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ORNL B-391
CONF-571-14
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OCT 51964
A FUSED -SALT TLUCRIE-VOLATILITY PROCESS FOR RECOVERING URANIUM
FROM SPENT ALUMINIUM-BASED FUEL ELEMENTS*
1
LEGAL NOTICE -

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by
M. R. Bennett, G. I. Cathers, R. P. Milford
W. W. Pitt, Jr., J. . üllmann
Chemical Technology Division
Oak Ridge National Laboratory
**
Wi
To be presented at the 148th National American
Chemical Society Meeting, Division of Nuclear Chemistry
and Technology (Prod.) in Chicago, Tllinois,
September 3, 1964.

(Fcz oral presentation--not for publication in this form.)
-
*Research sponsored by the U. S. Atomic Energy Commission under
contract with the Union Caroide Corporation.
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IIVI RODUCTION
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The ork to be described io pirt or an AXC-sponsored program to
develop 2.10ride volatility methods as c. Iternatives " queous methods
foi reprocessing spent nuclear reactor fuels. Varicua approaches are
coin studied at Brookhaven, Arconne, and Oak Ridge National laboratories.
We in the Chemical Technology Division at Oak Ridge National Laboratory
here, since 1955, been concentrating on a method in which the fuel to be
processeá is either a mixture of molten fluorides or is dissolved into a
fluoride melt by HF. The uranium is then converted to the volatile hexa-
i'luoride with fluorine, and further purified by passage through beds of
Vürst and mista. Mr. Carr just presented an account of the application of
such a method to the processing of 2r-U alloy fuels. I will discuss the
qevelopment of a molten-salt fluoride-volatility process for Al-U alloy
fuels through laboratory and semiworks scales. Although an aqueous process
for aluminun-based fuels is in use, a volatility process for these fuels
could provide additional load for a commercial volatility plant.
- Slide 1.
Let us examine for a moment some of the advantages and disadvantages
of the molten-salt fluoride-volatility process for Al-U alloy fuels. The
process, like its counterpart for Zr-U alloys, appears particularly
attractive from the standpoint of directly yielding its highly radioactive
waste as a low volume of solids. The process has minimal problems of
nuclear afety. From the standpoint of chemical safety, the reactions are
easily controlled, there are no reservoirs of liquid oxidants, and the
process operates at practically utmospheric pressure. By analogy to the
Zr-U alloy process, degree of decontamination of the uranium from f'ission
products should be exceptionally high, and uranium losses have been shown
to be low.
- Slide 2 -
As in most fue I recovery processes, corrosion is a point of concern.
By normal standards, corrosion in molten-sa It fluoride-volatility processes
is high. However, our data indicate that corrosion in the dissolution or
ta

ti
2
.
hydrofluorination step is lower in the aluminum process than in the
zirconium process. Unfortunately, one recent study indicates that
corrosion during the fluorination step may be worse.
The proximity of the temperature of the relt during the dissolution
step to that of the melting point of the Al-i alloy has been of concern,
but laboratory tests and calculations indicate that the inadvertent melt-
ing of a fuel element during full-scale operation should not lead to any
serious consequences. (Slide Off)
Our conclusions thus far are that the molten-salt fluoride-volatility
approach is ſeasible for use with Al-U allcy fuels. Although we do not
at this stage claim superiority over either the aqueous process or the
other volatility processes, demonstration of the process with highly
irradiated, short-decayed fuels seems in order, and work is underway in
our Volatility Pilot Plent to that end.
.
.
.
- Slide 3 -
As to the details of our studies thus far, Mr. Thoma has presented
results of his phase equilibrium studies which culminated in our use of
the KF-2rF2-A1F, system. I will (1) summarine laboratory studies made
to determine dissolution rates of aluminum in that system, (2) briefly
discuss the reaction mechanisms postulated for the dissolution step, (3)
describe alternative flowsheets for the steps involving molten salt,
- Slide 4.
(4) present results of laboratory fluorination tests, (5) describe a
demonstration of the process at a semiworks scale, and (6) mention our
corrosion studies.
- Slide 5 -
CHOICE OF KF-ZrF4-A1F, AS THE SOLVENT
As you have already heard, the system KF-ZrF,-A1F, was chosen based
on its high solubility for A1F, as evidenced by liquidus temperatures less
than 600°C from 0 to at least 35 mole % A1F, Its low cost made possible
by the commercial availability of ZrF2 •27 at 50$ per pound (67€ per pound
of contained ZrF), and its low viscosity and vapor pressure at the
operating temperature.
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DISSO JIIO
Summm.ry Ol' vooratory-Scale Dissolution mate Tesis
Next in importance after choice of a salt system is determination of
rütc oi dissolution of the alloy in the cult by II. A total of 25 such
tests were made. For reasons wirich will be apparent later when I discuss
the details of the alternative flowsheets, the tests were made in three
groups related to composition of the initial melt. The tests consisted
of the partial reaction of 3-g specimens of aluminunn in 60 to 70: 3 of
salt held in a 0.93-in.-ID' reactor. The tests were conducted at 600°C,
arů hydrogen fluoride was passed through the melt at about 100 std ml/min.
- Slide 7 -
The first series of tests centereä around an initial relt of 60-40
moie F-Zri'. Interestingly, u maximum dissolution rate of 51.2 mils/hr
was obtained at that composition. In the second series of tests using 65
to ??O mole E"-ZrF2, addition of 4 to 10 Alf, was necessary to maintain
liquidus tenperatures below 600°c. In this region, another maximum but
lower dissolution rate was found.
- Slide 8 -
In the third series, dissolution rates over a possible process path
increased steadily from 7.8 mils/nr at 12 to 42.6 at 29.0 mole ' Alfgó
- Slide 9 -
Reaction Mechanisms
Variations in the rate of hydrogen evolution with initial melt com-
position and formation of an intermediate reaction product at some melt
compositions led to the conclusion that Equation i wais not the only one
occurring, but that the zirconium fluoride was also being reduced according
to Equation 2.
2A1 + 6HF – AlF3 + 3H,
(1)
KAI + ZZ/F- 4A9F2 + 327
"
"
..
The intermediate reaction product was a black material that was
never positively identified. Its chemical analysis was inconclusive
because of the presence of the salt matrix. Lack of an X-ray diffraction
pattern indicated that it was amorphous. It liberated hydrogen from
water and nitrogen oxides from nitric acià. The l'ormation of the black
material, delayed evolution of hyürogen, dissolution rates, and melt
composition were interrelated. Generally speaking, when the evolution
of hydrogen was delayed, the black material was formed and dissolution
rates were high. Side reactions occurring as a consequence of Equation 2
probably formed zirconium hydride by Equation 3.
Zr + ZH, -- Zr H,
Some indications of the formation of a transitory Zr-Al intermetallic
were also noted.
(3)
- Slide 10 -
A comparison of Hr consumption, hydrogen evolution, and metal dis-
solved during one indicated that the composition of the zirconium
hydride formed was ZrH, 22• This is a reasonable value based on the
low average partial pressure of hydrogen during the run.
- Slide 11 -
When hydrogen was retained and the black material was formed,
continued hydrofluorination resulted in evolution of all of the hydrogen
and disappearance of the black material. In the runs made during the
third series of tests, as previously described, the evolution of hydrogen
was not delayed, and no black material was formed.
"STEP" AND "PARTIAL TRANSFER" PROCESS FIOWSHEETS DEVELOPED
Two methods for obtaining a reasonable capacity of Air, in the
'melt were developed. Both were based on the phase diagram for the
KF-ZrF2-AIF, system, the use of commercial 63-37 mole % XI-ZrTw, recycle
of the salt from one dissolution to the next, and operation at 575 to
600°c. The specific flowsheets and compositions about to be described
were based on charging an integral number of Oak Ridge Research Reactor
II
,
""
fuel elements to the Volatility Pilot Plant hydrofluorinator for each
dissolution step.
- Slide 12 -
The "step" process is pictured on this diagram. Note that only
the lower left quarter of the overall composition-liquidus diagram is
shown. Changes in comosition are indicatcd by the path TGHIJK. The
initial melt (point F) is 60-40 mole ' KP-Zr7. Iwo cycles of dissolving
one element and diluting with Kresult in reaching point J. Two more
elements are dissolved to produce a salt containing 30.5 mole % AlF
and 3,000 ppm of uranium when using irradiated elements. After
fluorination the salt is discarded.
- Slide 13 -
The "partial transfer" process actually starts at M with an initial
melt composition of 66-22-12 mole % KF-Zrf;,-AIF, and extends to N, but
when starting a series of runs, the initial relt is obtained by following
the path BIM. The path MN represents the dissolution of two elements
to yield a melt containing 29.2 mole % AIF, and about 2,600 ppm of uranium.
The uranium is removed from this salt by fluorination. Then about
two-thirds of the salt (by weight) are discarded. The other one-third is
recycled and diluted with 63-37 mole % F-ZrF, and KT to 66-22-12 mole '
to become the salt charge for the next cycle. This sequence of operations
can then be continued indefinitely. The location of point M may have to
be changed slightly, since, as the diagram indicates, the most recent
phase-diagram studies indicate & liquidus above 600°C for that particular
composition.
- Slide 14 -
FLUORINATION STUDIES
The ability to easily fluorinate uranium from the proposed melt is a
requirement for any new application of the molten-salt fluoride-volatility
process. Laboratory-scale tests were made to determine the completeness
and rate of removal of uranium from KF-ZrI' -AlF, melts. Conditions and
results of the tests are summarized here. The results show that the
wiunium wus easily volatilized.
C
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The first tiro tests shown were made with relt compositions expected
at the end of the first part of the step process, the third and fourth
tests simulated conditions at the end of the step process, and the last
test was typical or the relt composition at the end of a dissolution using
the partial trenufer method. The highest l'inal value for uranium con-
centration in any of the fluorination tests was 30 ppm after 1 hr of sparging.
This me.lt initially contained 5300 ppm ož uranium.
- Slide 15 -
SEMIWORKS-SCALE TISTS
i
As the next step in developrcent of the molten-salt Iluoride-volatility
process for Al-U alloy fuels, tests of the entire process were made at an
engineering or semiworks scale. Shorü lengths of full cross-section fuel
elements were first dissolved into a salt melt by HF. Both the step and
partial transfer procedures were tested. The uranium was removed from
the melts by sparging with fluorine.
These tests were highly successful; both overall penetration rates
of metal during hydrofluorination and degree of uranium removal by
fluorination were excellent.
- Slide 16 -
Here is a photograph of the reaction vessel used. The lower part is
5-1/4-in. II), compared with 5-in. Il for the 9-1/2-ft-high lower section of
the hydrofluorinator in the Volatility Pilot Plant. The insert photograph
shows an 8-in. length of a full cross-section fuel element typical of
those used in the tests. In contrast to the Volatility Pilot Plant where
the hydrofluorination, or dissolution, and fluorination steps are performed
in separate vessels, in these tests both steps were performed in the same
vessel. The section of fuel element rested on a perforated plate over
the HF inlet point. The salt level varied from barely covering the
element to midway in the 9-3/4-in.-ID expanded section, depending on the
process used and the length of element section. The constructional
material for the vessel is INOR-8, or Hastelloy-N.
- Slide 17 -
The test of the step flowsheet consisted of three dissolutions and
one fluorination. Overall penetration rates varied from 3.5 to 9 mils/hr
of HF exposure time, and overa 11 utilization of HF ranged from 9.5 to
44.816.
- Slide 18 -
After the last dissolution, the resulting seit was sparged with
fluorine at 2 std liters/min. After three hours, the uranium concentration
had been reduced from its original value oi' 6210 ppm to 65 ppm.
- Slide 19 -
The partial transfer procedure was tested next by making six
dissolution-fluorination cycles following an initial step dissolution-
ailution to obtain the desired corrosition. Overall penetration rates
were 3 to 6 mils/hr of exposure to HF, and HF utilization varied from
15 to 37%.
- Slide 20 -
To study the Iluorination part of the partial transfer procedure, a
total of eight runs were made using the salt produced by the dissolutions.
Data from six typical runs are shown here. Note the low final concentrations
of uranium obtainable after only two or three hours of i'luorination.
From an operational standpoint, the runs were very smooth. The
exceptions were two temperature excursions that were controlled by
stopping the flow of HF until the temperature returned to normal.
- Lights -
CORROSION
The relative corrosivity of the proposed melt to the container
materials is of great importance when considering new molten-salt fluoride-
volatility process conditions. Five separate studies were made at ORNL
and at Battelle Memorial Institute under subcontract to determine the
corrosivity of the rea gents in the aluminum process. The metals of
interest were INOR-8, alloy 79m (Isnown commercially as HyMu 80 and
Moly Permalloy), and nickel 201, or I-ivickel. Three of the studies

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were muc with molten salt and HF'; one of these comored corrosion
rates with sind without aluminu? úissolving. Anocher study cc 2011
simulatců the Iluorination step ai a laboratory scale, and the fifth
one was during the semi works-scale cycles of hydrofluorination and
iluorination in the same vessel, is previously described.
let me surmarize all of the hydrofluorination corrosion studies,
by saying that, in general, the corrosivity of the compositions of
KF-CTI",-AF, and HT toward INOP-8 is less than that of the NaF--Zri
system used for zirconium Fuels.
- Slide 21 -
Shown here are times, temperatures, and the salt compositions used
for the laboratory-scale determinations of corrosion during fluorination
for both the zirconium and aluminum processes that were made at BHI.
- Slide 22 -
We present here the results of this test. Note the significantly
greater rates of attack found for the aluminun process.
- Slide 23 -
More encouraging is the comparison of rates of corrosion of test
burs exposed at a semiworks scale to repeated cycles of hydrofluorina üion
and fluorination during tests of both processes. Again the times,
temperatures, and salt compositions are presented.
- Slide 24 -
This slide presents the corrosion rates calculated on the basis of
time of exposure to fluorine. This gives a conservative value that we
feel is appropriate because of the much greater corrosion experienced
during the fluorination step. The data show the greater resistance of
alloy 79-4 as compared with INOR-8, and the lesser corrosivity of the
melt used in the aluminum process as compared with the oile used for
zirconium.
- Lights -
Let me conclude by saying that the process is now being operated
in the Volatility Pilot Plant using unirradiatea : uel elements, and I
hope that the successful results of this series of tests will be the
subject of another paper at some future meeting.
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Slide 1
ADVANTAGES OF MSFV PROCESS FOR AI-U ALLOY FUELS
RADIOACTIVE WASTE - LOW VOLUME IN SOLID FORM.
SAFETY - EXCELLENT FROM BOTH NUCLEAR AND CHEMICAL STANDPOINTS.
SEPARATION OF U FROM FISSION PRODUCTS - VERY HIGH.
URANIUM LOSSES - LOW,
M
WITT
Slide 2
POINTS OF CONCERN WITH MSFV PROCESS FOR AI-U FUELS
CORROSION
PROXIMITY OF MELTING POINTS OF SALT AND FUEL ELEMENTS
..
... .....
.....
..
...
..
.
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8lide 3
OUTLINE
CHOICE OF SALT SYSTEM - R. E. THOMA
DISSOLUTION OR HYDROFLUORINATION
RATE STUDILS
REACTION MECHANISMS
FLOWSHEETS
Slide 4
OUTLINE (CONTINUED)
FLUORINATION STUDIES - LABORATORY
PROCESS DEMONSTRATION - SEMIWORKS
CORROSION DE TERMINATIONS
"
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811de 5
ADVANTAGES OF KF-ZrF-AlF3
HIGH SOLUBILITY FOR Alf,
LIQUIDUS TEMPERATURE OF <600°C FROM O
TO >35 MOLE % Alfa
LOW COST - ZIF 2KF AT 50€/lb (674/16 OF ZIF}
LOW VISCOSITY AND VAPOR PRESSURE AT 600°C
811de 6
Determinations of Dissolution Rates for Aluminum
Conditions:
Reactor - 0.93 in. DD
Specimens - 38 rods
Salt wt - 60 to 70 8
Temperature - 600°C
Hr Flow - 100 ml(STP)/min
t:
1.
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Point K
Comp. (mole %)
rF AF
Dissolution
Rate (mi18/hr)
A-
50 -
60
62.3
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30.7
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7.0
51.2
37.2
DISSOLUTION RATE, GRAVIMET:0:-::s/n.:)


When present, initial ...
AIF, content 18 as
indicated.
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FIRST SERIES →
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-SECOND SERIES I
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65
70
KF CONTENT (mole % in kl.214 linory syair.)
Effect of Melt Composition on Rate of Aluminum Dissolution with AF at 600°C
-... -ch
55
12
Slide 7
ت ین
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DINL Diiû, 6., 37:4

Point K
Com. (mole $)
ari
Dissolution
Rate (mi18 /ar)
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DISSOLUTION P.?:TE, CAVINC(m3/::)

in.
20
AlF3 CONCENTRATION (mole %)
Erfect of Melt Composition on Rate of Aluminum Dissolution with HF at 600°C
(third test series).
Slide 8
Slide 9
REACTION MECHANISMS FOR DISSOLUTION
OF ALUMINUM IN KF-ZrF,,-AIF, with HF
(1)
211 + 6HF – AlF3 + 344
4A1 + 32.67% - 411F3 + 327
Zr + x/2 H -- Zrty
.
.
.
.
.
.
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Slide 10
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UNCLASSIFIED
ORNL-DWG 64-7578
ESTIMATED COMPOSITION OF ZIRCONIUM
PRODUCED DURING ONE RUN
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LISSCHUTION 1/10, Livinilic (til:/hr)
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5-60.6-19.4-20.0

(Values are mole % KF-ZrF2-ALF3)
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.
AlF3 CONCENTRATION (mole %)
Black Material not Formed During the Auns 100 the Third Series of Dissolution Rate
Testo.
slide 2
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UNCI.ASSIFIED
ORNL-DWG 61-6533
KF.Alfis
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301
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Alfz (mole %)
21F4 (mcle %)
COMPOSITION (molo %)
POINT
KF
AlF3
104
60
40
34
60
xc-la
120
2 1.5
18.0
30.5
27.3
24.3
20.4
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------
KF (molo %)
KF L
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STEP PROCESS FOR DISSOLVING AI-U ALLOY IN KF-ZrFa WITH ME AT 575 °C
81 do 12
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AlF3 (mole %)
ZrF4 (mole %)
POINT
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COMPOSITION (mole %) M
ZiF4 A1F3
63 37
52.4 30.8 16.8
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, PARTIAL TRANSFER PROCESS FOR DISSOLVING AI-U ALLOY IN KF-ZrF4-A1F3 WITH HF AT 575 °C
Slide 13
"WW"-TYAPUD
"
Slide 14
Results of Selected laboratory Tests Show Nearly Complete Removal of
Uranium from KF-ZrF,-A1F, Melts with Fluorine
Conditions: 50 to 70 & of salt in a 0.93 ID nickel reactor.
Fluorine flow rate - ~100 ml(STP)/min.
Fluorination
Salt Composition
(mole %)
KF 2rF4 AlFz
Temp.
Time
Uranium Concentration
(ppm)
Initial
Final
(hr)
575
0.5
1530
1.2
51
51
34
34
15
15
0.5
1480
15.0
28
575
3200
51.5
51.5
20.5
20.5
3500
51.8
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600
1.0
3900
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2.2
Slide 15
PROCESS DEMONSTRATION - SEMIWORKS SCALE
Procedures
Step
Partial Transfer
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Slido 17
TESTS OF STEP PROCODURI:
Dissolution (3 runs)
Temperature
500 to 610°C
1.36 kg/hr
HF Flow Rate
Overall penetration rates
3.5 to 9 mils/hr
9.5 to 44.8%
Overall lif Utilization
::: -1moms ---.---
-------********...
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le
s condimen
de min
nie
manteriormente
commissariamente commencement there is reason to internacionaliniame
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811do 3.0
.
TESIM Qr STIP PROCIDURIS (CONI'))
575
Fluoxl.nnt.lon (ono zun)
salt temporature (°C)
9:1180 (min)
Fa Flow Rate (Std 1/min)
Litors or F,/kg or Salt
180
U Concentration (ppm)
Initial
6,210
Final
3.3
F. Utilization (%)
Fa Half tino (min)
28
4W

Blido 29
9153T OF PAMIL TAM MWIER PROCKDURE
Dissolution (Inttial fitop + 6 cycl.co)
Torpornturo
530 to 630°C
1.36 kg/11
ID Flow Rato
Ovorall Pono tantilon Ratoo
3 to 6 m2.18/12
15 to 37%
Overn... IM UL111mation
!
31
N
*
.
Slide 20
TEST OF PARI'IAL TRANSFER (CONI'D)
Fluorinat:lon (selected runs)
Temperature - 550 to 600°C
F, Flow
Rate
(Std L/min)
Fa Util-
Ization
Fluorination
Half Time
Time
(min)
Liters of F.
Ke of Sale
U Conc. (ppin)
Init. Final
(min)
360
o
240
240
w aw w
24.3
32.1
79.1
151.6
33.6
8,380
1,410
6,200
6,900
3,380
240
-
-
-
-
120
I
!

Slide 21
EXPOSURE CONDITIONS FOR CORROSION
DURING FLUORINATION IN LABORATORY STUDY
Process
Zirconium
Alumi mum
NaF-IF-ZrFM
27.5-27.5.145
KF-Z5F2-A1F3
52-16-32
Salt
(mole %)
Temperature (°C)
Time (hr)
500
600
248
116
UF, added to produce us by reaction with F, sparge.
-
womandante
e
.
.
-
811de 22
CORROS ION RATES OBTAINED DURING JABBORATORY
SIMULATION OF FLORINATION STEP
Maximum Penetration Rates (mils Ihr)
Process
INOR-8
Nickel 201
Alloy: 79-4
0.0058
Zirconium
0.0154
0.0332
0.1578
Aluminum
0.1166
0.0965
"Weight loss data, no intergranular attack.
"By micrometry or metallography, whichever greater.
Slide 23
EXPOSURE CONDITIONS FOR CORROSION TEST BARS IN
SINGLE VESSEL STUDIES
Processes
Zirconium
Aluminum
Salt, initial
NaF-LiF-Zrt.
35-35- 30
KF-ZrT4-A1FZ
(variable)
500 to > 700
550 to 575
Bulk salt temp. (°c)
Exposure (hr)
Melt
1060
907
1112
238
66
34.8
5..10e 24
CORROSION M19 Y'ON LAST RARS IN
SINGLE VESSEI STUDIES
PROCOSSOS
Zircon:lum
Aluminun
INOR-- 8
79-11
7904
0.19
INON-3
0.11
0.33
0.03
Corrosion Witoli, by Hicronety:
(m111 por of 12)

ra
34.!!
12
*
1-
.
D
ALS
R
er
25
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PS
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4
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4:...
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KA
14.
ONU
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JANNE
41
.
PM
UN
LIS
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SP
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hr
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1:1.
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!
"L
DATE FILMED
11/25/164
A
.
"
LEGAL NOTICE —
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- Hator, nor the Commission, nor any person acting on behalf of the Cou mission:
A. Makas any warranty or representation, expressed or implied, with respect to the accu-
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B. Asnumas any liabilities with respect to the une of, or for damagui rosulting from the
um of any information, appuratus, method, or procesu dieclosed la this report.
Ao wood in the abovo, "person acting on behalf of the Commission" includes any «A-
ployee or contractor of the Commission, or omploys of much contractor, to the extent that
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END