WSRC-MS-95-0185 CON+ 4-50

Defining the Glass Composition Limits for the CaO-A1 203-Si02 Ternary System (U)

by C. A. Cicero Westinghouse Savannah River Company Savannah River Site Aiken, South Carolina 29808 M. K. Andrews

D. F. Bickford

D. J. Meunier Clemson University/Clemson Research Park SC USA

A document prepared for THIRD BIENNIAL MIXED WASTE SYMPOSIUM at Baltimore from 08/08/95 - 08/11/95.

DOE Contract No. DE-AC09-89SR18035

This paper was prepared in connection with work done under the above contract number with the U. S. Department of Energy. By acceptance of this paper, the publisher and/or recipient acknowledges the U. S. Government's right to retain a nonexclusive, royalty-free license in and to any copyright covering this paper, along with the right to reproduce and to authorize others to reproduce all or part of the copyrighted paper.

DISC LAIMER

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DISCLAIMER

This report was prepared as an account of work sponsored by an agency of the United States Government. Neither the United States Government nor any agency thereof, nor any of their employees, make any warranty, express or implied, or assumes any legal liability or responsibility for the accuracy, completeness, or usefulness of any information, apparatus, product, or process disclosed, or represents that its use would not infringe privately owned rights. Reference herein to any specific commercial product, process, or service by trade name, trademark, manufacturer, or otherwise does not necessarily constitute or imply its endorsement, recommendation, or favoring by the United States Government or any agency thereof. The views and opinions of authors expressed herein do not necessarily state or reflect those of the United States Government or any agency thereof.

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Keywords: RCRA, low level mixed wastes, vitrification

DEJ3NING THE GLASS COMPOSITION LIMITS FOR THE CaO-AlZO3-Si02 TEWARY SYSTEM

Connie A. Cicero, Mary K. Andrews, and Dennis F. Bickford Westinghouse Savannah Ever Company Savannah River Technology Center P.O. Box 616 Aiken, SC 29808

David J. Meunier Clemson University Clemson Research Park Anderson, SC 29634

A Paper Proposed for Publication in the Proceedings of the Third Bienkal Mixed Waste Symposium, August 8 - 11,1995, in Baltimore, Maryland.

This paper was prepared in connection with work done under the U.S. DepQNnent of Energy - O f f i of Technology Development Technical Task Plan No. SR1-3-20-04. By acceptance of this paper, the publisher and/or recipient acknowledges the U.S. Government's right to retain a nonexclusive, royalty-free license in and to any copyright covering this paper, along with the right to reproduce and to authorize others to reproduce all or part of the copyrigkdpper.

Defining the G l a s s Composition Limits for the CaO-Al203-Si02 Ternary System

C.A. Cicero, D . J . Meunier, M.K. Andrews, and D . F . Bickford

ABSTRACT

V i t r i f i c a t i o n i s being inves t iga ted a s an a l t e r n a t i v e wasteform fo r Department of Energy low-level mixed wastes. S i n c e these wastes of ten contain s ign i f i can t amounts of calcium, the CaO-Al203-SiO2 ternary s y s t e m may be used when t r y i n g t o d e t e r m i n e s u i t a b l e g l a s s compositions. The objective of t h i s research was t o determine a leach-resistant glass forming region i n t h e CaO-Al203-Si02 sys t em. Several g lasses w e r e f ab r i ca t ed and charac te r ized f o r chemical composition and durabi l i ty t o ensure tha t the glass-forming region was completely covered.

A t o t a l of twen ty -n ine compositions w e r e s tudied, w i t h eighteen producing glass . Eleven of t h e glasses passed a l l t h e durabi l i ty tests performed and could be characterized as durable and leach resis tant . Five addi t ional glasses passed the Product Consistency T e s t (PCT), b u t did not m e e t the most r e s t r i c t i v e l i m i t s f o r t h e Toxicity Character is t ic Leaching Procedure (TCLP) . However, t hese g l a s s e s were a l s o c l a s s i f i e d as acceptable because of the conservative sample s i z e used fo r the tes t . The other two glasses performed w e l l on the PCT, but had excessive releases on the TCLP.

When plot ted on t h e CaO-Al203-Si02 ternary, these compositions provided a good s ized glass forming region, which w i l l be u t i l i z e d fo r fur ther low-level mixed waste s tudies .

INTRODUCTION

The g lass composition l i m i t s fo r safe disposal of Savannah River S i t e ' s ( S R S ) and other Department of Energy (DOE) s i t es ' Low-Level Mixed Wastes (LLMW) must be determined before l a rge sca l e v i t r i f i c a t i o n of t h e wastes can be performed. LLMW i s cu r ren t ly being s to red i n la rge quant i t ies a t t h e SRS and other DOE s i t e s u n t i l a permanent disposal method is selected. A t p re sen t , a f a c i l i t y which can s t o r e o r process LLMW from DOE s i t e s does n o t e x i s t . V i t r i f i c a t i o n i s being inves t iga ted a s a n a l t e r n a t i v e wasteform, s ince it produces a durable, leach r e s i s t a n t product t ha t may be capable of being del is ted w i t h respect t o Environmental Protection Agency (EPA) requirements. These requirements a r e specif ied i n the Resource Conservation and Recovery A c t (RCRA) of 1 9 7 6 and apply t o the hazardous const i tuents of the w a s t e . I f t h e waste i s d e l i s t e d s u c h t h a t it i s no longer c lass i f ied as hazardous, it can be

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disposed of i n ex is t ing low-level radioactive waste disposal f a c i l i t i e s .

Because a large amount of t h e LLMW i n the DOE system consist of s ignif icant amounts of calcium, the CaO-Al203-Si02 ternary s y s t e m may be u t i l i z e d when t r y i n g t o determine g l a s s compositions t o be tes ted . T h i s system i s used for special ty g l a s ses i n t h e g l a s s making indus t ry because of t h e re la t ive ly durable glasses it produces. However, before t h i s t e rna ry system can be appl ied t o LLMW, which contain hazardous and radioactive materials, the composition l i m i t s f o r producing durable, leach r e s i s t a n t g lasses m u s t be determined.

T h e C a O - A l 2 0 3 - S i O 2 sys tem has three major eutect ic points, which provide a s t a r t i n g point f o r compositions t h a t may produce g lass , s i n c e they correspond t o points w i t h t h e lowest melting temperatures. Preliminary s tud ie s with compositions r e l a t i v e l y close t o the eutect ic points w e r e performed by Cicero and Andrews (1) using simulated Oak Ridge Reservation (ORR) W e s t End Treatment Fac i l i t y (WETF) sludge. They found t h a t durable g lasses could be produced i n t h e region located between t h e two eutectic points ( a t about 42% and 63% S i O z ) , a s long as the g lass composition wasn't too close i n composition t o the l o w e r (429 ) eutect ic point. The other eu tec t ic point d i d not -seem t o be of t h e correct composition t o produce g lass . Studies w e r e a l so performed by Cicero and Andrews ( 2 ) w i t h simulated Los Alamos National Laboratory (LANL) sludge using t h i s s y s t e m . ' The durable glasses t h a t w e r e produced w e r e located i n t h e suggested glass making region a s determined from the ORR studies.

I n order t o be t te r define t h e glass making region, additional durable and leach r e s i s t a n t g l a s s compositions had t o be determined. Additional g lass compositions w e r e selected tha t surrounded these e u t e c t i c po in ts o r t h a t w e r e i n regions where homogeneous glasses w e r e known t o form. These studies were performed on a crucible-scale, and several glasses were fabr ica ted t o e n s u r e t h a t t h e glass-forming region was completely covered. R e s u l t s of the previous work by Cicero and Andrews (1,2) w i l l be reported as necessary throughout the paper.

EXPERIMENTAL

A s mentioned above, preliminary attempts t o def ine t h e durable glass making region w e r e made by Cicero and A n d r e w s (1,2) using simulated LLMW wastewater treatment sludges. I n order t o better define t h e g lass processing region of t h e C a O - A l 2 0 3 - S i O 2 s y s t e m f o r DOE LLMW, add i t iona l g lasses conta in ing t h e major c o n s t i t u e n t s of DOE LLMW w e r e fabr icated. F i f teen elements were selected f o r t h e glass batches. The three major elements u t i l i z e d were calcium,

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aluminum, and s i l i c o n . O t h e r LLMW c o n s t i t u e n t s i n c l u d e d i n t h e g l a s s b a t c h e s w e r e i r o n , magnesium, p o t a s s i u m , a n d sodium. T h e haza rdous n a t u r e of the waste w a s assessed by a d d i n g bar ium, cadmium, chromium, lead, n i c k e l , and s i lver . These are the haza rdous metals found m o s t f r e q u e n t l y i n DOE LLMW. Cerium w a s u t i l i z e d as a stable s i m u l a n t f o r p lu tonium a n d uranium, w h i c h a re t h e p r i m a r y radioactive e l e m e n t s p r e s e n t i n LLMW. Boron, a t y p i c a l glass addi t ive, w a s a l so i n c l u d e d .

The CaO-Al203-SiO2 t e r n a r y p h a s e diagram w a s reviewed t o d e t e r m i n e t h e compos i t ions t o be tes ted. P r e v i o u s l y tes ted DOE LLMW s l u d g e c o m p o s i t i o n s were u t i l i z e d t o locate t h e g e n e r a l r e g i o n of t h e diagram t o s t u d y . When p l o t t i n g p o i n t s on t h e t e r n a r y , it w a s assumed t h a t a l l a l k a l i a n d a l k a l i n e earth o x i d e s (BaO, CaO, MgO, K 2 0 , and Na2O) act as CaO, Fez03 acts as Al2O3, and B2O3 acts as Si02.

Ba tches c o n s i s t i n g of 100 grams of feed w e r e used t o e n s u r e tha t enough glass w a s produced f o r a l l a n a l y s e s . The batches were made f o r m r e a g e n t grade chemicals. I n a l l b a t c h e s , the weight p e r c e n t s of t h e i n d i v i d u a l h a z a r d o u s metals a n d radioactive s i m u l a n t w e r e f ixed a t 0.05 w t % (500 p p m ) . T h i s c o n c e n t r a t i o n is h i g h e r t h a n amounts t y p i c a l l y found i n DOE w a s t e streams, t h u s , t h e r e s u l t s o b t a i n e d s h o u l d be c o n s e r v a t i v e . Ana lyses of t y p i c a l DOE wastes w e r e u s e d t o g e n e r a t e re la t ive weight p e r c e n t s of the o t h e r o x i d e s (Fe2O3, MgO, a n d K 2 0 ) . The c o n c e n t r a t i o n s of t h e p,r imary o x i d e s (CaO, A l 2 O 3 , a n d S i02 ) w e r e varied t o y i e l d d i f f e r e n t glass compos i t ions . Amounts of s o m e of t h e minor o x i d e s (B2O3 and Na2O) w e r e a lso varied b u t n o t on a batch t o batch basis. T h e batch c o m p o s i t i o n s are l i s t e d i n Table 1 on a w e i g h t p e r c e n t o x i d e basis.

S e v e r a l changes were made t o the b a t c h compos i t ions beg inn ing w i t h batch #11 t o h e l p enhance glass making. S i n c e it seemed as though a w h i t e s u r f a c e l a y e r w a s fo rming as a r e s u l t of S i 0 2 n o t r e a c t i n g c o m p l e t e l y , a powdered f o r m of S i02 w a s t r i e d i n t h e g lass b a t c h i n g , r e p l a c i n g t h e g r a n u l a r f o r m which had been u s e d p r e v i o u s l y . I n a d d i t i o n , t h e r a t i o of N a 2 0 t o CaO i n t h e glass w a s i n c r e a s e d , s i n c e N a 2 0 serves as a better f l u x i n g a g e n t f o r S i 0 2 . The B2O3 c o n c e n t r a t i o n w a s a l so i n c r e a s e d because B2O3 i s a good g l a s s - f o r m i n g additive a n d a c o n s t i t u e n t i n a n i n d u s t r y - a c c e p t e d s t a n d a r d g lass . A l l of t h e changes had a posi t ive effect on glass fo rma t ion , and t h e r ema inde r of t h e compos i t ions tes ted p roduced glass w i t h no u n r e a c t e d o r w h i t e l a y e r s . Composi t ion #16 w a s one of t h e glasses w h e r e t h e c h a n g e s w e r e p o s i t i v e , it co r re sponded t o compos i t ion #8. Composi t ion #16 produced a good d a r k glass, w h i l e #08 produced glass w i t h a w h i t e l a y e r across t h e top.

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P l a c e T a b l e 1 Here

Two of the compositions batched (#09 and 810) consisted of simulated ORR WETF sludge made for the large-scale vitrification demonstrations mixed with additives. Additional additives were used to adjust the composition of the sludge because of problems with devitrification upon cooling. Perlite was used in both batches, as per the recipe, and small amounts of CaF2 and Na2SiOg were used in batches #09 and #lo, respectively, to remediate the feed compositions.

Once all the chemicals were added, the batches were mixed thoroughly and transferred to covered high purity (99.8%) alumina crucibles. The crucibles were placed in a progFammable Lindberg furnace and melted for 4 hours at 1300 C. The melting temperature was determined based on the isotherms of the ternary diagram. The melting time was selected to simulate residence times in a melter. After 4 hours, the crucibles were removed from the oven and air- cooled to room temperature.

Once the glasses were cooled and separated from the crucibles, they were analyzed for chemical composition, phase assemblage, durability, and leachability. Standards were submitted with each set of samples to determine the accuracy of the results. The total constituent analysis of the glass was performed using Inductively Coupled Plasma - Emission Spectroscopy (ICPES) and Atomic Absorption (AA) 'Spectrometry, so an accurate composition determination could be made. X- ray Diffraction analysis (XRD) was performed to determine the crystalline phases present in the glass. Scanning Electron Microscopy (SEM) was used to confirm the XRD results and chemical composition of the crystalline phases present in the glass. The TCLP was used to determine the durability of the glass in an acidic environment per USEPA ( 3 ) . The TCLP results were compared to the TCLP procedure limits, RCRA Land Disposal Limits, and the newly established Universal Treatment Standards, which became effective September 9, 1994.

Durability of the glass in an alkaline environment was measured by performing the PCT per Jantzen et al. ( 4 ) . The PCT evaluates the chemical durability of homogeneous and devitrified glasses by measuring the concentrations of the chemical species released from a crushed glass to a test solution. The PCT is required by DOE for High-Level Waste (HLW) . Using the high-level criteria provides a conservative estimate of the glass durability. The results were compared against the Environmental Assessment (EA) glass accepted values for HLW as determined by Jantzen et a1 (5).

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RESULTS AND DISCUSSION

I n c l u d i n g t h e c r u c i b l e s t u d i e s performed b y Cicero a n d Andrews ( 1 , 2 ) , a t o t a l of t w e n t y - n i n e c o m p o s i t i o n s w e r e tested, w i t h e i g h t e e n p r o d u c i n g glass. T h e e l e v e n c o m p o s i t i o n s t h a t d i d n o t p r o d u c e g l a s s w e r e e i t he r he te rogeneous , n o t comple t e ly reacted, or had ei ther a large u n r e a c t e d l a y e r o r a S i02 l a y e r across t h e u p p e r s u r f a c e . The glasses f r o m t he ORR WETF s t u d i e s w e r e n o t c o m p l e t e l y reacted and he terogeneous , compos i t ions C02, #05, and #07 had large u n r e a c t e d l a y e r s , a n d c o m p o s i t i o n s #01, #06, a n d #08 had Si02 l a y e r s . The e i g h t e e n compos i t ions which did produce glass w e r e s u b m i t t e d f o r t h e v a r i o u s a n a l y s e s described above. T h e chemical compos i t ions are shown i n Table 2, w i t h t he ORR WETF glass deno ted by t h e OR i n f r o n t of t h e glass number and t h e LANL glasses deno ted by t h e LA i n f r o n t of t h e g l a s s numbers . The a n a l y z e d c o m p o s i t i o n s y i e l d e d oxide weight p e r c e n t s close t o the desired v a l u e s . The s l i gh t d i f f e r e n c e s , u s u a l l y 2-3%, were p r o b a b l y due t o a n a l y t i c a l o r b a t c h i n g errors. The a n a l y z e d c o m p o s i t i o n s f o r glasses #9 and #10 diverged f r o m t h e e x p e c t e d v a l u e s more t h a n t h e other glasses p roduced i n t h i s s t u d y . T h i s c o u l d have r e s u l t e d f r o m u s i n g a sample of s l u d g e which w a s n o t r e p r e s e n t a t i v e of the p r e v i o u s l y a n a l y z e d composi t ion .

P l a c e T a b l e 2 Here

XRD a n a l y s e s were performed i n d u p l i c a t e and volume p e r c e n t a n a l y s e s for each phase detected w a s reported.’ The glasses which were fabricated i n t h e s t u d i e s performed by Cicero and A n d r e w s (1 ,2 ) w e r e o n l y a n a l y z e d once and o n l y q u a l i t a t i v e r e s u l t s w e r e available. The p h a s e s detected for e a c h glass are shown i n Table 3. Only t h r e e of t h e compos i t ions , #03, #15, and LA7, had any detectable c r y s t a l l i n e p h a s e s . I n a l l cases, t h e c r y s t a l l i n e p h a s e s were p r e s e n t i n r e l a t i v e l y s m a l l c o n c e n t r a t i o n s . The q u a r t z i n glass 803 w a s p r o b a b l y d u e t o s o m e u n r e a c t e d s i l ica , w h i l e t h e a n o r t h i t e composi t ion i n glass #15 and LA7 w a s l i k e l y due t o incomple t e r e a c t i o n of the p r i m a r y glass c o n s t i t u e n t s , calcia, a lumina , and s i l i ca . The c r y s t a l l i n e p h a s e s detected did n o t s e e m t o s i g n i f i c a n t l y affect t h e d u r a b i l i t y r e s u l t s . SEM a n a l y s e s ver i f ied the p r e s e n c e of t h e c r y s t a l l i n e p h a s e s i n glasses #03, #15, and LA7.

P l a c e T a b l e 3 Here

T o assess t h e d u r a b i l i t y of t h e glasses i n a n a l k a l i n e env i ronmen t , t h e y w e r e s u b j e c t e d t o t h e PCT i n a c c o r d a n c e w i t h J a n t z e n e t a l . ( 4 ) . The PCT i s a c r u s h e d glass leach t e s t t h a t measu res t h e releases of bo ron , sodium, s i l i c o n , and other e l emen t s i n 90°C ASTM Type I water over a p e r i o d of seven d a y s . Each glass was run in t r i p l i c a t e for t h e PCT, and t h e r e s u l t s w e r e averaged and t h e n n o r m a l i z e d u s i n g t h e

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a n a l y z e d e l e m e n t a l c o m p o s i t i o n s . The b l a n k s and s t a n d a r d g l a s s e s run s i m u l t a n e o u s l y w i t h t h e test g l a s s e s showed t h a t no s i g n i f i c a n t errors o c c u r r e d du r ing t h e t e s t i n g .

The average normal ized r e s u l t s f o r boron, sodium, and s i l i c o n are g iven i n Table 4 for e a c h o f t h e glasses and for t h e EA g l a s s . S i n c e no a c c e p t a n c e c r i t e r i a have been e s t a b l i s h e d fo r LLMW, t h e d u r a b i l i t i e s o f t h e glasses p roduced w e r e compared a g a i n s t t h e HLW cri teria which states t h a t t h e glass produced must be m o r e d u r a b l e t h a n t h e EA glass. A s can be s e e n from t h e r e s u l t s , t h e normal ized releases f o r a l l of the g l a s s e s w e r e s u b s t a n t i a l l y less t h a n t h e EA g l a s s . For t h e RCRA metals of concern, no detectable release w a s measured by t h e PCT.

P l a c e Table 4 Here

TCLP e x t r a c t i o n s w e r e per formed on t h e glasses per USEPA (3) and t h e r e s u l t i n g l e a c h a t e s w e r e ana lyzed by ICPES. The TCLP w a s performed on >150 jLm c r u s h e d glass, w h i l e t h e s t a n d a r d E P A t es t s are u s u a l l y performed on l a rge r s i z e g lass specimens (1 c m ) . Thus, t h e r e s u l t s p rov ide a c o n s e r v a t i v e estimate of t he l e a c h r e s i s t a n c e s i n c e m o r e glass s u r f a c e area i s exposed t o t h e l e a c h i n g s o l u t i o n . The r e s u l t s fo r t h e a p p l i c a b l e metals are shown i n Table 5 , a l o n g w i t h t h e associated EPA, TCLP p r o c e d u r e l i m i t s , and t h e U n i v e r s a l Treatment S tanda rds (UTS) l i m i t s .

P l a c e T a b l e 5 Here

Applying t h e m o s t c o n s e r v a t i v e l i m i t f o r each m e t a l , o n l y e l e v e n of t h e e i g h t e e n glasses passed t h e TCLP. S e v e r a l of t h e glasses had o n l y one e lement t h a t s l i g h t l y exceeded t h e m o s t c o n s e r v a t i v e l i m i t . G l a s s #10 exceeded t h e RCRA l i m i t fo r n i c k e l and UTS l i m i t f o r l e a d , wh i l e glasses #17 & # 1 9 exceeded t h e RCRA l i m i t f o r cadmium. Glasses #09, #11, #18, & 820 f a i l e d f o r m o r e t h a n one e l e m e n t . I f t h e less s t r i n g e n t of t h e l i m i t s i s a p p l i e d , s i x t e e n of t h e e i g h t e e n g l a s s e s c o u l d be c o n s i d e r e d as p a s s i n g t h e TCLP. Only glasses #11 & #20 fa i led a l l sets o f c r i te r ia f o r an e lement . T h i s c o n s i d e r a t i o n can be made because o f t h e c o n s e r v a t i v e n a t u r e of t h e t e s t t h a t w a s performed, s i n c e much smaller particle s i z e samples w e r e u s e d d u r i n g t h e t e s t i n g . T h i s allowed much more s u r f a c e area t o be exposed f o r l e a c h i n g .

A f t e r t h e modified TCLP r e s u l t s w e r e r e c e i v e d , g lass mono l i th s of t h e samples w e r e placed i n ace t ic acid f o r 2 4 hour s t o see how t h e glass i n t e g r i t y would be affected. T h i s t es t s i m u l a t e d t h e TCLP l e a c h a n t and s u r f a c e area t o volume r a t i o m o r e c l o s e l y t h a n t h e m o d i f i e d t es t . None of t h e glasses showed any s i g n s of d e g r a d a t i o n a f t e r 2 4 h o u r s and t h e l e a c h a t e s had no d e t e c t a b l e amounts of RCRA metals r e l e a s e d when a n a l y z e d by I C P E S . These c o n c l u s i o n s l e n d

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support t o t he believe t h a t these glasses may have been acceptable i f t h e standard TCLP conditions were used.

Using t h e available composition data from Table 2 , the glass compositions were p l o t t e d on t h e CaO-Al203-Si02 te rnary diagram. All compositions were plot ted tha t w e r e considered acceptable. However, a d i s t i nc t ion was made on t h e p l o t between those glasses t h a t met a l l c r i t e r i a and those t h a t did not . T h i s ternary diagram i s given as Figure 1. These p l o t s were used t o determine a good s ized expected g lass forming region for t h i s ternary system.

P l a c e F i g u r e 1 Here

CONCLUS IONS

Eleven of t he eighteen glasses fabricated m e t t h e c r i t e r i a established fo r determining whether a glass w i l l be durable and leach r e s i s t an t . The compositions of these glasses were p l o t t e d on a te rnary diagram, found i n Figure 1. Five a d d i t i o n a l g lasses were a l s o considered acceptable and p lo t t ed on the ternary. These w e r e the f ive glasses t h a t f a i l e d t h e TCLP by s l i g h t l y exceeding t h e most conservative l i m i t fo r j u s t one element. Acceptability of these glasses w a s based on-the following .reasons:

0 high concentrations of metals tha t w e r e used i n the glass batches, since typical LLMW would have lower concentrations of these hazardous metals; ’

a t he pa r t i c l e s i z e of the glass samples used f o r t h e TCLP test were smaller than that typical ly used i n t h e TCLP procedure, which r e su l t ed i n a much larger surface area t o volume r a t i o and thus exposed more of t h e glass t o the leaching solution; and

a the posit ive resu l t s of the monolith tes t ing, which showed no appreciable glass degradation o r RCRA metal releases.

ACKNOWLDE GMENT S

T h i s work was sponsored under the South Carolina University Research and Education Foundation, which was funded through contract A A O O 9 O O T . Funding for t h i s contract was provided by t h e Department of Energy - Office of Technology Development Mixed Waste Integrated Program under operating contract N o . DE-ACO9-89SR18035.

REFERENCES

1.

2.

3.

4.

5.

Cicero, C.A.; Andrews, M.K. ORR WETF Simulated Sludge Crucible Studies. Aiken, SC: Westinghouse Savannah River Company, WSRC-TR-93-0647, Revision 1; 1994.

Cicero, C.A.; Andrews, M.K. LANL TA-50 Simulated Sludge Crucible Studies. Aiken, SC: Westinghouse Savannah River Company, WSRC-TR-94-0313, Revision 1; 1994.

USEPA (U. S. Environmental Protect ion Agency) . Method 1131 Toxicity Characteristic Leaching Procedure (TCLP) . 40 CFR 261 App. 11; 1991.

Jantzen, C.M.; Bibler, N.E.; Beam, D.C.; Ramsey, W.G. Nuclear Waste Glass Product Consistency Test (PCT) Method - Version 7.0. Aiken, SC: Westinghouse Savannah River Company, WSRC-TR-90-539, Revision 3; 1994.

Jantzen, C.M.; Bibler, N.E . ; Beam, D.C.; Crawford, C.L.; Pickett, M.A. Characterization of the Defense Waste Processing Facility (DWPF) Environmental Assessment (EA) Glass Standard Reference Material. Aiken, SC: Westinghouse Savannah River Company, WSRC-TR-92-346, Revision 1; 1993.

8

TABLE 1 - BATCH COMPOSITIONS (WT%)

&A 0.05 7.00 0.05 0.20

13.35 0.05 0.05 0.05 3.00 2.00 1.20 3.40 0.05 0.05

69.80

ItB 0.05

25.00 0.05 0.20

23.35 0.05 0.05 0.05 3.00 2.00 1.20 3.40 0.05 0.05

41.80

u 0.05

27.00 0.05 0.20

13.35 0.05 0.05 0.05 3.00 2.00 1.20 3.40 0.05 0.05

49.80

flp N/A

12.77 0.06 0.00

22.65 0.00 0 .11 0.00 1.58 3.82 0.80 4.50 0.08 0 .01

52.60

iL3 0.05

22.00 0.05 0.20

23.35 0.05 0.05 0.05 3.00 2.00 1.20 3.40 0.05 0.05

44.80

u N/A

13.05 0.06 0.00

19..70 0.00 0.12 0.00 1.65 3.79 0.87 5.98 0.08 0.01

53.60

lt9 0.05 7.00 0.05 0.20

23.35 0.05 0.05 0.05 3.00 2.00 1.20 3.40 0.05 0.05

59.80

u 0.05

19.00 0.05 1.00

20.75 0.05 0.05 0.05 3.00 2.00 1.20 7.00 0.05 0.05

46.00

fi 0.05 9.00 0.05 0.20

13.35 0.05 0.05 0.05 3.00 2.00 1.20 3.40 0.05 0.05

67.80

11l2 0.05

17.00 0.05 1.00 9.75 0.05 0.05 0.05 3.00 2.00 1.20 7.00 0.05 0.05

59.00

iui 0.05

22.00 0.05 1.00 9.75 0.05 0.05 0.05 3.00 2.00 1.20 7.00 0.05 0.05

54.00

4 U i 0.05

25.00 0.05 1.00

19.75 0.05 0.05 0.05 3.00 2.00 1.20 7.00 0.05 0.05

41.00

&.ILL 0.05

12.00 0.05 1.00

14.75 0.05 0.05 0.05 3.00 2.00 1.20 7.00 0.05 0 . 0 5

59,oo

;iLtB 0.05

24.00 0.05 1.00

12.75 0.05 0.05 0.05 3.00 2.00 1.20 7.00 0.05 0.05

49.00

u 0.05

10.00 0.05 1.00

19.75 0.05 0.05 0.05 3.00 2.00 1.20 7.00 0.05 0.05

56.00

&§ 0.05

22.00 0.05 0.20

18.35 0.05 0.05 0.05 3.00 2.00 1.20 3.40 0.05 0.05

49.80

m 0.05

12 .oo 0.05 1.00 9.75 0.05 0.05 0.05 3.00 2.00 1 .20 7.00 0.05 0.05

64 .OO

&u 0.05

26.00 0.05 1.00

15.75 0.05 0.05 0.05 3.00 2.00 1.20 7.00 0.05 0.05

44.00

&LL 0.05 9.00 0.05 0.20

26.35 0.05 0.05 0.05 3.00 2.00 1.20 3.40 0.05 0.05

54.80

u 0.05 7.00 0.05 1.00

14.75 0.05 0.05 0.05 3.00 2.00 1.20 7.00 0.05 0.05

64.00

9

TABLE

4 . u 0.049

24 .383 0 .061 0 .173

21.714 0 .029 0.060 0.058 3.116 1 .745 1 .156 3.455 0.074 0.019

45.916 102.008

m 0.077

11 .055 0 .063 0 .951 9.176 0.042 0.028 0.072 3.419 1 .884 1 .134 6.665 0.110 0 .055 65.890

100 .621

lilp 0 -030

11 * 019 0.100 0.942

18 .115 0.029 0.022 0 .131 4.252 1 .822 1.105 6.402 0.195 0.070 56.838

101.072

2 - COMPOSITION

iK!A 0.044 8.064 0.062 0 .135

21 .433 0.030 0.025 0.159 3.712 1 .894 1 . 1 4 1 3.427 0 .133 0.024

59.862 100.145

itls 0.028 6.722 0.059 0.959

13.717 0.029 0.028 0 .085 3.526 1 . 8 0 3 1 .128 6.339 0.112 0.066 65.925

100.526

Kul 0 .083

26 .784 0 .091 0 .945

14 .526 0.030 0.029 0.128 4.318 2 .018 1.133 6.449 0 .193 0.066

44.902 101.695

u 0.002

18.830 0.049 0.075

21.167 0.001 0.030 0.067 2.635 3 -228 0 .703 2.976 0 .161 0.062

51.864 101.850

u3 0.029

20.018 0.051 0.966 9.285 0 .035 0.027 0.080 3 .503 1 .873 1 .144 6.615 0 .121 0 .041 56.509

100.297

PBZ 0.029

20.018 0 .051 0.966 9.285 0.035 0.027 0.080 3 .503 1 .873 1.144 6.615 0 .) 1 2 1 0.041 56.509

100 -297

OF GLASSES

UQ 0.002

1 8 -377 0.077 0.070

18 .091 0 .001 0.026 0.034 2.196 3.347 0.767 4 .911 0.115 0.076

55.086 103.176

Ku 0.027

22.552 0 .051 0.949

18.367 0 .035 0.042 0.114 3.712 1 .917 1 .125 6.427 0.154 0.046 42.191 97.709

2311 0.027

22.552 0.051 0.949

18.367 0.035 0.042 0.114 3.712 1 .917 1.125 6.427 0.154 0.046 42.191 97.709

(Wt%)

11l1 0.037

20 .615 0.049 0.972

19.777 0.029 0.027 0.065 4.110 1 . 8 5 9 1 .144 6.482 0.139 0 .061

47.812 103.178

L u 0 .025

12 .597 0 .091 0.989

13 .612 0.049 0.028 0 - 2 2 3

1 .967 1.133 6.489 0 .288 0 - 0 5 1 60.270

103.126

u . 0 0.025

12 .597 0 .091 0.989

13 .612 0 .049 0.028 0 - 2 2 3 5 .314 1 . 9 6 7 1.133 6 .489 0.288 0 .051 60.270

103.126

5,314

1112 0.017

17 .804 0.077 0.956 9.138 0.032 0 .028 0.068 4.200 1 .889 1.133 6.513 0.136 0.078 61.032

103.101

ua 0.033

24.970 0.055 0 .961

12 .063 0.033 -

0.025 0.087 3.756 1.818 1.151 6.161 0.124 0 .041

50.978 102 -256

LAA 0.033

24.970 0.055 0 .961

12 .063 0.033 0.025 0.087 3.756 1 .818 1.151 6 .161 0.124 0 .041 50.978

102.256

10

TABLE 3 - XRD PHASE ASSEMBLAGE RESULTS

u 3 4 9 10 11 12 13 14 15 16 17 18 19 20 OR7 LA7 LA8 LA9

V S l S #l. 0.2 wt% Quartz

Amorphous Amorphous Amorphous Amorphous Amorphous Amorphous Amorphous

0.7 wt% Anorthite Amorphous Amorphous Amorphous Amorphous Amorphous Amorphous Anorthite Amorphous Amorphous

s ctp 0.1 wt% Quartz

Amorphous Amorphous Amorphous Am0 rphou s Amorphous Amorphous Amorphous

0.5 wt% Anorthite Amorphous Amorphous Amorphous Amorphous Amorphous

N/A N/A N/A N/A

11

TABLE 4 - NORMALIZED PCT RESULTS - 03 04 09 10 11 12 13 1 4 15 1 6 17 18 1 9 20

OR7 LA7 LA8 LA9 EA

B 0.113 0.099 0.129 0.000 0.095 0.083 0.184 0.117 0.095 0.090 0.117 0.081 0.100 0.079 0.000 1.200 1 . 1 4 3 0.118

16.695

KO 0.098 0.134 0.124 0.145 0.158 0.162 0.248 0.315 0.159 0.144 0.247 0.163 0.245 0.144 0.063 0.069 0.082 0.072

13.346

si 0.053 0.058 0.052 0.063 0.065 0.068 0.076 0.075 0.063 0.057 0.070 0 .061 0.065 0.060 0.580 0.000 0.136 0.000 3.922

12

G l z m % d 03 04 09 1 0 11 12 13 1 4 15 16 17 18 1 9 20

OR7 LA7 LA8 LA9

TABLE 5 - TCLP RESULTS (mg/L)

RCRA L i m i t 0.072 TCLP L i m i t 5.00 UTS L i m i t 0.30

13

arr <o. 020 eo. 020 eo. 020 KO. 020

2.510 <o * 020 eo. 020 <o. 020 eo. 020 eo . 020 <o. 020

0.467 co .‘020

1.192 N/A N/A N/A N/A

Ea 0.489 0.654 1.620 1.424 6.765 2.914 0.415 0.578 0.500 0.517 0.700 1.664 0.812 7.124 0.840 0.506 0.625 0.398 N/A

100.0 7.6

sa <o. 010

0.039 0.026 0.019 3.125 0.056

<o. 010 0.011

<o. 010 0.036 0.086 0.856 0.092 2.790

<o. 010 0.028

eo. 010 eo. 010

0.066 1.00 0 .19

XO.040 <O .040

0.510 0.190 2.793

<O .040 <O. 040 <O. 040 <O. 040 <O. 040 <O. 040

0.562 0.048 2.216

<O. 040 <O. 040 <O. 040 <O. 040

5.20 5.00 0.86

Ki < O . 050 <O. 050

1.370 0.457 3.406

<O. 050 e0 .OS0

0.061 <O. 050

0.062 <O. 050

0.698 <O. 050

2.587 0.171

<O. 050 <O. 050 K O . 050

0.32 N/A

5.00

Ek <o -200 <o. 200

1.074 0.417 4.802

eo. 200 eo. 200 <o .200 eo. 200 eo. 200 e0.200

0.793 <o. 200

5.397 eo . 200 eo .zoo

0.214 e0.200

0.51 5.00 0.37

FIGURE 1 - CaO-Al203-Si02 TERNARY DIAGRAM

0 CaO

14