ML20235M356
ML20235M356 | |
Person / Time | |
---|---|
Issue date: | 01/31/1989 |
From: | Tokar M NRC OFFICE OF NUCLEAR MATERIAL SAFETY & SAFEGUARDS (NMSS) |
To: | Voit R LN TECHNOLOGIES CORP. (FORMERLY LONDON NUCLEAR SVCS |
References | |
REF-WM-99 NUDOCS 8902280222 | |
Download: ML20235M356 (10) | |
Text
_ -_ _ _ _ _ _ _ - _ _ - _ - _ - _ _ _ - _ _ - _ _ _ _ - - _ _ - - -
WM99LTR2.00C
~Mr. Regan E. Voit
' Vice President, Operations JAN 311989
~LN4 Technologies Corporation-
- 1501 Key Road Columbia, SC 29201
Dear Mr.-Voit:
SUBJECT:
LN TECHNOLOGIES REPORT " TOPICAL REPORT ON 10 CFR 61 QUALIFIED RADIOACTIVE DECONTAMINATION RESIN WASTE FORMS,"
LN-88-001,. JUNE 1988; DOCKET N0. WM 99 The subject report was reviewed by our technical consultants, Brookhaven National Laboratory (BNL) and National Institute of Standards and Technology (NIST), and the review comments were sent to us recently. Because of other
- high priority work and resource limitations, our staff has not completed the review of either the subject report or the consultant's comments on the report.
Therefore, our staff has not yet prepared a formal " Request for Additional Information (RAI) " to be sent to you. It will be prepared after the staff has reviewed both the report and the consultant's comments. However, we are providing you with copies of our consultant's comments. They should be considered as informal comments on your topical report. You have informed us s
- that LN Technologies is conducting some additional tests to supplement the information in the subject report. The NRC would like to review this additional databeforepreparingformalcomments(RAI)onthisreport. We hope the enclosed informal comments will be helpful to you in formulating your response to a formal request by the NRC for additional information on your Topical Report. . You may expect to receive the formal comments and RAI in May 1989.
Once again, these are advance copies of preliminary comments on your topical report and.should be treated as such.
i If you have any questions on this, please call me or Dr. Banad Jagannath of my staff (301 492 0593).
Original Signed By Michael Tokar, Section Leader 'i Technical Branch Division of Low Level Waste Management and Decommissioning, NMSS
Enclosures:
.As stated Distribution:
w/ enc 1. w/ encl. w/o encl.
NM55 r/f JJ5urmeier MKnapp LLTB r/f MTokar JGreeves i 7 E LLWMir/ft BJagannath PLohaus
+ MBell CCdiRAL FILECl NM W $UdI I Wl=il h /kDOne' MM-%
- LL :LLTB : : : :
i'FC :LLTB g; . . . . . : _ _ . . . . . . . . . . . : . g....:...______...:______......:.._____.....:_......____
_A ,W. ...:-___
LAME :BJagannath/jl:MTokar :JJSur ier : : : :
' ATE:(/p/89 : : : :
j;
- / /74/89 l/2f89 :
OFFICIAL RECORD COPY j L
h0,23gjpg89o131 p/3pgg
- L flLil
g
- g *
- :,;
4
, q 1
BROOKHAVEN NATIONAL LABORATORY MEMORANDUM
.DATE: January 5, 1989-To: File'#84 FROM: D. R. MacKenzie sueJECT: Comments and Questions Regarding the LN Technologi,es Corp.
Topical Report, " Topical Report on 10 CFR 61 Qualified Radio-active Decontamination Resin Waste Forms," LN-88-001 Generalj It appears that this topir.al report contains most of the information required to qualify cement waste forms made with LOMI resins and with CAN-DECON resins. - The information on testing methods and results obtained is systematically laid out.in the body of the report, with detailed calculations-
< and testing documentation .given in Appendices, along with PCPs .for the LOMI and CAN-DECON resin este' forms. The information thus provided satisfactorily :
addresses most,' but in BNL's view'not all of the requirements.of 10 CFR 61 and the Technical. Position on Waste -Form (see TR conclusionsSection VIII). In
. addition, the information -is not.' sufficient to comply fully with the addi-tional. requirements referred to on page 5 of the TR, including those set forth in M. Tokar's . letter of December 18,'1987..to R. E. Voight of LN. That letter ;
requested LN to submit, by May 30,.'1988, data to support LN's maximum waste ' l y loading, in view of.. observed surface and bulk degradation phenomena and a 4
typical cement. behavior which appears to be associated 'with excessive waste loading of. cement waste ' forms. The starred (*) items below are the ones BNL considers most significant.and most seriously need to be resolved.
Specific Questions and Comments Replicate Samples
- 1. On page 5 (Section III) it is mentioned that test results should be at least in duplicate, except for irradiation testing, and that the LN test program complies with this requirement. In fact, LN did not do, or at least report . test results of, thermal cycling, bacterial expcsure, fungal exposure and 90-day water immersion, for duplicate specimens of any formulation, either LOMI or CAN-DECON. A relatively large number of specimens were tested by water imersion, for similar formulations (i.e., differing only slightly in water, lime or cement co'ntent), but not for the same formulation. What is the i rationale for this? (Is it considered, for exampl e, that compressive '
strengths of tested specimens averaging almost an order of magnitude higher
'than the 60 psi minimum of NRC's Technical Position makes duplicate testing unnecessary?) ;
7, i ,
Page'll,'2nd Paragraph
~
- 2. What is the significance of the use of the term ALARA in this connec-tion? Does it refer to- the use of non-radioactive isotopes for the leach tests, which result in zero radioactive release and is thus even better than ALARA release?
-Section V.C.5.b, Page 13,1st Paragraph
- 3. -
- rectly as 10 On8 line 5, the radioactivity contgnt in parentheses is given incor-uCi/ liter. This should be 10 pCi/ liter or 10-3 C1/ liter.
- Section V.C.5.b, Page 13 >
- 4. Section C.2.e of the TP on waste form states, in part, "it is prefer-able that radioactive tracers be utilized in performing the leach tests." All the leach _ testing for LN's LOMI and CAN-DECON resin waste formulations were done using nonradioactive Cs, Sr and Co ions. As a rationale for using the nonradioactive ions, LN presents results of leaching of'Na250g waste specimens containing cesium, which showed that the leach indices obtained using non- i radioactive cesium were comparable to, but slightly lower than, those obtained j using Cs-137, and concludes that results obtained with nonradioactive cesium !
appear to be more conservative.
Two points should be made. First, the results apply to only one of. the ,
three ions for which leach indices need to be determined, albeit the ion wLich '
is likely to be most critical. Second, the comparison of the radioactive versus the nonradioactive' method was carried out on specimens of a waste stream (Na250g) not under consideration in this topical report. Cement forms made from decontamination: resin wastes are se different from those made from Na 2S0g waste that it is not at all clear that a direct extrapolation can be made from one to the other.
Does LN.have any-evidence that the results for Na S0 2 g waste specimens are applicable to specimens of the . decontamination resin waste formulations? If not, . and if such a demonstration is required, it'is suggested that two specinens of LOMI and/or CAN-DECON formulations already tested using nonradio-active ions be given abbreviated leach tests .using the radioactive tracers Cs-137, Sr-85 and Co-60 to establish _ correlation between the two methods for decontamination resin waste specimens.
Section V.D, Page 13
- 5. LN refers to the correlation of specimens with full-scale waste forms i (required by Section C.2.1 of the TP on Waste Form) and also to the demonstra-tion of homogeneity of full-scale products (required by Section C.2.j of the TP). LN then states that samples from 1" full-scale powdered and bead resin products have passed the acceptance criteria, and argues that because of these tests and the successful solidification of actual LOMI decontamination w:ste, ]
additional full-scale liner tests with LOMI or CAN-DECON should not be neces- '
sary. LN presents, u. Table S of the TR, compressive strength data for three
! samples from two full-scale products in support of their position.
I (Page 2 of 6)
b BNL does not consider that these tert results provide sufficient informa-tion to satisfy the Section C.2.1 and C.2.j requirements. Interpretation of the wording of Section C.2.1, in particular the meaning of " characteristics,"
is debatable. It could be argued, as LN apparently does, that the compressive strength " characteristic" is all that is rquired to demonstrate correlation.
However, it could also be argued that other characteristics such as resistance to radiation, biodegradation, and immersion in water as specified in the TP, must also be shown to be correlated. If the latter position is taken by NRC, sections or cores of full-scale products will have to be tested in accordance with the TP stability guidance of Section C.2. If the former position is taken, LN should present compressive strength data from several cores from a single full-scale waste form. To meet the homogeneity requirement, a minimum of five samples should be tested, one each from the top and bottom center, and three from the side of the cylinder near the top, middle and bottom and at different radial positions.
Also note that these results should be presented in the "Results and Discussions" section (Section VI) rather than in Section V. It is understood that the Table 8 results are presented more as an example to indicate why, in LN's opinion, further efforts in full-scale correlation testing should not be necessary, rather than as data to support demonstration of sati sfying TP requirements per se.
Section VI, Page 15 ff
- 6. The discussion of results in this section of the TR refers to the tables and ternary phase diagrams given in Appendix A. It would be a Great help to the reader if these tables and diagrams were given at the appropriate locations in Section VI, rather than collected together after the references, so that one would not have to keep turning back and forth to the end of the report. While it is considered that this would be an improvement in the TR, the present format is obviously acceptable.
Section VI.A, Page 15, and Tables 2 and 3
- 7. On page 5 of the TR (last line), LN has stated that their test program complied with the requirement that loss in strength during testing be
<20%. In most cases this is so, but it is not in the case of 5 LOMI formulations, as shown in Table 1 which summarizes all the relevant results.
For biodegradation, thermal cycling and irradiation testing, specimens measured after the tests invariably had compressive strengths greater than those of the controls. However, for immersion testing, the only formulations for which specimens had clearly higher strengths after testing were those with considerably lower waste loadings than the standard formulation (i.e., much higher cement: waste ratio). A good deal of scatter is evident in the results, but the fact remains that, as presented, the LN data contain some results showing that compressive strengths after testing were lower by >20% than before testing. Does LN have any arguments to suggest how these results show that the formulations involved " comply with the additional requirements ," as stated on page 5 of the TR?
(Page 3 of 6)
3.
' Table 1 Test Results for LOMI Formulations:
Compressive Strength Change During Specific Tests Wt. Cement % Change in in Formu- Compressive Test lation, 9 Control Tests Strength Biodegradation 85 340 380,390 +12, +15 Thermal . Cycling 85 600 ave., 1444 +98 from 730 highest highest control Irradiation 85 600 ave., 870 +19 from 730 highest highest control
'Imersion/ Leaching 85 600 ave., 280(DIW) -26 from 730 highest lowest control
-62 from highest control 710(sea water) -3 from highest control 85 340a 250(DIW) -26 300(sea water) -12 300a 250DIW) -17 180 sea water) -40 320a 280 DIW) -12 280 sea water) -12 85 290b 200(DIW) -31 180(sea water) -38 132 470 440(OIW) -6 580(seawater) +23 171.8 710 1070(DIW) +51 890(seawater) +25 formulation containing additional water l bF ormulation containing additional water and line i
I I
)
(Page 4 of 6) j
\
- 8. Also in~ this connection, control specimens for formulations RLS-23,24 and RLS-41,42 (with 75 and 65 g cement, respectively) were not tested. Does LN have a rationale for expecting that these formulations with less than their
" standard" amount of cement which might yield a lower-quality product would comply with the <20% strength loss requirement?
Section VI.A.1, Page 15, Paragraph 2, and Section VI.A.6, Page 18
- 9. LN reported cracking in waste forms from at least 2 different LOMI fo rmul ations , namely that used to prepare biodegradation test specimens
(" standard" fonnulation), and one or two others which were not specified (page 15). These should be specified and their compressive strengths given. (In addition, one of the 7-day cure specimens is said (page 16) to have exhibited cracking after the leach test in demineralized water.) For all cracked specimens an evaluation should be given of the extent to which their stability was degraded as a result of their cracking. Also, were any other specimens, either LOMI or CAN-DECON and whether for specific tests or for controls, observed to exhibit cracking or other surface or bulk degradation? If so the I foregoing procedure should be followed for these also.
Section VI.B, Page 20, and Tables 5 and 6
- 10. The results of tests on CAN-DECON waste forms given in Tables 5 and 6 contain no data for control specimens. Were control specimens prepared and tested for compressive strength? If not, it is not possible to show that loss l of strength during tests was <20%, although on page 5, LN states that its test !
program complies with this <20% loss in strength requirement. LN should either present data to support the <20% strength loss claim, or else justify the position that such a demonstration is not necessary for the CAN-DECON formulations.
Section VI.B.3, Page 21
- 11. The reader is referred to Section IV.D for a discussion of the validity of leach indices determined with specimens cured for less than 28 days. The discussion is actually in Section VI. A.4, not in IV.D.
Tables 3 and 6
- 12. Tables 3 and 6 have a column headed "FSW at 24/48 hrs," in which the entry is always "No." It is assumed that FSW refers to free-standing water, but this does not seem to be a standard abbreviation. It would be helpful to '
have a footnote to the tables explaining the meaning of the initials.
Appendix' A-I, Leach Data for Samples RLS 13 and RLS 14 !
- 13. The surface areas, and thus the volume / surface ratios, appear to be i incorrect for these specimens. For example, the surface area for RLS 13 is t given as 152.10 whereas it apparently should be 149.98. (These small inaccu- l' racies do not affect the final values arrived at for the leach indices.)
i l
(Page 5 of 6)
4 Appendix A-II, First Entry (Microbac)
- 14. In the report from Microbac on its thermal cycling tests of LN's specimens, severe surface cracking is said to have occurred with sample RCD 19T. Hairline fissures are reported to have appeared and began to increase in size and depth after about 10 cycles. Then _ in later cycles the condition worsened to such an extent that large surface pieces fell off the specimen.
The results for this specimen are not mentioned in the body of the TR. Sampl e RCD 19T was subsequently sent by Microbac to West Penn Testing Laboratories, Inc., along with Samples RCD 9T and RCD 14T (see 8 pages after Microbac report). Compressive strengths were determined for the last two samples but not for RCD 19T. Was this because Specimen RCD 19T had deteriorated to the point where it could not be tested? What was the formulation of this specimen, e.g., was it one of the four listed in Table 7? What was its history? What is suspected to be the reason for its degradation, particularly in terms of its formulation and as this relates to other similar formulations?
Atypical Cement Strength Behavior
- 15. Our interpretation of M. Tokar's December 12, 1987, letter is that LN shoulu demonstrate that the atypical cement strength behavior observed by BNL does not occur with LN's formulations, particularly at the maximum loadings they wish to qualify. LN has not provided such a demonstration in their TR.
It should be done for at least the formulation with maximum waste loading for each of the LOMI and CAN-DECON resin wastes. Room temperature cures of 7, 14 and 28 days are appropriate for preparation of specimens for the 90-aay immersion testing and for controls. [ Note that compressive strengths would have to be determined on control specimens for each of the cure periods, as well as for the tested specimens after 90 days immersion.]
A possible alternative for LN would be to demonstrate that actual full-scale waste forms prepared from their formulations undergo substantial heating for an initial period of one or more days. If specimens prepared under the same temperature-time conditions did not exhibit the atypical strength behavior (of decreasing strength with increasing room temperature cure time after an initial heating period), then specimens for qualification testing could be prepared by using such conditions.
)
(Page 6 of 6)
v
>9 y
12/15/88 Review of: " QUALIFIED RADI0 ACTIVE DECONTAMINATION RESIN WASTE FORMS" LN-88-001, Submitted by LN Technologies Corporation Review By: James R. Clifton NIST Comments:
- 1. Pg 1,
Introduction:
the decontamination processes CAN-DECON and LOMI should be briefly described in terms of what is being decontaminated and additional information on the resins used.
- 2. I would like to see a Scope section following the introduction that clearly and concisely explains the purpose of the topical.
report and what is included in it.
- 3. Pg. 5, 3rd line from bottom: I recommend that test results should be in triplicate for all tests, no exception for irradiation testing.
- 4. Pg. 6, A. Types of Cement-let paragraph: Why is not. type V included in discussion. I am sure that there is no type IV available in-the US. Very little, if any Type III is available, as well as Type V. About 95% of the cement available is Type 1 and about 4% is Type II.
- 5. Section A, 2nd paragraph: The statement " Type I is readily available at's reasonable cost in most areas of the country
" should be revised to state " Type I is readily available at a reasonable cost throughout the country "
- 6. Pg. 7, 1st paragraphs Tricalcium aluminate reacts very rapidly with water and gypsum is added to retard the reaction, otherwise a "falso set" can take place. Tricalcium aluminate is the most reactive major component of portland cement. The given '
discussion of its reaction is wrong. Also, tricalcium aluminate can severely affect the dimensional stability of cement if sulfate ions penetrates the cement matrix after it has set.
- 7. Pg. 7 & 8, C. Alternative Cements for Radwaste Solidification:
I am not sure of the intent of this section, it seems to imply that cements can be interchanged. However, different Types of portland cements and different cements of the same Type can and often exhibit different behaviors, and thus, should not be substituted for each other without performance testing. Therefore, if the cement of any qualified solidified LLW mixture is changed, I recommended that it be regarded as a new mixture and needs
s undergo complete qualification testing.
- 8. Page 9, 1st paragraph: in the normal proportions of cement used in cementitious products rarely will the amount of cement control the set time.
- 9. Pg. 9, 3. Amount of Water: The sentence "With slurry wastes, it is often " is not clear. What is meant by "to add
" additional" water above the surface of the solids"?
- 10. Pg. 10, B. Sample Preparation, 1st paragraph: explain why vanadium, formate and picolinate were used to load the resins.
- 11. Pg. 10, B., 2nd paragraph: what is does HI refer to?
- 12. Pg. 10, 3. Sample Preparation: how were the waste forms mixed?
describe the procedures thoroughly, the equipment used, and the batch size. How many specimens were made from each batch?
- 13. Pg. 11, 1st paragraph, 1st lines what is being poured into the molds? Undoubtedly, the molds are themselves not being poured.
- 14. Pg. 11, let paragraphs it appears that molds were sealed twice, once after being filled and then again after removal from the oven. Explain. ,
- 15. Pg. 11, 2nd paragraph: What does "ALARA" mean?
- 16. Pg. 13, b. Chemical Versus Radioactive tracers, 2nd para, third line from bottom: should be " comparable" not "comaprable"
- 17. Pg. 15, A. LOHI Resin Test Results, 2nd para.: give water-to-cement ratio
- 18. Pg. 15, I. Compression, 1st paras when averages are presented, also should give the standard deviations. The standard deviation gives an indication to the level of variability in the testing.
- 19. Pg. 15, I. Compression, 2nd para: I recommended that LN submit photographs of the cracked specimens.
- 20. Pg. 19, let para., last sentence: "This degree of loss of compressive strength during immersion is acceptable." What is the basis for this statement? I recommended that it be deleted.
- 21. Pg. 19, 8. Water for Cement Ratios, 1st para., last sentence:
replace "for" in "__are unique for the type _ " with "may be".
Where is the data supporting the statement on uniqueness?
- 22. Pg. 19, B., 2nd para., 3rd line,: I do not understand the sentence " Water-saturated resin is defined as resin containing water so that the water and resin levels are equal." What is meant by equal, e.g., same weight, same volume, or same height?
t
- 23. Pg. 19, B. 2nd para.: at what temperature is the resin dried?
How is the resin dried on an analytical balance, and what is an i analytical moisture balance?
- 24. Pg. 19, B., 3rd para., 2nd sentence: what affect did the fines have on the amount of water?
- 25. Pg. 19, last para: same comment as no. 23.
- 26. Pg. 10, last para.: specimens immersed in sea water had compressive strengths ranging from 180 to 710 psi. I regard this to be a large range of data that needs to be explained. Were the specimens from the same mix batch, were they tested at the same time, was the cracking responsible for the range in data? It appears to me, that the making of the specimens, or their curing, or their testing was not adequately controlled. Again give standard deviations, i
- 27. Pg. 13, B. 2nd para.: I do not understand why the radioactive tracers were less leached than the non-radioactive nuclei. Please explain.
- 28. Table 2: I would like the water-to-cement ratios to be included.
- 29. Table 3: define "FSW".
- 30. File No. 1001, from Microbac: During the thermal cycling bleeding was observed. What is meant by bleeding - accumulation of moisture droplets? Bleeding usually occurs while cement or concrete is hardening.
APPENDICES A & B
- 31. Pg. 3, 3.62 What is the significance of the oil content?
- 32. Pg. 6, 9.2.1 When action will be invoked if oil is found to l be present?
- 33. Pg. 7, 9.2.8: What does the technician do if more than 7.0 grams of line needs to be added to attain a pH of 107
- 34. Pg. 7, 9.2.12: The method for determining if a sample resists penetration is very subjective, and undoubtedly, the results are operator dependent. I recommended that a less-subjective test be developed.
- 35. Pg. 7, 9.2.13 to 9.2.15: What will Pappen if none of the samples meet the acceptance criteria? Acceptance of formulation should be based on at least triplicate specimens passing the criteria, especially if non-compliance was previously found for other formulations.