[en] Eight tests using different HLW feeds were conducted on the DM100-BL to determine the effect of variations in glass properties and feed composition on processing rates and melter conditions (off-gas characteristics, glass processing, foaming, cold cap, etc.) at constant bubbling rate. In over seven hundred hours of testing, the property extremes of glass viscosity, electrical conductivity, and T_1%, as well as minimum and maximum concentrations of several major and minor glass components were evaluated using glass compositions that have been tested previously at the crucible scale. Other parameters evaluated with respect to glass processing properties were +/-15% batching errors in the addition of glass forming chemicals (GFCs) to the feed, and variation in the sources of boron and sodium used in the GFCs. Tests evaluating batching errors and GFC source employed variations on the HLW98-86 formulation (a glass composition formulated for HLW C-106/AY-102 waste and processed in several previous melter tests) in order to best isolate the effect of each test variable. These tests are outlined in a Test Plan that was prepared in response to the Test Specification for this work. The present report provides summary level data for all of the tests in the first test matrix (Matrix 1) in the Test Plan. Summary results from the remaining tests, investigating minimum and maximum concentrations of major and minor glass components employing variations on the HLW98-86 formulation and glasses generated by the HLW glass formulation algorithm, will be reported separately after those tests are completed. The test data summarized herein include glass production rates, the type and amount of feed used, a variety of measured melter parameters including temperatures and electrode power, feed sample analysis, measured glass properties, and gaseous emissions rates. More detailed information and analysis from the melter tests with complete emission chemistry, glass durability, and melter operating details will be provided in the final report. A summary of the tests that were conducted is provided in Table 1. Each of the seven tests was of nominally one hundred hours in duration. Test B was conducted in two equal segments: the first with nominal additives, and the second with the replacement of borax with a mixture of boric acid and soda ash to determine the effect of alternative OPC sources on production rates and processing characteristics. Interestingly, sugar additions were required near mid points of Tests W and Z to reduce excessive foaming that severely limited feed processing rates. The sugar additions were very effective in recovering manageable processing conditions, albeit over the relatively short remainder of the test duration. Tests W and Z employed the highest melt viscosities but not by a particularly wide margin. Other tests, which did not exhibit such foaming Issues, employed higher concentrations of manganese or iron or both. These results highlight the need for the development of protocols for the a priori determination of which HLW feeds will require sugar additions and the appropriate amounts of sugar to be added in order to control foaming (and maintain throughput) without over-reduction of the melt (which could lead to molten metal formation). In total, over 8,800 kg of feed was processed to produce over 3200 kg of glass. Steady-state processing rates were achieved, and no secondary sulfate phases were observed during any of the tests. Analysis was performed on samples of the glass product taken throughout the tests to verify composition and properties. Sampling and analysis was also performed on melter exhaust to determine the effect of the feed and glass changes on melter emissions.

[en] The principal objectives of the DM100 tests were to determine the processing characteristics of several C-106/AY102 feeds derived from simulants prepared by different methods, which result in different physical characteristics of the feed. The VSL simulant used in a previous test was prepared by the direct hydroxide method, which was the method used for feed preparation in the bulk of previous VSL melter testing. The NOAH Technologies Corporation modified-rheology simulant was prepared to the same composition as the VSL simulant using a method that resulted in rheological properties closer to those of certain actual waste samples. The SIPP simulant was produced by processing a co-precipitated waste simulant through a non-radioactive pilot scale semi-integrated pretreatment facility. The general intent of these tests was to provide a basis for determining whether the variations in rheology or other feed physical characteristics arising from the different methods of simulant preparation have significant effects on the processing characteristics of the feed in the melter. Completion of the test objectives is detailed in a table.

[en] This report provides data, analyses, and conclusions from a series of tests that were conducted at the Vitreous State Laboratory of The Catholic of America (VSL) to determine the processing rates that are achievable with AZ-101 HLW simulants and corresponding melter feeds on a DuraMelter 100 (DM100) vitrification system. One of the most critical pieces of information in determining the required size of the RPP-WTP HLW melter is the specific glass production rate in terms of the mass of glass that can be produced per unit area of melt surface per unit time. The specific glass production rate together with the waste loading (essentially, the ratio of waste-in to glass-out, which is determined from glass formulation activities) determines the melt area that is needed to achieve a given waste processing rate with due allowance for system availability. Tests conducted during Part B1 (VSL-00R2590-2) on the DM1000 vitrification system installed at the Vitreous State Laboratory of The Catholic University of America showed that, without the use of bubblers, glass production rates with AZ-101 and C-106/AY-102 simulants were significantly lower than the Project design basis rate of 0.4 MT/m²/d. Conversely, three-fold increases over the design basis rate were demonstrated with the use of bubblers. Furthermore, an un-bubbled control test using a replica of the melter feed used in cold commissioning tests at West Valley reproduced the rates that were observed with that feed on the WVDP production melter. More recent tests conducted on the DM1200 system, which more closely represents the present RPP-WTP design, are in general agreement with these earlier results. Screening tests conducted on the DM10 system have provided good indications of the larger-scale processing rates with bubblers (for both HL W and LAW feeds) but significantly overestimated the DM1000 un-bubbled rate observed for C-106/AY-102 melter feeds. This behavior is believed to be a consequence of the role of heat transfer in rate attainment and the much greater role of wall effects in heat transfer when the melt pool is not agitated. The DM100 melter used for the present tests has a surface area of 0.108 m², which is approximately 5 times larger than that of the DM10 (0.021 m²) and approximately 11 times smaller than that of the DM1000 (1.2 m²) (the DM1000 has since been replaced by a pilot-scale prototypical HLW melter, designated the DM1200, which has the same surface area as the DM1000). Testing on smaller melters is the most economical method for obtaining data over a wide range of operating conditions (particularly at extremes) and for guiding the more expensive tests that are performed at pilot-scale. Thus, one objective of these tests was to determine whether the DM100 melters are sufficiently large to reproduce the un-bubbled melt rates observed at the DM1000 scale, or to determine the extent of any off-set. DM100-scale tests can then be used to screen feed chemistry variations that may serve to increase the un-bubbled production rates prior to confirmation at pilot scale. Finally, extensive characterization data obtained on simulated HLW melter feeds formed from various glass forming additives indicated that there may be advantages in terms of feed rheology and stability to the replacement of some of the hydroxides by carbonates. A further objective of the present tests was therefore to identify any deleterious processing effects of such a change before adopting the carbonate feed as the baseline. Data from the WVDP melter using acidified (nitrated) feeds, and without bubbling, showed productions rates that are higher than those observed with the alkaline RPP feeds at the VSL. Therefore, the effect of feed acidification on production rate also was investigated. This work was performed under Test Specification, 'TSP-W375-00-00019,, 'HLW-DM10 and DM100 Melter Tests' dated November 13, 2000 and the corresponding Test Plan. It should be noted, however, that the RPP-WTP Project directed a series of changes to the Test Plan as the results from previous tests were reported. As a result, the test matrix that was executed differs from that in the Test Plan.

[en] The corrosion of the glass-contact refractory Monofrax K-3 in two sodium-rich aluminosilicate melts has been studied at 1,208 and 1,283 C using a modified ASTM procedure with constant agitation of the melt by air bubbling. The results for the monolithic refractory indicate a fast initial stage involving phase dissolution and transformation and a later passivated stage in which the surface of the refractory has been substantially modified. The composition of the stable spinel phase in the altered layer on monolithic coupons of K-3 is almost identical to the equilibrium composition bracketed by the dissolution of powdered K-3 into under-saturated melts on the other. The temperature and melt shear viscosity were found to have significant effects on the rates of K-3 dissolution and transformation

[en] The design and construction of a wide-range, automated film balance and a set of experiments on a well-documented material to test the instrument during its development are described. The balance can be operated in the temperature range 5-50⁰C. It can measure surface tension differences up to 50 mN m^-1 with an imprecision of +/- 0.01 mN m^-1. The measurements of the liquid-expanded (LE)-liquid-compressed (LC) and the liquid-vapor transitions in pentadecanoic acid monolayers on water to confirm recent suggestions that long-standing ideas about these two transitions might be in error and that a thorough reexamination of many classic measurements will be necessary

[en] This Test Plan describes work to support the development and testing of high waste loading glass formulations that achieve high glass melting rates for Hanford high aluminum high level waste (HLW). In particular, the present testing is designed to evaluate the effect of using low activity waste (LAW) waste streams as a source of sodium in place ofchemical additives, sugar or cellulose as a reductant, boehmite as an aluminum source, and further enhancements to waste processing rate while meeting all processing and product quality requirements. The work will include preparation and characterization of crucible melts in support of subsequent DuraMelter 100 (DM 100) tests designed to examine the effects of enhanced glass formulations, glass processing temperature, incorporation of the LAW waste stream as a sodium source, type of organic reductant, and feed solids content on waste processing rate and product quality. Also included is a confirmatory test on the HLW Pilot Melter (DM1200) with a composition selected from those tested on the DM100. This work builds on previous work performed at the Vitreous State Laboratory (VSL) for Department of Energy's (DOE's) Office of River Protection (ORP) to increase waste loading and processing rates for high-iron HLW waste streams as well as previous tests conducted for ORP on the same waste composition. This Test Plan is prepared in response to an ORP-supplied statement of work. It is currently estimated that the number of HLW canisters to be produced in the Hanford Tank Waste Treatment and Immobilization Plant (WTP) is about 12,500. This estimate is based upon the inventory ofthe tank wastes, the anticipated performance of the sludge treatment processes, and current understanding of the capability of the borosilicate glass waste form. The WTP HLW melter design, unlike earlier DOE melter designs, incorporates an active glass bubbler system. The bubblers create active glass pool convection and thereby improve heat transfer and glass melting rate. The WTP HLW melter has a glass surface area of 3.75 m² and depth of ∼1.1 m. The two melters in the HLW facility together are designed to produce up to 7.5 MT of glass per day at 100% availability. Further increases in HLW waste processing rates can potentially be achieved by increasing the melter operating temperature above 1150 C and by increasing the waste loading in the glass product Increasing the waste loading also has the added benefit of decreasing the number of canisters for storage. The current estimates and glass formulation efforts have been conservative in terms of achievable waste loadings. These formulations have been specified to ensure that the glasses are homogenous, contain essentially no crystalline phases, are processable in joule-heated, ceramic-lined melters and meet WTP contract requirements. The WTP's overall mission will require the immobilization oftank waste compositions that are dominated by mixtures of aluminum (Al), chromium (Cr), bismuth (Bi), iron (Fe), phosphorous (P), zirconium (Zr), and sulfur (S) compounds as waste-limiting components. Glass compositions for these waste mixtures have been developed based upon previous experience and current glass property models. Recently, DOE has initiated a testing program to develop and characterize HLW glasses with higher waste loadings. Results of this work have demonstrated the feasibility of increases in waste-loading from about 25 wt% to 33-50 wt% (based on oxide loading) in the glass depending on the waste stream. It is expected that these higher waste loading glasses will reduce the HLW canister production requirement by about 25% or more.

[en] This report provides data, analysis, and conclusions from a series of tests that were conducted at the Vitreous State Laboratory of The Catholic University of America (VSL) to determine the melter processing rates that are achievable with RPP-WTP HLW simulants. The principal findings were presented earlier in a summary report (VSL-00R2S90-l) but the present report provides additional details. One of the most critical pieces of information in determining the required size of the RPP-WTP HLW melter is the specific glass production rate in terms of the mass of glass that can be produced per unit area of melt surface per unit time. The specific glass production rate together with the waste loading (essentially, the ratio of waste-in to glass-out, which is determined from glass formulation activities) determines the melt area that is needed to achieve a given waste processing rate with due allowance for system availability. As a consequence of the limited amount of relevant information, there exists, for good reasons, a significant disparity between design-base specific glass production rates for the RPP-WTP LAW and HLW conceptual designs (1.0 MT/m²/d and 0.4 MT/m²/d, respectively); furthermore, small-scale melter tests with HLW simulants that were conducted during Part A indicated typical processing rates with bubbling of around 2.0 MT/m²/d. This range translates into more than a factor of five variation in the resultant surface area of the HLW melter, which is clearly not without significant consequence. It is clear that an undersized melter is undesirable in that it will not be able to support the required waste processing rates. It is less obvious that there are potential disadvantages associated with an oversized melter, over and above the increased capital costs. A melt surface that is consistently underutilized will have poor cold cap coverage, which will result in increased volatilization from the melt (which is generally undesirable) and increased plenum temperatures due to increased thermal radiation from the melt surface (which mayor may not be desirable but the flexibility to choose may be lost). Increased volatilization is an issue both in terms of the increased challenge to the off-gas system as well as for the ability to effectively close the recycle loops for volatile species that must be immobilized in the glass product, most notably technetium and cesium. For these reasons, improved information is needed on the specific glass production rates of RPP-WTP HLW streams in DuraMelterJ systems over a range of operating conditions. Unlike the RPP-WTP LAW program, for which a pilot melter system to provide large-scale throughout information is already in operation, there is no comparable HLW activity; the results of the present study are therefore especially important. This information will reduce project risk by reducing the uncertainty associated with the amount of conservatism that mayor may not be associated with the baseline RPP-WTP HLW melter sizing decision. After the submission of the first Test Plan for this work, the RPP-WTP requested revisions to include tests to determine the processing rates that are achievable without bubbling, which was driven by the potential advantages of omitting bubblers from the HLW melter design in terms of reduced maintenance. A further objective of this effort became the determination of whether the basis of design processing rate could be achieved without bubbling. Ideally, processing rate tests would be conducted on a full-scale RPP-WTP melter system with actual HLW materials, but that is clearly unrealistic during Part B1. As a practical compromise the processing rate determinations were made with HL W simulants on a DuraMelter J system at as close to full scale as possible and the DM 1000 system at VSL was selected for that purpose. That system has a melt surface area of 1.2 m², which corresponds to about one-third scale based on the specific glass processing rate of 0.4 MT/m²/d assumed in the RPP-WTP HLW conceptual design, but would correspond to larger than full scale if the typical Part A test results of about 2.0 MT/m²/d were realized. The DM 1000 system was used with the existing off-gas treatment system in order to expedite the collection of this information; while that system is somewhat different from the RPP-WTP conceptual design, that should have no effect on the processing rate measurements. Subsequent tasks supported the later modification of that off-gas system to obtain large-scale system performance information on the baseline off-gas design and those modifications are now complete. Work planned for Part B2 includes similar pilot-scale testing with the prototypical off-gas system. Three HLW simulant compositions were used in the present tests: the tank AZ-101 waste (the first B2 HLW feed to the RPP-WTP), the 106-C/AY-102 blend (the largest B2 HLW tank), and the HLW composition processed at West Valley.

[en] The Minimum Additive Waste Stabilization (MAWS) Program is an innovative program involving development and demonstration (beginning in mid 1993) at the Fernald Site of an integrated, multiple-technology system (vitrification, soil washing, and water treatment) to treat blends of waste streams to achieve significant reductions in treatment and disposal costs. All contaminant streams are directed to a final stabilized glass waste form using a Duramelter vitrification system. Vitrification provides superior product leach resistance and very large volume reductions which significantly reduce life-cycle remediation costs. Vitrification of Fernald soils alone would typically require additional fluxing agents, however, in the MAWA approach, the pit sludges provide those agents. Contaminated soils undergo further volume reduction by pretreatment in a TRUclean washing system (supported by regenerative ion exchange); the contaminant-enriched minor fraction is then used as feed for the vitrification process. This paper discusses the major concepts underlying the MAWS approach, its main objectives, and the progress that has been made to date. The cost savings and wasteform performance benefits realizable with this approach should be widely applicable to other sites. 11 refs., 3 figs., 2 tabs

[en] The principal objective of this report was to summarize the testing experience on the DuraMelter 1200 (DMI200), which is the High Level Waste (HLW) Pilot Melter located at the Vitreous State Laboratory (VSL). Further objectives were to provide descriptions of the history of all modifications and maintenance, methods of operation, problems and unit failures, and melter emissions and performance while processing a variety of simulated HL W and low activity waste (LAW) feeds for the Hanford Waste Treatment and Immobilization Plant (WTP) and employing a variety of operating methods. All of these objectives were met. The River Protection Project - Hanford Waste Treatment and Immobilization Plant (RPP-WTP) Project has undertaken a 'tiered' approach to vitrification development testing involving computer-based glass formulation, glass property-composition models, crucible melts, and continuous melter tests of increasing, more realistic scales. Melter systems ranging from 0.02 to 1.2 m² installed at the Vitreous State Laboratory (VSL) have been used for this purpose, which, in combination with the 3.3 m² low activity waste (LAW) Pilot Melter at Duratek, Inc., span more than two orders of magnitude in melt surface area. In this way, less-costly small-scale tests can be used to define the most appropriate tests to be conducted at the larger scales in order to extract maximum benefit from the large-scale tests. For high level waste (HLW) vitrification development, a key component in this approach is the one-third scale DuraMelter 1200 (DM 1200), which is the HLW Pilot Melter that has been installed at VSL with an integrated prototypical off-gas treatment system. That system replaced the DM1000 system that was used for HLW throughput testing during Part B1. Both melters have similar melt surface areas (1.2 m²) but the DM1200 is prototypical of the present RPP-WTP HLW melter design whereas the DM1000 was not. In particular, the DM1200 provides for testing on a vitrification system with the specific train of unit operations that has been selected for both HLW and LAW RPP-WTP off-gas treatment.

[en] A range of compositions of high-zirconia borosilicate glasses were formulated and their structures investigated by a combination of techniques. These compositions have potential applications for high-level nuclear waste storage in combination with advanced reprocessing methods. Raman and Zr EXAFS data were collected for a series of glasses spanning a range of zirconia concentrations. The Raman spectra indicate that Zr acts as a silicate network modifier, where the silicate tetrahedral network depolymerizes as the zirconia content increases. Zr EXAFS analysis indicates that Zr is found in octahedral sites, and to a minor extent, seven-coordinated sites. As the zirconia content increases, the fraction of seven-coordinated Zr-sites increases; this may be the cause of ZrO₂ baddeleyite crystallization that was observed in some Zr-rich glasses investigated