.22 Tube No. A 78-32 2 None After cleaning Whole tube 11.4876 0.86 15.0 2.170 6.91 fube No. A 88-11 None After cleant-g Whole tube 13.5018 0.76 26.0 2.551 10.1g Tube No. 8 8-25 None After cleaning h ie tube 11.1300 0.76 12.0 2.114 5.68 l

l Tube No. A 111-13. Sample No. 3-2 lausunol/Espanded After cleaning 3 tube pieces (a) 7.3728 1.82 77.5 1.393 55.64 Tube No. A til-13. Sample No. 3-4 Isununol/ Expanded After cleaning h ie tube 1-1/16 9.823 1.51 47.0 1.856 25.32 Tube No. A III-83. Sample 100. 3-9 Isamunol/ Expanded After cleaning Whole tube 1-3/32 10.2216

1. 31 27.0 1.9 31 13.98 Tee No. A 111-13. Saaple No. 4-3 Espanded After cleaning Whole tube 1-1/16 10.0831 1.19 14.5 1.905 1.61 Tube No. A Ill-13. Sample No. 3 lemunol/ Expanded As received Whole tube 1

9.4987 2.12 37.0 1.795 20.61 f

Tube No. A 111-13. Sample No. 4 Espanded As received Whole tube 1

9.4566 1.47 37.0 1.787 20.71 p

W 26.0.(C].0(c)

Tube No. A 111-13. Sample No. 3-8 laununol/Espended Cleaned / Polished Whole tube 1-1/4 10.7237 0.91

?.026 12.83,19.25 Tube No. A 111-13. Seaple No. 3-9 lemunol/Empended Cleaned / Polished b le tube 1 1/4 9.9434 0.88 23.0 1.879 12.24 Tube No. A 111-13. Sample No. 21 Espanded As received Whole tube 1

9.5116 0.91 8.0 1.797 4.25 Tube No. A ll1 13. Saaple No. 2 11 Espanded As received Whole tube 1

9.4533 0.82 14.0 1.786 1.04 fube No. A 111-13. Sample No. 5-3 Isununol/Empanded As received h ie tube 1

9.5154 1.11 14.0. 11.0 1.798

7. 79.f l2 Tee No. A 111-13. Sample No. 5-9 Issusnol/Espanded As received Whole tube I

9.5391 1.07 12.0. 24.0 1.8n2 6.6b.13.3z q

Tube No. A 111-13. Sample No. 2-2 Espended Af ter cleaning Spilt tube halves 1.1 9.0048 0.97 18.0, 240 l.701 10.58.14.11 i d e No. A Ill-13. Sample No. 2-10 Espanded*

After cleaning Split tube halves 1.1 8.7183 0.90 16.0 1.657 9.66 Tube No. A 111-13. Sample No. 5-2 Insuunol/Espended After cleaning Spilt tube halves 1.1 9.3753 1.10 22.0 1.171 12.42 Tube No. A 111-13. Saaple No. 5-10 Isununol/Espended* After cleaning spilt tube halves 1

10.1655 0.92 24.0 1.921 12.49

......................................................................................1

• Espansion transttton zone.

(a) 29/32.15/16, 25/32 in.

l (b) Average of blanks sebtracted l

(c) 81 ants not subtracted a

E l

i l

4

k 14

-corresponded closely to total sulfur measurements made on a representative sample from the same tube. In the case of the pH 10 experiments, more peroxide addition was required to maintain the 20 ppm target level.

SEM/EDAX Studies SEM/EDAX examinations were performed on both as-received and hydrogen-peroxide cleaned samples. A photomicrograph and x-ray maps for sulfur, iron, chromium and nickel are shown in Figures 5 through 7 for a representative area attacked by sulfur in the cross section of Tube Number 146-6.

These results show sulfur penetration into the Inconel surface along the grain boundaries. The x-ray maps indicate that the regions exhibiting significant sulfur levels were also depleted in both nickel and iron. Figures 8 and 9 show EDAX spectra for Inconel-600 base metal and a sulfur contaminated region in an uncleaned sample from Tube 146-6.

The sulfur level in the contaminated. region was measured as 5.2 weight percent.

Direct EDAX measurements on the ID tube surface gave an average sulfur concentration of about 0.7 weight percent.

SEM/EDAX examination of sanples from Tube Run-1 and -3 showed no sulfur above the detection limit of 0.1 - 0.2 weight percent. Typical areas of. sulfur ~ attack in the sample from Tube No. 88-11 (Tube Run-3) after cleaning at pH 10 are shown in Figures 10 and 11.

An EDAX spectrum obtained at Point 2 in Figure 11 is presented in Figure 12.

Even at the extreme depths of attack, no residual sulfur was observed.

Infrared Studies An infrared reflectance spectrum obtained for a sample from Tube Number 146-6 is given in Figure 13.

This sample is considered to be representative of the uncleaned and untreated tube samples as removed from the TMI-l steam generttor. The spectrum shows weak infrared bands in the 2600 - 3000 cm-1 region which indicate a thin hydrocarbon film.

i 15 CLEANING SERIES 2 The samples used in this series of beaker cleaning experiments

~

were taken from pieces 3 and 4 from TMI-l steam generator Tube Number'A 111-13.

Piece 3 was treated with Immunol and - then exposed to debris from an explosive tube expansion while piece 4 was exposed to explosion debris without Immunol treatment.

ihe beaker cleaning experiments were all carried out at-pH 8

- with three samples from tube piece 3 and one sample from tube piece 4.

Each of the four beakers contained a single whole tube sample 1-1/4-inch in length. The volume of the peroxide cleaning solution used in each beaker was 200 ml.

The beaker cleaning experiments were conducted at a temperature of 130*F using the same procedures as described for the first series of cleaning experiments.

The results of the peroxid_e and sulfate measurements associated with the Series 2 cleaning experiments with Immunol treated tube samples are summarized in Figures 14 - if. Immunol Run-1,

-2, and -3 which involved immunol treated tube samples show greater hydrogen peroxide stability than Immunol Run-4, which involved an untreated tube sample. Sulfate production was about the same in.the four runs. The maximum anticipated sulfate pro-duction based on total sulfur analyses on uncleaned representative samples is considerably lower than the final concentrations measured in the beaker cleaning.

This discrepancy is currently being investigated.

Total su'1 fur measurements on the cleaned samples showed presence of residuol sulfur. In the case of sample number 4-3 from Immunol Run-4, the residual sulfur amounted to about 14.5 vg as sulfate. The Br HNO 2

3 oxidation procedure for the sulfur analysis dissolved about 120 mg of the sample.

If the Inconel-600 contained the maximum level of sulfur of 0.015 percent, as listed in Table 3, this could account for as much as 55 pg of sulfate. Total sulfur measurements made on the Inconel-600 base metal gave sulfur contents in the range of 0.03-0.04 w/o.

f l

16 SEM/EDAX Studies Both uncleaned and peroxide cleaned samples were examined by SEM/EDAX. Within the limits of sensitivity, no appreciable residual sulfur was detected on the cleaned samples. Details on these measurements will be presented in the final report.

Infrared Studies To provide background for examining Immunol coated samples, spectra were run on two different lots of Immunol (Lot Numbers B-2-62 and B-46-99) supplied by Babcook and Wilcox. Lot Number B-2-62 was used for the treatment of the satpJes involved in this program. The spectra in Figures 18 and 20 were obtained in transmission on thin films of the two different Immunol solutions, and are characterized predominantly by strong water absorption. Water constitutes about 95 ' percent of these solutions.

Transmission spectra for Immunol residues prepared by evaporating the two solutions on ZnSe substrates are shown in Figures 19 and 21.

A diffuse reflectance spectrum for Lot Number B-46-99 Immunol smeared on an Inconel-600 plate and then dried under an infrared lamp for one hour is shown in Figure 23.

The infrared spectra show no significant differences between the two dif-ferent lot numbers of Immunol.

Infrared diffuse reflectance spectra on an uncleaned section from piece 3 from Tube A 111-13 and sample Numbers 3-1, 3-3, and 3-6, which were peroxide cleaned, were all similar and showed no evidence of Immunol.

A typical spectrum for these samples is shown in Figure 23.

The spectra were bands with intensity ratios in the range from characterized by CH2 and CH3 2:1 to 3:1. The intensities of these bands are quite low, indicating the presence of a very small amount of material.

The only evidence for the presence of anything besides a hydro-carbon was observed on sample Number 3-3.

In this case, the spectrometer beam was focused on a dark spot on the ID surface of the tube sample.

1 17 -

The. spectrum is given in Figure 24.

The strong broad band centered at 1250 cm-1 is characteristic of inorganic material..The band frequency is indicative of either a nitrite or possibly a bisulfate.

The infrared diffuse reflectance spectra for an uncleaned sample of tube piece 4 and the peroxide cleaned samples were essentially identical.

-1 A typical spectrum is given in Figure 25(a).

The weak doublet near 1000 cm is characteristic of isotactic polypropylene (Figure 25(b)).

Relative

-1 intensities of the bands around 2900 cm differ somewhat from those usually found in normal isotatic polypropylene films.

The transmission spectrum of a small dark-colored. particle removed from the ID surface of uncleaned tube piece 4 is presented in Figure 27.

This spectrum, which was obtained using a microtransmission technique, is identical to that for isotatic polypropylene. The relative intensity difference in the spectrum in Figure 25 may be associated with crystallinity differences in the material coated on the tube surface.

Another possible explanation is speceral distortions that are sometimes observed with the diffuse reflectance technique due to optical interference effects.

CLEANING SERIES 3 The Series 3 cleaning experiments were performed with pieces 2 and 5 from the same tube (A 111-13) as the samples used for the Series 2 experiments.

Piece 5 was treated with Immunol and explosively expanded while piece 5 was expanded without Immunol treatment. Sample Numbers 2-10 and 5-10 used in Immunol Expansion Run-2 and -4 were from the expansion transition zone, and Sample Numbers 2-2 and 5-2 used in Immunol Expansion Run-1 and -3 were from a distance of about 14 inches from the explosively expanded transition zone.

For the beaker cleaning tests, the tube samples, which were about 3-inches long, were split in half axially.

In each beaker, the cleaning solution volume was 150 ml.

18 l

Debris from the explosive expansion was collected from the ID l

surfaces of the samples before cleaning and examined using both SEM/EDAX 1

and micro-FTIR.

The Series 3 beaker ' tests were conducted in the same manner as the previous beaker cleaning experiments. In the Series 3 experiments, total sulfate production was nearly the same and followed similar sulfate concentration / time curves for all four beakers. The sulfate and hydrogen peroxide concentration data are given in Figures 27-30.

The curves tended to level off asymptotically after about 50 hours5.787037e-4 days <br />0.0139 hours <br />8.267196e-5 weeks <br />1.9025e-5 months <br />, then after about 100 hours0.00116 days <br />0.0278 hours <br />1.653439e-4 weeks <br />3.805e-5 months <br /> increased again, leveling off after a total reaction time of nearly 250 hours0.00289 days <br />0.0694 hours <br />4.133598e-4 weeks <br />9.5125e-5 months <br />.

In general, sulfate production persisted longer than was observed with either the Series 1 or 2 beaker cleaning tests. At about 215 - 220 hours0.00255 days <br />0.0611 hours <br />3.637566e-4 weeks <br />8.371e-5 months <br /> into the runs, the apparent hydrogen peroxide concentrations in the beaker cleaning solutions increased to nearly 200 ppm in the case of the Immunol treated tube samples,and to about 80 ppm with the untreated samples, and then decayed over a period of about 170 hours0.00197 days <br />0.0472 hours <br />2.810847e-4 weeks <br />6.4685e-5 months <br /> to values approaching the peroxide target level of 20 ppm.

This anomalous transient in the peroxide concentration is tentatively attributed to build up of nitrite in the cleaning solution due to a catal; tic surface re_ction on Inconel between nitrogen and atomic oxygen from the peroxide to form nitrate with nitrite as an intermediate. The nitrite produces a false indication of peroxide with the color test used to determine the hydrogen peroxide concentration.

Formation of nitrate is observed in the cleaning solutions by ion chromatographic measurements for sulfate. The nitrate formation data are currently being collected and analyzed.

l l

SDI/EDAX Studies Uncleaned and cleaned samples were studied by SEM/EDAX.

Results will be presented in the final report.

r-19 ESCA Studies ESCA studies were conducted on tube sample numbers 2-5 and 5-5 to investigate the nature of the residual film on the surface of the untreated and Immunol treated tubes after exposure to explosive debris from the expansion process. Results from these studies are being correltted with the infrared data and will be reported in the final report.

Infrared Studies The uncleaned sample Number 2-7 and the peroxide cleaned sample Number 2-10 both showed the same polypropylene material as observed with untreated samples from piece 4 of tube number A 111-13. A typical spectrum for sample number 2-10 after cleaning is presented in Figure 31.

Presence of the Immunol prevents adherence of the polypropylene material. Once formed, the polypropylene is unaffected by the peroxide cleaning process.

However, presence of the polypropylene does not appear to appreciably influence the rate of removal of sulfuy by the hydrogen peroxide cleaning process. The absorption spectrum for sample Number 2-7, which was an un-cleaned sample fror about 5 inches from samp3e Number 2-10, was diminished in intensity indicating a lower density of polypropylene. These spectra dif fered significantly from those obtained for sample Number 2-2.

The spectrum for sample Number 2-2 is given in Figure 32.

The intensity of the absorption is considerably less than that observed with sample Numbers 2-7 and 2-10 with negligible a. sorption at 2960 cm-1 The spectrum for sample number 2-2 indicates that less material is present on the sample surface and that fewer methyl groups are present. The spectrum appears to show a contribution from polyethylene.

The spectrum for sample Number 5-7 is also quite similar to that observed with samples from piece 4.

A diffuse reflectance spectrum for the uncleaned sample is shown in Figure 33.

This spectrum also shows the presence of polypropylene. Particles removed from the ID surface of this sample were also identified as isotactic polypropylene.

l 20 Spectra for the two peroxide cleaned sample Numbers 5-10 and 5-2 and the uncleaned sample Number 5-5 showed both similarities and differences among themselves and with sample Number 2-7.

The spectrum of sample numbed 5-2, which is also fairly representative of 5-5 and 5-10, is given in Figure 34.

This spectrum shows a decreased intensity at 2960 cm-1 due to less methyl absorption. Debris particles removed from the ID surface of sample Number 5-10 before cleaning were composed of either polyethylene or polypropylene. A transmission spectrum of a polyethylene particle is shown in Figure 35.

The infrared spectra showed ne evidence of Immunol on the tube sample surfaces.

CORROSION RESULTS As a result of the tests described in the Experimental Section, no corrosion due to the cleaning process was observed. Highlights of the data are summarized in Tables 3-12 in Appendix B.

35 Addition of H 022 30- b kbk E

'N

• N25:

m

~

H0 Target Level 22 2 y

, _ - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - ~ - - - ~ - - - - * - ~ ~ ~

o a

2 15-E 8

8 10-u N

o, 5-2 0-9 5D 10b 160 200 256 o

E 3-e7 m

T 8

"u-2-

E ecg Total SO e

4 8

1. 'l-o

'-t 0

50 100 150 200 250 Reaction Time, bours Figure 1.

Hydrogen Peroxide and Sulfate Concentrations as a Furction of Reaction Time for Tube Run-1 at pH 8 and 130 F.

y v

-3

+

,e.-

f 35-Addition of H 0 22 N

30 -

J!!

o" 2&

W H0 Target Level 22 80-

_o

%s bl 5 -

5 c"

S10 -

U~

r5-t 0=

0 50 100 150 200 250 3-E'e 8,

S t

(

s2 -

3 l

b 5

u l

C81 -

I e'

Total SO4 m

l l

l 4

l l

0 50 100 150 200 250 Reaction Time, hours l

Figure 2.

Hydrogen Peroxide and Sulfate Concentrations as a Function of Reaction Time for Tube Run-2 at pH 8 and 130*F.

35-i.

Addition of H 0, 9

l l

}l l

l}

ll ll l

l 30-k R25-

c C1

> --- -- --- --- -- - L2 Targe t Level H0 s

.20<

8

~

3 215-

"c o

O 810-m o

=

C SU l'00 15'O 260 280 f

1 E3

'e 8

l T

d o3 3

Total SO4 2

e I,

8 c8 y

8 6

l

~

150 150 25'O 0

50 Reaction Time, hours Figure 3.

Hydrogen Peroxide and Sulfate Concentration as i

a Furction of Reaction Time for Tube Run-3 at pH 10 and 130'F.

k 35-30-Addition of H 0, 9

l Il ll I

l l

25-g H0 Target Level 22 I 20- - - - - - - - - - - -. - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - -

2 T

l 15-v E' 0 -

E 5-6 00 60 100 15D 20D 250 l

3-E

)

att P

t 8

g 2-8 Total S0, U

(est.)

E E

1' 8

s 4

q 0

0 50 100 150 200 250 Reaction Time, hours Figure 4.

H.ydrogen Peroxide and Sulfate Concentrations as a Function o' Reaction Tilne for Tube Run-4 at pH 10 ind 130*F.

i

l

1

)

l 9

J i

1s ;;,.'

l

. ($ ' f5~)

b

%w $4 l. *: l -

. lg.-

)

j L.

'S'"

Ih

~ '

E'

't 7

l

,t

~.

h.y =.u-. > :-

y,-

u i

rw l

yt h.r..55' 4

dj

,,/

l T ' ip,Y [,

c.

s, 1 -

~ ;. q ';...,,

AiNk.b[.f.) f(

f, l/ Nffk,s ' Mr.

k.Q: 'lf uk j : ' 'h,i.:

% y...

e e

r-U

~

6 i

...,s

.\\

_.... -, =.

2.

l j

l 36296 500X 36212 500X j

Photomicrograph Sulfur X-Ray Figure 5.

SEM Photomicrograph and X-Ray Map for Sulfur Contaminated Area in Cross Section of As-Received Inconel-600 Tube Sample.

/

t

. q

.7.".;

i?)k'h$kfif,!:'k'E.$f0f

• L

' ~

.,. '.. ~,.

'<n5y W,q 'y' :;g.;~ ;f.::17.::,4.'.>.3

_*Q

• R.. 3.,,. Q '

_~.

~

s

,c,".4 3.-

...,.,..: :r

..,.e c

Qg.,[- * * ;.,,

'. _.,3y.a,

• '4,, j :

l

~ ~,.g. y's;c,.a.,,.y..:p1.',,l*.-

1

, hp

... e ;;. : : s.;.%

a, itky'y-_lW., & ;'[,_;. ?- Q 4 ' ;.

'.,.. _ ?,'. M,

\\,

. n

. ~ :

)

Am,

~ ' u Q. '. *f, ' 1). :

4

.f

..s l

f.c,.',.,-,., '-,

...;4

' *f, i

i 3

,4

.,.. J*,.'^

..c..-.

-,s -. f'y r. x f y

2 y4 k tf,

.s,( j.' g.

1.

a

.. +., ',,. g;. a

....,,. -. -,

.. - ; e, _.f ',

R '

,'*'r t.

g-L'f.';; t.,,, ','

.l - ; f f y.

.. ' l N..~. \\(

i

.h ". r. 'j.: - *

}'..

s,

'. } }, '..

'q^!'. p,

,' > f:h,.(.

[' ;:.T ~ ' *' ~ ',,,.

y.t,

. 5, m -.: ', + ~i.)'

s -

-..g.'%,f>._, 1y ~;;y._. :.

,.t.;-

s

< fy.. %p ;.O,/,.

3.

.s

~2

's -^, ;..,.;%c'p

'; r,

.;a

>y'.

w+,. pr$e?< x,. 3.[

.:,. u.

,q.

.. - A.

.'.,- ~.. ' ~

• s

.u.

;

t.q,.t i

<:,_.r....

y.

g,.

? s.'w:. u,..;,..:

...: 4 r.

y?

= s :.:...

r;r

......s..

t

' Q ^,0..m :, a

. ~.

. _ i. ;

,s

%w'$..,

e

f.. % ^,, ;;^:,: '.,.c

[ '. L '

1

, - i..,

..?

_{f.Qv,Qa} jg24,, * -

.4.1 f,,,q.y l?.

c

.i n

.y, imp

,,d

'6 f., p.., f'% (.

j

'h.(

,9...

ll..k ;,'.

- 6:j;/.k'h.'h,klh'\\/h'U N h'['

f

's D,

h;$ $ $?$ $ h.h h

%}.b.2hj'Qfj;N,I:-[:.9.l(

(5%[%QfWK%?&^

0MEdEW W W l

36219 500X 36218 500X Iron X-Ray Map Chromium X-Ray Map Figure 6.

X-Ray Maps for Sulfur Contaminated Area in Cross Section of As-Received Inconel 600 Tube Sample.

(

s i

i 1i

l l

l i

I l

l

9,p;-l.

y

+- -

+.,

,, J o:.

y,:7,.'; +q :

-n-

.e.

> : < 14.,

14.v

,h'

$> b'

" G:

h

~

,':1[ y '.

k'

_'l

< 'J&f f ' ^ ' ' :}'3'\\ fv ' ' '. '. f %}d{t"f ' _,., ^ l L b,- fs l u;y' , l3tIg). -... V.' '. 74g1)g .p? r, Y,,.: p.o !:b ~r. h .t x ; $5 Rfb;p<,h@?.O?% ! O'll.-jl:'y y,zg h:2 'o d.1j il~ ~ i u.h i .y.. < ;.pt[y ' 'i v4:s

':.s.

5f-w$',($ a/ V 8tu ~' . h,k-f I a, -e ' ' <51.:.'l%1;,? .9 \\ f, qts 7 M' !j&.'N 2 &. 4f.

k h

6.:.i g. T;15. fA \\

t. N.N: e F:.

3-s4 1 36217 500 1 Figure 7. Nickel X-Ray Map for Sulfur Contaminated Area in Cross Section of As-Received 1 Inconel-600 Tube Sample. I i i 1

8000 - N I 7000 6000 Element Weight Percent ~ SI 0.8 i 5000 CR 16.9 TE 7.7 i 4000 C NI 74 7 ~ i R 1 3 3000 1 2000 F E N I i C i 1 N S R F l I I E j

y; c = = =j LA qL l

0.000 5.000 10.000 15.000 20.000 Energy (kev) 1 j Figure 8. Energy Dispersive X: Ray Spectrum for Base Metal in As-Received Inconel-600 Tube. i

5000 N I ~ C 1 R ~ j 4000 i Element Weight Percent AL 0.9 SI 2.2 3000 S 5.2 Tl 0.7 CR 27.8 m e E FE 5.9 Oo 2000 NI 57.4 S j F t C N E 1000 S R y Al T p LL U g_ _ ~, 0 0.00 5.000 10.000 15.000 20.000 Energy (kev) Figure 9. Energy Dispersive X-ray Spectrum for Sulfur Contaminaat Area C) in Cross Section of As-Received Inconel-600 Tube.

L i I J i 1 4 k 'l ] 1 A i f_ 's' g 4 J g,

3... g.

s a k... ...s: \\.' e..g' l e 4 \\. a. l' 3'

• k,.

.~ E T.. i. ',' i. .<s .. g.. ;.J; ~ -j t i b. (- j< ~ r n- , : 4 :- A > r. ~,,4 rf,n = - b, * :;. r+'

..i. '.

1 ;'

4:.;!@? y.. 7@4 ~ 18$!]7.J,;.

v..

.. W,. s k.. e...edMN)N/[Nd[h'.[1. .,.. _.,.;M2jh)h'A.g a rkNi l 36441 2000X i Figure 10. SEM Photomicrograph of Sulfur Contaminated Area in Cross Section of Inconel-600 Tube Sample after Cleaning with H 0 at pH 10. 22 1 I

9 r g y. s ^ ^a i 2 J f ~- ~ , ~, r <- sl .e;- i L ~.- t.. 9 f,, .,s ) / hh.** ' L.'f([tb l '5$ Cl ui k l i 36432 7500X Photomicrograph { Figure 11. SEM Photomicrograph of Sulfur Contaminated Area in Cross Section of Inconel-600 Tube Sample after Cleaning with H 0 at pH 10. 22 I 4 i e 1

N I ~ l 40K R Element Weight Percent AL 0.5 SI 0.9 p 0.2 Tl 0.3 30K CR 23.7 3 FE 14.2 l NI 60.3 l v i ~ p 20K E ~ i b N' 10K 1 R I 4 F 4 S CT . N 3p E i I R I uLLAUL I ^- -N g 0.000 5.000 10.000 10.000 15.000 Energy (kev) j Figure 12. Energy Dispersive X-Ray Spectrum for Sulfur Contaminated Area (Area 2) in Cross Section j of Inconel-600 Tube Sample After Cleaning with H 022 at pH

• 8 i

'..i i ', '.,,.4!l i t. h,.ll'! I' j I! 1'j j l: lpt ijl

,, p.

lN t .n .et s v . i.. BA ".TEl.E!! COL !! !! ,l l, I l l l ]l' ll6 i;.h. lllI qh. ;lh ,h .;i I i Ig I q[' i,;t ::' I j. l Il; I - m!!! ! i:U :!:+ i[,j ;!!i i:,. J i, i i; i M lt I l 1; i ~ UjI+y, i , !. '.n 'il i <4 l p, .- { qh lll :jj;,i j t is t li j T (' "- i Gi.i'i ;p; n n! 4p h h, l a !: ;n a r. .3,-

1. lllh !ll

'il jlfT;F, p gI 7-(.%+ I l l l [ tl

p1

.y - ips pN.lD ' rt '

t

!I M8,

.i lN 4 h 1: .r i.; ~l,t I(;. 'i 2 :: t i:

p'i STY.n p

.i- !m!; fqf ;-1ID

uj.

o e, 'p /

, hh

,i j l 1 dQ q ! i 1 i; 1 j U i i, .r n .j; t +,- N Me!l 10Ul!i!H !Hi !N Wi W: !!!; 1,-- A- # ?Hidi! p 1, li L i. o'i 8_ 7.-.R., %q..A..P 1 i. .%. W...M- ' d' 1. ~' pH l-l .%.S i!.! od' hh tb Ii 'i ' r o i. Hi 1 i !T i,- >' i + l x. [ r v;.ii 'lli i: h!! ':: 1: l' [ 4.,lJ i i - l r.pl Yl}-i.g l'i:Il'1 i. re - t _A t

p-

,.t i ' q t. i: 0 .!j' !n- ]!:.3 i{l ]' ] [ l l l j lj Il jg tp] {t j iN pll jj1 q

l 4

>!;' !H . n._ q ,.,i__ ;_S ,i r t,i 2 i 3. 1 tIl l'I

f

}, I i t I l l l ] h; l} 't H I,j +- rg t;l- +t i l.y t I:.b II,!! !! N' h t i l N ',) . i _t; l !...!i . t.. 3[ .i .I 3, .j:

).q

j,,!

Jji d. ip i Id.. qI P: i.g 5-I .i l i I u ( l l l !.h . !!l "i 1 !f!! :.I, l ~ l, ~ ~ ~ ~~ T- ~~ [ ] l "! h j fl db..'l i l I

i illi ':4:

, j p' idl III 1 j lID:l 9' e! [di t'!' i I j b I dl1

...l! b: i!:

19; ,p. H: l'- ' 't b l

1 i-t

]; pll @' '.'i j i!ll !!! Oll Il.l l 'll l lj. [ ]! li ;;!j ;[ h h $ i$ [h 'td (j !'li $ ( 3600 3200 2600 2400 2000 1600 1200 800 500 Wavenumbers Figure 13. Infrared Diffuse Reflectance Spectrum for Dark Region on ID of Sample from Tube 146-6 (J Run 146A).

I ] l 39-30 - Addition' of H 0 22 III I I E 25 - 'N o z" {0 ~-- -- ----- =*-- ~ ~--~ ------ --- ---- g Ta rg e t Le ve l H 2 .g 15-

• B g

y 10 - 8$5 N N I C:

• )

CD 106 1*^ 206 2!!n 360 35'O 3-o l 4 l j 2 en l s 4 ~ c 3 u )- 2 a l g-Total SO4 l E O o e c2 0* 56 150 250 303 'A Reaction Time, hours Figure 14. Hydrogen Peroxide and Sulfate Concentrations as a Function of Reaction Time for Immunol Run-1 at pH8 and 130*F (Immunol Treated Tube Sample). _ - _ =.

r 35 a{ 3' Addition of H 0 l l ll l ll lp2

• 25-o H0 Target Level 22 g 2{$ ~ ' - - - - - * - - - - - - - - - - * * - - * - - + - - -

- - + ' * - - - - - + - - + - = - - - - - - - * - - - - * - D 2 15 - T 8 3 10 - e"E 3-0 5'O 100 150 200 250 300 350 3-I E e3 2 ~ ~ .2 1; l - g u 5 Total SO4 o Dm ' i l' 0 15d 2d0 250 300 350 O 5'O 0 Reaction Time, hours FIGURE 15. HYDROGEN PER0XIDE AND SULFATE CONCENTRATIONS AS A FUNCTION OF REACTION TIME FOR DiMUNOL RUN-2 0F pH 8 AND 130 F (IMMUNOL) TREATED TUBE SAMPLE).

r w 30-Addition of H202 4 25 I I ll l lll l l T 20+- - --. - - - - - - - --..+ -.. - - - --- - -. - "gT,a,rg e t Le ve l E S 15-b 10-g o y 5-0., e, a, c., s. = 3- -EE M T k 2-B 2' Y 8 8 u 1 g Total SO4 0 50 100 155 20b 25'O Reaction Time, hours FIGURE 16. HYDROGEN PER0XIDE AND SULFATE CONCENTRATIONS AS A FUNCTION OF REACTION TIME FOR IMMUNOL RUN-3 AT pH 8 AND 130"F (IMMUNOL TREATED TUBE SAMPLE).

l 35 '- T Addition of H 022 y 25 - l }}}} }Ill llll lll l l!! o" E - - ----- - -- --- - - -- -- - - -- - ' - - _ _ _ H g0,g Ja,g} }e vp, _, - 20 g z 315 - 5 E 10 -- 8 E

1. 5 0

g, a. 4. A. d-3. T% 8 2. T c' 3 Total SO4 i 8 v E m o 0 50 100 1da 2b1 N Reaction Time, hours FIGURE 17 HYDR 0 GEN PER0XIDE AND SULFATE CONCENTRATIONS AS A. FUNCTION OF REACTION TIME FOR IMMUNOL RUN-4 AT pH8 AND 130*F (UNTREATED TUBE SAMPLE).

r--- .l..~;" n. i. n i. I .;:1 4 3.,l -

1, i... !. l. i. i. -

I ! e!"li,.!. l '. i, sp ' J s 'li t. 1 i 1..

p i.

!i .i . BATTEt.I Cat . i. -- -- t-

• di.j-'

iI... .m p o. i;:

p i.

i.., 'l - l&d-5- i- - ---M-bb N --h O-Y +--J-k,[ p i. q ~l- { [--

l -- -h h, h

l7!

-- J --h g, ht :1.: u; ;!. ri D'i ;!; r

n!:;

it;, 9- .i' Dr T ilii W ': in lih fl!! ( ':il ~ i.!. k !. k. Il h f. b Y I Y' h !Y! h.n;[.a b: --e+U Ii!lh- !!n 4- : s:=,r m.- m ?- us,ni mi e! a: 9.- m .ip "t- !!!i !$ --I!! 'l!: I N!! NN :ii- -- ,il.h,ii h! l'l Y; fi; N t i r--

• r! t'i. h-

.i-OI hw::m' ;." ".A .- - -*~ n: 1-tr- !:n!-in :onaa n M iii ii 1 r - r' m il -j-n .s-~~--* t1j.. h; e,' l[l'I p! ; i. n lji.'": p~

, j.

i

n. i '] !'..

P T'" i .j:l,; . t li.j !P.! i

• .'7'i!.li i..

i.g

i l a

t i

.l h. ..ll p1j gli a l.

t.g?

_j! 1 a

.i 41 11L, . a g n

_2..

ns

1_;

ut 'i i n e,p p'!

. u i"

l o' fi > ln

. '~h

+ f*' .u. 5 .p! q

hl.

l! s t iy t,I-1. '. p. - l p' p' g r ::a l i ni in-o , p' in }... .I i si r l '.. - D' l lll

i -;p

._h,-. f i.

i

,;I

h '.

2,. ,! n; hi, . 1l;. i 1; .a:

-. 3..

. r.. 4, 1 'D' I.' . g. .jp u j lp :i !. j ob

r i.

'*v i '; i;.l Id ibsi .i. t.P i: .j

l

t. i:h -ld;.d E'.:d ilk

& d!i. J :i._2.; I n- :!UI :.n 1. 8.i. __ h . j.g: MS ?" D ;!h 'i bi..it:! o-o'; '.i ih h !p.G';. L 2_ c i 4 ' lii .2 , u.j i m"uh 2E : u t h,,"i: Ua:- '; ? ? [ it. is ol w i" e' 9-n h;j t;p n n. ed g i.. 7, '. l

I;h i.ti

.,h iM. '.i !H: . l ". . I. - ... i t !...! P.t; E 11 o,l.ll- "* - q.l .4 j":; !!'. 'u d": n:) ... W]. !m 'e. -m 'l y!! illj fp i ! ,,1 i.S; 'd.:.b: t .j:. b.:.a:!.m* : h

- '4 [J i

1 ij M m un;

t..

'I q L s 4 _ i;' "F-M 'i.l ') ~. .y. 'P' i '9 1l: IU:l ' j il. hd.. ".F 'H6 III~ l~v ' '. W: El.i. P:.- 'M .t 9 a.. r- .tn rh .h ?, i:

i

'.4. l ni: ..;g,!,

n

. t,.: 'i.!,.j: a-h;. !,,- p- ,i; 's. ..t;!i.

i. ;n r

a_- _n. - i p h. _ ;,' - o::n ph s o, "d [' - 2.; O. S,... s.:. .i T g: j m n_ t

i. au J

'"i

!- T

..t. 2._ 4_ u_w. ii g g', -. i:r ;, l'

' q.H :iii,i'il,j j.;. j;j ifi

_/J t !.. iii =m a '" ,;p i e i._:py %gg

:_ _._ %.h.

J_'.:_.__ m . f..1.'I' _ ; ::'.he:'l! h'i ilj.. . o' U* 31' _: _p. 11L .i.... !..a 1. . g.. .2. n. n.,. u. ' 'n

c. :. r. o. r. rel n'l

. m.i :,. i-g d-

t

,2 i i - i a " ~, mi.:- i l j.. , 6 o;..

a. an.

11.,. :.. p.n.h.c.

6, f e ls. .N es 11Jeg ,s. . 9:e 'j', ! l 1#av0di.pects '{-l. iT< mse l 2n ies ..Wi nie. I' i;i, ;;' 2t nis ~~ if: l! e l: -~iTy . l. 2t uisl.ill li en hns. Seens . 3E mis, 4 i1-.. f.ji'.[.l j {' '!h 'lhi f b.. r - $ Ik-- ..i ,p!U .,P. 'is !...:lI. .:1 ..- ""+.. ~ ~(-~' M[-- ' M"b,. YW- ' *. b-1f f M -II: ~ i i DD

d.. h.

!)ll I:i!

---

1r1.asractitis-Ni.!.-

f .lj. h...lllt-I tifA' ,.., :t 2

l: s,esensem,,ie,s..t...-

T:t I! l l m -.1 .l. l, r, ~'r,W v1. h a-N lH on

n. la. ;.q j";

.n i - 'm';.g n p .. ar:ar:3=ig -l. n. n FIGURE 18. INFRARED TRANSMISSION SPECTRUM 0F DYED IMMUNOL SOLUTION LOT B-2-62 (THIS MATERIAL USED TO PREPARE TUBE SANPLES SUPPLIED TO BATTELLE BY B&W).

l 1 ,. pr t' - ;f @ Hl@;' il,llliH' %l" f i

l. l',l

[] l t- .l: l l - - i a .g l;.j . l ' ;.[;ti C t,1, d, q,l ]l;. 1

i

p. b.

i.l: q. ; l.,

t..

BATTEL.J. ' COL. o .. ; j ,i N J s.!l.I:i'( i 1 .a + +- 7l . l lil g!.i: i.i.t 4 j {.!!.l. t :.:.i.; '...I. -t. q

p.M,.l 9.

2 i t - l, '.". ' i I.,,!:- i t l .o _L. _" l :.', l c' t E m o '. i ' : g-.,; {; l i a, i g l I i.; jesi d::.;!: gp- ;:,]: q- [ i, .i

)

s

.i [- p g; c. c !j. sis ;s: 1: lit a. ...i .y i T.M T h ~ i .i-p. i f ;;,h'q.,. y l. hj. l o. ...:l4.. g g.. t .t-S.) :+1. N., h.,.:,j-l. h. 15 k ,f h.l; :jN. E ll I ,, [- h.- ._i-E [. dI_l4 ttt If-

n..

di e. ,j. I t 1 . l Hi. ..g. ..!! ! b,. :'t .? p .g til; il,! *ll:

p g;

' i; 'l i;h !. 6. .i l ---+ = tei !t: t .i ft t.;,: l ll ll i:

• 4:.1., - li.

h. s.i;l.i e...

Ii i.. [i , l,g, i is. (p- ".p. t. l. g.,p : i 1 . *j i i '.1 ;. ir i ';. - .:.3 i o i. ,.j ti : j! g. i.: el. ;_. g.." . iI. al it:i lF 1 s. .o r'. ..:4..::,;.,}l", ji - '[L 6 i L 2* i .p. LlI '.# :3d '. "} .1 ..i , }I i d_.r .i. f,.p .i., ii;' j-.: tl

l.

in

o y, : e

.1 ,i. t..i.!.!

l.

I !! 4.. E r... i. si

e. i p

i' .n teF ti j l [ n iqi.i i, . nu .. a.

a

+ ";:. !;.!.n'."' q+ . : p-i = .n- 'b. :... n- !l

p:-

n. m il -it i t.;. - :ir 3... .i a: -: k: :;-~i. - r-- i. Y m ip "h!;;iqi.8:

,p M

r t--- ...,!i:

i

..v-l- '! l lin IP-1F i ..d p 't a i g. .ii. 1 - ". "**l a* l l'. g .l ...e 1 I l I

h. I

_h,l[l L;.b4.

R .Il!.. gg-

• s t

8-g t &{ i;, r ,u. g: [

..l

,;di. th '. o- . 3. 50

!)

I l.. a T;, pl i it. ..I i i: .t- .c

p i:

w nl:..i- .L.: d'.- i_ p:_:.$e]i in. [ i y;[p. g.M w:.I N. G .t i .p - %.1.. N:hi'g!.E. J M. d; ..i

.L.I ;.9 4 1

.c w.. I:.; Itl-8: i. 1 .i . q , p-j l ,c _. -N_ ,1 :. + .t pi. f p:? C ,.p .. d,ig!. 9, pl- ..... J,.

.; ij;

i.

%-J _mq / i.

t

3. _

o i. j: y .... -. __ l..... _. g -_ .q ..;2 m g_. g.. p.

l

..i.: a-m -M ..'.t t o. : i t. g R .!]I ill i 1-e,- i. ..p i ele. l. e is. ,n.j].Ities;, ;ge suas t<m ; l mise une jj. L: ses,j;;;. g 4

um mes.

6 !. !ys m !I iii! i!D M 1 i% i j f-i b #+%.!

lI

.F.;!!'!!. .I' N i

J..

!i' '!i, 'il 6;I. "[ '!?, ',..snarsco w----N 4 A il1lpi .,*' t . ns=m,,s.ia.s..:._. l\\."", :. il.l O d ' ';l.tp!LP 2 M T.- / '-- --; b_ _., .. i i. tii s l,ii: u.i

4,

l

t.?

..l . n, cs=<: o.r 1 ies... n. o -ii. .m_ ou y FIGURE 19. INFRARED TRANSMISSION SPECTRUM FOR RESIDUE FROM DYED I MUNOL LOT N0. B-2-62. SAMPLES EVAPORATED ON ZeSe PLATE. (THIS MATERIAL USED TO PREPARE TUBE SAMPLES SUPPLIED TO BATTELLE BY B&W). i

l;!

ii t

i .I! i i I l ! ni i m- :n l

p

! t r. li:' BA'TO.1i COL l l l .I

l. ll ll!

ll:: O!' i.,. c *n . I a. .., ;,::,q: i i n !!l 'li. l! ! .j:t l e m

;;;; !;t,l

- i 1, l 'l l ll...l.:l.lij lll; j l i -i 9 T,i:.I.H! ?!i i. i ~ I i i i![I llil ITii fis T

a. an i i

_r j j i t I j ii,ij ny ng gp :.. + i j'- o.j u!: nj, y i n o j m

g. _.q t i

4 u 1i i1 !!! ",a .5-u. n.', ' l

$ ill.

1 il k.:i 'i lil! d-l l !j I! h. 'l } ! I! !.i I l !! !L' m-

t+. -(m

.y %a-y-f i-i ,. u, i .n ,n i i q l ..,. n. i [i,. ]J. i {i. i. r - fr-h { - j J. i -i t i r j 1.g= 'r 11 . g

-- j

,ni I. l il gl 3 l . i

l 1

i. i i 1 .n i. i

• l.. '

La 4,

I

..l u-

i',,l., I li,.!_ r l l fi 8

ll' .l ! j,I ~l

.l.

t HI l l l l/, i:.; ci;:

i.

i J .is i I 1 yl;"I -l'l 9 b ' 'f l I'f lli l l .'li *? I l 8 .j. i+ l ] l i lll. i t! i.

ri

.r 'k !h lI f dl ! ] gl l 4.!4 m. fi l j ]O ih h 1 .it. l i;. J,- l.i d..' m'+I.,.:- i i:i,- m y 3 i .l o~ A J.j' :!.i i l i ! g il 1 l i i i i i a i i l ll! l k f "~ [ a h l l.I ij: . u!hiliil 'l li ,ll i i 1 i,i

n' n

'i 1 .i i .S liL %g.ii[.IMl.b [.., :IL . l4 __ q h ! ,[h l "h u v@ l i t.! n u ii.m un e ai ! In n i : i ! i n ! im e t_ a 1 .e r

. i

. g-a.

i p-i ii :r n m' n.. e .a. .i 3

m. mi ::

.. n., o.

a. ip i

i a.t.i t u. .r l

iii.ii. i!. ! ', '

WW!: i!i 3ll ,1dN.! lll il ; j i j11Mi l' !! EN' fM tij iPN. s.,' '!.lj; lji ll:82 j! j' l

• ! ,.S W '

. i '.. 1:'. 4j l 'vAVN&Er.fd .li: e? m'-- .i' f o Mf, '. ; NA, M*dM 4N % C% $4' N' N...1l r n r- ,fi r e-- f .l %j!{F .mA,h.. l l I I 'I! i!f lhi IU E,tr + .i + t.,r,4 ,o:,y =,y;..j lj; h..j t e.

• p.

u a.. I sg: W I,eg;. qo. i g .... r. ;.i g. aw-x .i e m.,,,. n a,. ,y FIGURE 20. INFRARED TRANSMISSION SPECTRUM OF DYED IMiUNOL SOLUTION LOT NO, B-46-99 (THIS MATERIAL SUPPLIED TO BATTELLE BY SANDY P0TTERTON OF B&W).

.i T. T. . t. ... i . ~.. ..4... ... _ + g g. L.__ m, ._t-..... r ___,,,, ._ 4 . {. _ _,. i g .4.y o ._..... g. ....J__.._. o _..___a _,..___ _.. ._..A _ 6-.... _.. - _... l.... r W i ag. x o l~ .....r-- > B-a.'* Q ... _. ~... 3 .re e 4 < = .a i ._..... N.,g_.. . _ _.4... W ._ a W .-} .-,M. c. ._.._.._.4_. 1 .._. w... _. - .. y.. J E = _., _.. f,._.._p +_._,g-._ p__.g.._. ar .a m _u .( t 2 - 2 m. l gm _4 ,y ...s _. _-- g...y ee i i ac-CO L_,. 2 ,_ p .L.,--._ .. _4.s_ _ M 9 .O i i .'~'k gz y -u-- ____.(- r sg l 1 2 OW 4. .JH i i i . =,. ,,,,J oH 1, 2 1 m i 1 y _.. g. o c. z 1 i i c --d. D >- i i i w v> c l i i i y 'e z M a2' 1 i - m r a i 2 i =. m t a_. a _5". _m.y ' A C t 1 W >_ t ..m >. Ca l .4_.y._.. _4 O _.4.. __L___- ) _M .r-l-E _.J W 4 oJ e _.. 7 p. )., _ 4 J. L.<c. _%. Wg i 2 u EW j __._n .) q. A..e _. g i 8 i -- J ..A. W ar _ i i .._.1 i k. _...r i i i i r' .. _.._ K ' D CD i g ,_, o WW l W 4-w go g I l i oa 2 e ge __ _ i .,.1_ w. WQ 4_ 3g u Q. ._. p E> =,. _. _ a.. .i 5 N 4 _._..,.. 4._.. g..._,._.A eJ g.. o ag-y,,,,,

c. E MW

[__. g g .._... _. 4. _ ...e

4..

. 7.._. _. o_. ... _. ____.a_. e r-i i gg ~ _.. ..k_ b._ .m I .....2_.. _._ g ~. EH _...4_.. 7,.. 4 g as' z [ E

• t

.o ..p.__ 7 ] 3..___. &W 9_. i. H _.... o... e an. _A__.. .~, WJ g _ { az-ge .= -4.. ... 6 6M ...... l... i, ~_ z@ 1-. -,y e.. . 5 e. ._....L. ~ ..___.a.._., ...}._. i = m .4. _. - __.i. .4 .4. . 4 ___ i 4_. l e. 4.. y g ..g 4 ... g g.. W .e-i..i ._.4 g. 4,. _ . n g m .i. 4,.. J .j.... ..j... .c.e. __...;....h... W . - ~. -

.j ! I!if lll!! hll !! j!! !l ! ll !lf l! ff! l l l l fl f!f li!! !j'i lll Ii; iii I I

s I ;i-i '!

llij l ! !! l'! jl! 18': e t l E' COL 1: .i. BA"TEL 'i i ja l.Lf._1j! I!ll .i .!? l it i ! ]IT.li' !!ij !;l: li!! l .I, '8 i j 1 I T ul ne T:n ini i ni m-3.- u j j.s, ip i

a.

, j. j i h Ib hl j f.j -l,- h h ji't fi4

h h ',

. -r T f 7 U-i i

l-d lo

n un i!n un illi I!ir lI!

! !i I l li I . nu ,n i j!!: I "U 'I" S' .- f I !! Il

1. ihi it ni; :id-liilli 'il ji"lli li 7 it

- t-r 1 t tt jfj tti t-t tj t th !ti

• e i : e.

d,4 ut hy !! g n j y i i= g; ;d .t. _ 4 !,.2 a _ 4 f p ly; J! i! 4 _4 t iti l i i: n!; n. ni i m

o.

n.

o i i I l i e. i ,L ; i n 1 l l . l t!: ap ig 1 j l f L 4 t ut y la; 2 i B- [

j. ll0,i!, ll l -llhHI

.,l l-i h-l[ h '! I I i a l E 'l' ,!f ll !!.hi I 'i: t = L - Iii[i! %] ' I f,j; llJ .i M,i.e,. M-l .:;l %n '"T,

.,, c[.;

l ip -2 H, r -N-I r --+ n l T ili lp .ii n..; ou n. i

n. o y

n... o. e 5

_p ,.y g I ll I 'l l 8 l l l l ' ' fl ll1 !;l 1 1.! : l i.!

lll

j ljl! e,8, .f: ,ll I I l l

ll, 1;

g2 i

e. 8 ..g.g" g. - y _ 1 ll A 4 t _ g

,_ ;.;i

t

,~

4 i.,i l.g

. e....n

i..

.p 'n e n.. i. _J i i i i .o

i t

l l' l l w ni n a c! q i in:

1. liti

- Iq li j u Ij; :mUIh,- l

i

[:: I m: i t 1. If i ,y W..n-p. u 1. ] j,i i, li l, g 4( U! [(w.!;. iM w l m e j i lii kr ' t[ 'i: !!;. i' p. i $:4 _lMli e I : !' !I, j ' W.

• il le l

i \\ /. .I

!i,D '!!!

i. 'lj t; t. . i 't 'j;' .- ; j;. L ;l l' ll'! 'j;; i;.-.i; ]ll

I-

_.' h, ; l l ji i i i_g i T Q r. . ;l,4; 4 , _. g

• _ _m

.. u 2 u . p. g n 7 n H _g]-. ,lif il..l; . 'i: !i

h' !!I h! hj

[1i. I l j j ;q jj: 4 ;M i m, hi,l l l l i.j j 'l p, l ..Ii n' L :i !I 'ij i.

n..!!..

ni! il'

n. i hij ll:l ilij il.l l, i

i L i... .i. i 3 3_ . 3(M . i "KM.. ii I j ! ffM i 2dM lt t i 2fM 11(Mhl ! '1IM' ll l l: 'l : OE 71 E !:ia t'il n. yavj tjsjg_ M._j l l .i. i. g i / 4 ./P lli [i 'i I ' i h. ij. l-1,i ' 'l '.7. /j . o y. .i / .p o .i,

n i

'- 2 CANS 218H;l _l_ 3 .o ~__ ___, tem .g. mmg p._. .,,,l g,! !li T]l l' l } l elj. ft1mi IP

1. 3(ANSz IM.

• I i

i l. li cis m wr earm t I-w.d: .1 H ! FIGURE 22. INFRARED DIFFUSE REFLECTANCE SPECTRUM FOR DYED IPNUNOL FILM (LOT NO. B-49-99) ON INCONEl.-600 SURFACE AFTER DRYING FILM FOR 1 HOUR WITH INFRARED HEAT LAMP (THIS MATERIAL SUPPLIED TO BATTELLE BY SANDY POTTERTON OF B&W).

EJ BA TTELLE COC \\ J

b.

3600 3200 2800 240a 2000 1600 1200 800 600 Wavenumbers FZGURE 23. INFRARED DIFFUSE REFLECTANCE SPECTRUM FOR ID SURFACE OF TUBE SAMPLE 3-1 AFTER PEROXIDE CLEANING (IMMUNOL RUN-1).

l l l l l l BATTELLE COL 3600 3200 2800 2400 2000 1600 1200 800 600 Wavenumbers FIGURE 24. INFRARED DIFFUSE REFLECTANCE SPEClRUM FOR DARK SPOT ON ID SURFACE OF TUBE SAMPLE 3-3 AFTER PER0XIDE CLEANING (Im VNOL RUN-1).

I f g g BA TTELLE COL p { l 1 l Y t l 3600 3200 2800 2400 2000 1600 1200 800 600 Wavenumbers FIGURE 25a. INFRARED DIFFUSE REFLECTANCE SPECTRUM FOR UNCLEANED ID SURFACE OF SAMPLE FROM PIECE 4 0F TUBE NO. AS 111-13.

. r--- i. gii,, I ~~ [ .tlv

l,i l;;, ll.il 111 ii'i I.ti;g, j

t. l ,l, i. llie I I l}:s tai i i is t, EATIEllE I.I-IR l I {ji:, ll i]. ll I ' l '!' ,t ._.r,..__.-_ .__{'___. p; ,, e,- .. g l l II i i g ..i i i.' alt. ol t.ht..4 I'.. ). ' L..] .'L. I i -..i..- g. ._3 ' i!! !l l.!! !l. !ll '!.. .~ _.g l l I it i!' 4I' L.Il I r. g h _ __.1_ ._.d t j. .t i__ _. _b !.,k :.::h1 .LdM.Fl? q lil 'i }___ _. .___I .a ..... _. I

j' l

f.';;,-

. j,i.'

t.. l --44r~ .1 l:i . i. t. M..W ---4-- .t.._.._q_.. t . ' _- i.j ti-l 3 i .i .. __ 4.- ' .4.__ i l ..l'i:ll' i'!! I:; ?!l. .i i l _s g p _. i 1.;. 6l! l __.7 _a.._f. p_ . _L _.,,. M.. I.U_' t___ _L_ _.__.. it. 8 . g.... ' _.. __E. ( j 's g. 11 { 8_, .y _. 2_ ?, - !i l,. . Il !t-. l

t. i i,

'.l'--- r---- -- ~ ~ ~ ,,i l i l l s.. 4 'A g .4 a. .Q g Y' ,l.. o Y.l.. i i. g ..t, lg i. ll., a .e s - __.~. i it i: - l-i 4._* '..-_h' .p l. ). _._ % wpm 'J M ) p t ,s~m-y'. p w- %~ m a i v I i ( i 1 _e, 31ss sees 2Was ' j tssa i..itas. itse

ehe i ea ma

..I- ,_..._I___.

u. v_o_ age. t.ni o-i:

p j ec;' p i.g p-l riurnirg'c s l l 4: _i-. 4 i j m.:rci. race 4 a+ h.4 . -. j +- art.:= mens l!b !jl ibi $I"*9 _.d b,!!I Y_.7 b,ij bil bl$NMa i ! i i FIGURE 25b. INFRARED TRANSMISSION SPECT'RUN FOR POLYPPOPYLENE STANDARD L

1 l l i l l 4 BATTELLE COL t I i l c Q _- v u l l l l l l 3600 3200 2800 2400 2000 1600 1200 800 600 Wavenumbers FlGURE 26. INFRARED TRANSMISSION SPECTRU 1 FOR PARTICLE REMOVED FROM ID SURFACE OF PIECS 4 FROM TUBE NO. A 111-13.

4 4444 44. E' Addition of Hp02 0 16 !iM I!!il1 itil 1111 till lill i 25 ' 20"--------- HM2_T,a rget Level 15 JO 3 9 r . '-- --- g0._ Target Level ".2 5 0 0 50 10e 150 200 260 3d0 360 40'0 3 e 2 l ~ 1 n' -~ 0 50 100 150 200 250 300 350 400 { Reaction Time, hours i FIGURE 27. HYDROGEN PER0XIDE AND SULFATE CONCENTRATIONS AS A FUNCTION OF REACTION TIME FOR IMMUNOL EXPANSION RUN-1 AT pH8 AND 130 F (UNTREATED TUBE SAMPLE 14 in. FROM EXPANSION TRANSITION ZONE). i

444 ' 444 &&iS4 4.. ~ Addition of H 02 2 3 3U., ; 11111 !!illl 1!!!! ! 11 111I lill I l $'" 25 - 2 - - - - - - - - - - - H 0,2,,Tayp,e t, [ ey e l _,,,,,_,,, _ _,,,_ _ _ _ _ _,, _ __ _ _, _ _ _ _ _ _ _ _ _ _ _ _ _,, _ _ _ _ _,, 2 , i i 15 - 10 g_ ..l'...*"..Hg02,,, Tag,gd,L,"e_yel,,"_*

• f",,,,,;;,,,,

0 $0 100 15'O 200 2$0 300 35O 400 0 3-2- ? l3 1. 0 0 50 l'00 15'O 2'00 250 3b0 350 40d i* Reaction Time, hours h FIGURE 28. HYDROGEN PEROXIDE AND SULFATE CONCENTRATIONS AS A FUNCTION OF REACTION TIME FOR IPfiUNOL EXPANSION RUN-2 AT pH8 AND 130*F (UNTREATED TUBE SAMPLE FROM EXPANSION TRANSITION ZONE). f

1 W' ' 35< E3 Addition of H202 ~~ 30 8 I! llIll lll01 l0ll llll -llll ll l ", 25 ' 8 3 20"- - - - - - - - - 2'J 'l *#' D- - - - - - - - - - -- -- - e - - b 5 , g 15' u & 10- .g b' ---.'-_ ~~- g02.la.rget_ _Lgygl. [*_ _ _' ~_._,:._ _ _ _ H 0 ~ ld0 160 20'O 250 300 350 400' 0 5 l ),g3'

s P

'T I82-B 2 IY s8 8v 1-E 0J 0 50 100 150 200 250 300 350 400 Reaction Time, hours FIGURE 29. HYDROGEN PEROXIDE AND SULFATE CONCENTRATIONS AS A FUNCTION OF REACTION TIME FOR IMMUNOL EXPANSION RUN-3 AT pH8 AND 130 r (IMiUNOL TREATED TUBE SAMPLE 14 in. FROM EXPANSION TRANSITION ZONE).

141 4484 Mit E. 35 - ~ Addition of Hp0p 30 il IIlll Niill llll llll lill ill ll 25 - 2 arget Level T "------- g0 H 20 15 'l 10 " l 5' ....... 202.. Target Levei........ ". ".... H a.... 0 - ~ 0 5b 10d 150 200 250 300 350 400* l l f 3-2- 1-s 0< 0 50 100 150 200 250 300 350 400 Reaction Time, hours FIGURE 30. HYDR 0 GEN PER0XIDE AND SULFATE CONCENTRATIONS AS A FUNCTION OF REACTION TIME FOR IMMUNOL EXPANSION RUN-4 AT pHS and 130 F (IMMUNOL TREATED TUBE SAMPLE FROM EYPANSTION TRANSITI0d' ZONE).

BA TTELLE COL \\ J l ( i i l l 3600 3200 2800 2400 2000 1600 12d0 860 600 Wavenumbers FIGURE 31. INFRARED DIFFUSE REFLECTANCE SPdCTRUM FOR SAMPLE NO. 2-10 AFTER PER0XIDE CLEANING (IMMUNOL EXPANSION RUN-21

~BA T TE LE cod i N9 A ~ 1 W ( i 1 I 8 9 3 g 3600 3200 2800 2400 2000 1600 1200 800 600 Wavenumbers FIGURE 3 2. INFRARED DIFFUSE REFLECTANCE SPECTRUM FOR SAMPLE NO. 2-2 AFTER PEROXIDE CLEANING (IMMUNOL EXPANSION RUh-1).

W G B BATTELLE COL i I l ) 1 ( 3600 3200 2800 2400 2000 1600 1200 800 600 Wavenumbers FIGURE 33. INFRARED DIFFUSE REFLECTANCE SPECTRUM FOR UNCLEANED SAMPLE NO. 5-7.

I f BA T TELLE CO[ 1 r I 1 If J \\ L i ( 3600 3200 2800 2400 2000 1600 1200 ' 800 600 Wavenumbers FIGURE 34. INFRARED DIFFUSE REFLECTANCE SPECTRUM FOR SAMPLE N3. 5-2 AFTER PER0XIDE CLEANING (IMMUNOL EXPANSION RUN-3). -er,----ew---,---e- --,r--- --,--------r. .w v-,.,e- --+--ece------w--- - - - -- - -wrw--..-v

---

w-

--,s "e

BA T TELLE d;C S l l e 3600 3200 2800 2400 2000 1600 1200 800 600 Wavenumbers FfGURE 35. INFRARED TRANSMISSION SPECTRUM 0F POLYETHYLENE PARTICLE REMOVED FROM ID SURFACE OF SAMPLE NO. 5-10 BEFORE CLEANING.

PRELIMINARY CONCLUSIONS Results from the tube cleaning experiments are summarized below: TUBE CLEANING SERIES 1 These samples were in the same condition as when they were removed from the TMI-l steam generator. Sulfate production leveled off after approxima ely e 150 hours. Total sulfur acalyses and SFM/EDAX examinations indicate nearly complete remova? of sulfur from tube

samples, o The results from the FTIR diffuse reflectance measurement showed a small amount of organic contamination on the ID surfaces of the tube samples, as evidenced by the CH2 and CH3 bands at 2925 and 2960 cm-1, respectively, There appeared to be no difference in cleaning rate e

between pH 8 and pH 10. TUBE CLEANING SERIES 2 These tests involved Immunol treated and untreated TMI-l tube samples that had been exposed to eebris from the explosive expansion These tube sections were connected to the expanded tube during process. the explosive expansion by means of a Swagelok fitting containing a I restrictive orifice. Immunol treated tube samples in Run -3 gave the same e sulfate production rate as the untreated samples in Run -4. l Sulfate production appeared to be at completion after The Immunol treated tube samples from Run -1 and 50 hours. -2 followed roughly the same profiles as Run -3 and -4, except the sulfate started increasing again after about 150 hours and plateaued at about 230 hours. r .-~

I Hydrogen peroxide concentration was more stable for the e Immunol treated samples. The infrared results showed that the tube samples not e treated with Immunol retained a polypropylene material. The presence of the polypropylene did not appear to affect the peroxide cleaning process. Debris particles found on the tubes were identified as polypropylene. No evidence of Immunol on the sample surfaces were observed. Evaluation of SEM/EDAX and total sulfur data still in o progress. TUBE CLEANING SERIES 3 The tubes used in this saries of c1 caning experiments were explosively expanded with and without Immanol treatuent. Samples involved in these tests were from the expansioa transition zoae and from s distance about 14 inches from the transition zone. lhe nulfate concentratiosa/ tine cerves were essentially e the same for all four beaker tests. The sulfate concentration leveled off after about 50 bcurs but increased again after about 150 hours, becoming constant after 330 hours. Hydrogen peroxide concentration levels as measured by the e peroxide color test increased anomalously without any peroxide addition after about 200 hours, then decayed slowly to about 30 ppm by the end of the runs at 400 hours. SEM/EDAX and ESCA studies still in progress. e The infrared results showed presence of polypropylene on e tube sample ID surfaces. Debris particles were found to consist of both polyethylene and polypropylene. Analysis of spectra is continuing. I e

The detailed interpretation of the data covered in this report is still in progress,and along with additional data will be presented in the final report on this program. The additional data will also include another series of tube cleaning experiments. The tubes involved in the next series will be expanded tube samples with thicker Immunol coatings the'. are more representative of the coatings that will be used in the actual cleaning of the TMI-l steam generator tubes. In these next ex-periments, blanks will be run with clean Inconel-600 samples with no sulfur contamination and with only the peroxide cleaning solution without any Inconel. An important feature of future cleaning studies will be to direct more attention to the intermediate sulfur species that are formed. A number of the possible intermediates formed in the oxidation chain going from sulfide to sulfate are shown in Figure 36. The tetrathionate, thiceulfate, and possibly other species cam severely attack Inconel. A better under-standing of the concentrations of these intermediates and their influence on the cleaning process is advisable. l l i

1 ,l s0 s s j 36 25 27 s"2 8'3 s" s s 0", s" so" s S0" i S s,o"6 8 3 2 2s 2 (-2) (-1) (-2/3) (-2/x) (0) (+1.6) (+2) (+3.3) (+3) (+4) (+5) (+6) S0= 4 46 (+ 2.5) -8 e-i i Figure 36. Reaction Intermediate, for Oxidation of Sulfide to Sulfate. 4 1 J

l APPENDIX A The following figures ano tables presen; the results of the total sulfur analyses on the tube samples and summarize the results in terms of culfur cleaning efficiencies.

l TABLE A 1.

SUMMARY

OF SULFUR CLEANING RESULTS FOR THI-1 TUBE SAMPLE E (A) (B) (C) j Beaker Sulfur In Sulfur Removed Sulfur in C ea" " kr Unclean Sample, Bycleanjng, Cleaning,pgSO /in.2 Bi(B+C)x100 (A-C)?Ax100 Sample after Cleaning Efficiency, Percent pg SO /in. pg SO /in 9r Te 9, 4 4 4 1 Tube Run-1 28.6 51.0 8.2 86.1 71.3 Tube Run-2 22.8 39.1 6.9 85.0 69.7 l Tube Run-3 38.5 66.3 10.2 86.7 73.5 Tube Run-4 53.7 70.1 5.7 92.5 89.4 2 Immunol Run-1 20.6 105.6 55.6 65.5 Immunol Run-2 20.6 125.7 25.3 83.2 Immunol Run-3 20.6 64.8 14.0 82.2 32.0 Immunol Run-4 20.7 67.4 7.6 89.9 63.3 i j 3 Imm. Exp. Run-1 4.5 56.9 12.3 82.2 Imm. Exp. Run-2 7.8 48.0 9.7 83.2 Imm. Exp. Run-3 7.0 60.8 12.4 83.3 Imm. Exp..Run-4 10.0 62.3 12.5 83.3 l a

A nd 4.b. ..,Y tf

• e' W dd n oe. -

- f. ---+- - 96 -q, 2 To - ~ -go 76 - -Te 9 C Lo - - t.e 4 ya - -se B e i io - g -4e B -b 4 3o-g A to - -te A A io - -n L -c o-m..._.. FIGURE A -1.

SUMMARY

OF SULFUR ANALYSES AND CLEANING EFFICIENCIES FOR BEAKER CLEANING SERIES 1

{ len l 176 lu - l l Ira - I4a - 13 6 - p Ita - er} c L,.,sts $ *ge I n oe - l b 0W res - -ix Y Fz

n. -

b + o e, _ I_ enL

v. -

-d s h a- + b [3 c

y. -

-se t E l 4a - B -de ( x i \\\\ ^ C -1' 3- \\ -t' z_ ~a h m. 0-r-m u..1 Run-t Immue al R e-E. Immwael Run-3 Im mund Run FIGURE A-2 SLWiARY OF SULFUR ANALYSES AND CLEANING EFFICIENCIES FOR BEAKER CLEANING SERIES 2

I I t i f.x se oo 106 - o 9s - .4 ~ Eo - -Ce To - -T, c3 - -w Co - -ra B B 4o-- 0 -4< ' E 3*- -S e to - -4c C C c A q O= "O Iww. 6up kA==l I m m. EJr p 8v b*1 Imm. E,,. Re $ I ..he, % -4 FIGURE A-1

SUMMARY

OF SULFUR ANALYSES AND CLEANING EFFICIENCIES FOR BEAKER CLEANING SERIES 3

w -.a -0 e i } i e i i i 4 J J f t APPENDIX r 1 l 1 ] i ) I i i i f I i .,,....__...,_._..,.___.m.-.-_

1 TABLE 3. SPECIMEN ASSIGNMENT Test Cleaning U-bend No. ESCA-Auger No. Solution Beaker No. IN600 304SS C-Ring No. Specimen No. pH 8 3 6-01 3-01 l' armonium to to 1 hydroxide 6-03 3-03 B11-23 (1-3) B11-23 2 6-04 3-04 pH 10 to to lithium 6-06 3-06 B111-62-7A (1-3) B111-62-7A l hydroxide 3 6-07 3-07 A71-126 (1-2) i to to 6-09 3-09 A78-32-2 (1) A71-126 4 6-10 3-10 to to pH 8 6-12 3-12 A78-32-2 (2-4) A78-32-2 i Immunol treated 5 A11-13-5 (4,6,8) 2 pH 8 l non-Immunol 6 A111-13-2 (4,6,8) I treated 3 Thio, sulfate 7 6-24 3-24 A78-32-2 (5) l l [ i I

t t f. g TABLE 4. RESULTS OF THE METALL0 GRAPHIC EXAMINATION FOR THE I .RESENCE OF CRACKS ON THE EDGES OF THE STAINLESS STEEL TYPE 304 U-BEND SPECIMENS (MAG. = 250 TEST 1) Figure 8 identifies examined positions 1, 2 and 3 on the U-bend. Position Cleaning (0= No Cracks Observed) Solution Beaker No. Specimen No. Side-1 2 3 PH 5 1 3 1 0 0 0 ammonium 2 0 0 0 hydroxide 1 3-02 1 0 0 0 2 0 0 0 1 3-03 1 0 0 0 2 0 0 0 2 3-04 1 0 0 0 i 2 0 0 0 i 2 3-05 1 0 0 0 2 0 0 0 2 3-06 1 0 0 0 2 0 0 0 pH 10 3 3-07 1 0 0 0 lithium 2 0 0 0 hydroxide 3 3-08 1 0 0 0 2 0 0 0 3 3-09 1 0 0 0 2 0 0 0 4 3-10 1 0 0 0 2 0 0 0 4 3-11 1 0 0 0 2 0 0 0 4 3-12 1 0 0 0 2 0 0 0 i l

i l TABLE 5. RESULTS OF THE METALL0 GRAPHIC EXAMINATION FOR THE PRESENCE OF CRACKS ON THE EDGES OF THE IN600 U-BEND SPECIMENS (Mag. = 250X TEST 1) Figure 8 identifies examined positions 1, 2 and 3 on the U-bend specimen. Position Cleaning (x = No SCC Observed) Solution Beaker No. ' Specimen No. Side 1 2 3 pH 8 1 6-01 1 0 0 0 ammonium 2 .0 0 0. hydroxide i 1 6-02 1 0 0 0 2 0 0 0 1 6-03 1 0 0 0 2 0 0 0 2 6-04 1 0 0 0 2 0 0 0 2 6-05 1 0 0 0 2 0 0 0-2 6-06 1 0 0 0 2 0 0 0 1 pH 10 3 6-07 1 0 0 0 lithium 2 0 0 0 l hydroxide 3 6-08 1 0 0 0 2 0 0 0 i 3 6-09 1 0 0 0 2 0 0 0 4 6-10 1 0 0 0 2 0 0 0 4 6-11 1 0 0 0 2 0 0 0 i 4 6-12 1 0 0 0 2 0 0 0 ,s , -, - -, ~,,, - -,.,n.- --.-n,-,- -,n,,

f l l TABLE 6. RESULTS OF THE METALLOGRAPHIC EXAMINATION OF THE LEFT HALF-SIDES OF THE C-RINGS (TEST 1) Cleaning Solution Beaker No. Specimen No. Side No Cracks Found* pH 8 1 Bil-23 (1) 1 0 ammonium 2 0 hydroxide 1 Bil-23 (2) 1 0 2 0 1 Bil-23 (3) 1 0 2 0 2 Bill-62-7A (1) 1 0 2 0 2 B111-62-7A (2) 1 0 2 0 2 B111-62-7A (3) 1 0 2 0' pH 10 3 A71-126 (1) 1 0 lithium 2 0 hydroxide 1 0 3 A71-126 (2) 2 0 3 A78-32-2 (1) 1 0 2 0 4 A78-32-2 (2) 1 0 2 0 4 A78-32-2 (3) 1 0 2 0 l 4 A78-32-2 (4) 1 0 2 0 W 5 mall intergranular attack present. i

a TABLE 7. RESULTS FOR THE RIGHT HALVES OF THE C-RINGS, (TEST 1) Solution Beaker No. Specimen No'. No Crack Found* j pH 8 1 Bil-23 (1) C ammonium hydroxide 1 Bil-23 (2) 0 1 Bil-23 (3) 0 3 2 Bill-62-7A (1) 0 2 B111-62-7A (2) 0 2 Bill-62-7A (3) 0 pH 10 3 A71-126 (1) 0 lithium hydroxide 3 A71-126 (2) 0 3 A78-32-2 (1) 0 4 A78-32-2 (2) 0 4 A78-32-2 (3) 0 ( 4 A78-32-2 (4) 0 I

• Ir.tergranular attack present on all tubes.

l 1 m r-r- n ,p ---,, - ------, =

TABLE 8. AUGER AND ESCA ANALYSIS OF C-RINGS IN BEAKER 1 (TEST 1) Depth Below Surface Concentration ( m) (atomic %) Cu Ni Co Fe Cr 0 C Si Zn Al 0 3.6 4.2 1.8 1.7 1.3 55.2 14.0 9.0 4.9 4.4 0.005 5.1 11.9 nr 4.8 2.2 46.7 5.0 7.0 4.7 12.6 0.025 6.6 7.2 nr 8.6 5.0 55.5 2.8 6.8 2.3 5.1 nr = not reported TABLE 9. AUGER AND ESCA ANALYSIS OF C-RINGS IN BEAKER 4 (TEST 1) ~~~ D:pth Below Surface Concentration ( m) (atomic %) Cu Ni Fe F Cr O Ag C Zn Si Al 0 3.3 6.1 5.2 13.2 3.2 38.4 0.2 23.4 3.9 1.2 1.7 0.005 3.5 16.2 6.6 7.4 8.4 35.0 0.4 7.1 2.1 2.3 11.0 0.025 4.0 17.1 6.9 5.8 6.4 32.5 0.2 8.1 1.8 1.8 15.5-

L { ( ~ r l r L ( TABLE 10. RESULTS OF THE METALL0 GRAPHIC EXAMINATION r L OF THE LEFT HALF SIDES OF THE IMMUNOL AND NON-IMMUNOL TREATED C-RINGS FROM EXPLANDED TUBES (TEST 2) r L Stress Corrosion ( ' Cleaning Cracts Found Solution Beaker No.* Specimen No. Side No Yes ( pH 8 5 A111-13-5 (4) 1 0 Imrtunol 2 0 treated ( 5 A111-13-5 (6) 1 0 2 0 l 5' A111-13-5 (8) 1 0 2 0 l pH 8 6 A111-13-2 (4) 1 0 non-Immunol 2 0 treated l 6 Alll-13-2 (6) 1 0 2 0 l 6 A111-13-2 (8) 1 0 2 0 ~~ No sulfide additions to the solution, cover gas for the beakers was air. k

TABLE 11. RESULTS FOR THE OPENED UP RIGHT HALVES OF THE IMMUNOL AND NON-IMMUNOL TREATED C-RINGS (TEST 2) ~ Stress Corrosion - Cleaning Beaker No. Specimen No. Cracks Found Solution Beaker No. Specimen No. No Yes pH8 5 Alll-13-5 (4) 0 Immunol treated 5 A111-13-5 (6) 0 5 A111-13-5 (8) 0 non-Immunol 6 A111-13-2 (4) 0 treanted 6 A111-13-2 (6) 0 6 A111-13-2 (8) 0

TABLE 12. COMPARISON OF CONCENTRATION OF OXYGEN EXPECTED IN OXIDE FORM TO THE TOTAL MEASURED OXYGEN e . Beaker 1 Beaker 4 Probable Atomic % Total Measured Atomic % Total Measured Oxide Oxygen Oxygen Oxygen Cu0 3.3 3.6 Ni(OH)2 12.2 8.4 coo 1.8 Fe00H 10.4 3.4 Cr(OH)3 9.6 3.9 Sio 2.4 18 Ag0 0.2 Zno 3.9 4.9 Al 0 2.6 6.6 23 Total 44.6 38.4 50.6 55.2 __. -__.}}