ORNL-TM-0411.txt

 

OAK RIDGE NATIONAL LABORATORY
operated by

UNION CARBIDE CORPORATION
for the

U.S. ATOMIC ENERGY COMMISSION ,/
VAR

ORNL- TM- 411 ~ |

 

_* g CORROSION OF NICKEL-BASE SPECIMENS EXPOSED IN THE
. & VOLATILITY PILOT PLANT MARK 11l FLUORINATOR

"

- B

L

1“ o
a p

M. Kegley, Jr.
P

T.
A. P, Litman

2
4 2

DS WY A
LI L 2T T P RS S
el R

IS

) '
“ :
it N
s i-

?‘O “
5 p 3

./.‘

C e y
Roy
E '

e | 7

NOTICE

This document contains information of a preliminary nature and was prepared
primarily for internal use ot the Ock Ridge National Laboratory. It is subject
to revision or correction and therefore does not represent a final report, The
information is not to be abstracted, reprinted or otherwise given public dis-
semination without the approval of the ORNL patent branch, Legal and Infor-
mation Control Department,

 
 

 

 

LEGAL NOTICE

This report was prepored os an account of Gavernment sponsored work, MNeither the Unired States,

nor the Commission, noer any person acting on behclf of the Commissien:

A, Makes any worranty ar represaniation, expressed or implied, with respect to tha wccuracy,
completeness, or usefulness of the information contained in this report, or that the use of
ony information, apperatys, method, or process disclosed in this report may not infringe
privately owned righis; or

B. Assuymes ony liabilities with respect to the vse of, or for domages resulting from the use of
any information, apparotus, method, or orocess disclosed in this repart,

As used in the cbove, “‘person acting on behalf of the Commission® includes any employee or

controctor of the Commission, or employee of sueh contractor, to the extent that such employes

or contractor of the Commission, or employeo of such contractor prepares, disseminates, or
provides access to, any information pursuant to his employment or contract with the Cammission,

or his employment with such contractar,

 

 
ORNL-~TM=-411
Copy,.2 /

Contract No. W-7405-eng-26

METALS AND CERAMICS DIVISION

CORROSION OF NICKEL~-BASE SPECIMENS EXPOSED IN THE
VOLATILITY PILOT PLANT MARK IIT FLUORINATOR

T. M. Kegley, Jr., and A. P. Litman

DATE ISSUED

JAN 4 1963

OAK RIDGE NATTONAL LABORATORY
Oak Ridge, Tennessee
operated by
UNION CARBIDE CORPORATION
for the
U. S. ATOMIC ENERGY COMMISSION
ii

CONTENTS

INTRODUCTION ===- = e mm e e e e e e e e e e e e e e m e —m e
EXPERIMENTAL PROCEDURE -=-=----—me e e e e e e e e e o
Specimen Description —---cesmmmmmmmm e e e
Test Method ~wwecmmmmmm e e -
Test Conditions =--=--meemcce e e e e e e
RESULTS =--==-emmm e m e e e e e e e e e e e m e e —
Visual Examination ------=-m--ccmmmmmm e -
Dimensional Changes ~---=-—=-cm-mmo e e me e
Metallographic BExamination -—-----ec-omeommcmcmcm e
Surface FIlms =--------- e e e -
Surface Attack -------remmmm e
Intergranular Attack ---------mmmmmmmmm e
Grain-Boundary Modifications ==w=ecc-mmmommmcm e
Bend Tests ~emmemcmmm e e e e e -
SUMMAYY === == e e e e e ;e —cme—m = ———
DISCUSSION OF RESULTS ==r--meeer e e e e e e e e e e e e m e e e -
Comparison Between Group I and Group II Specimens --------
Comparison With Previous Studies ------——cmmmmmmmccmmee oo
Effect of Fluorine Conditioning on L Nickel and INCO-61
Weld Metal =~-~-memmmmm e e
CONCLUSTIONS ===m=mmem e e e e e e e e e e e e e e m e mm
ACKNOWLEDGMENT ~-~—-mmme e e mm e e e e e e m e e — e
APPENDTX -----m e e e e e e m e e e e e - o
CORROSTON OF NICKEL-BASE SPECIMENS EXPOSED IN THE
VOLATILITY PTLOT PLANT MARK ITI FLUORINATOR

T. M. Kegley, Jr., and A. P. Litman
TNTRODUCTION

For several years the Volatility Pilot Plant has demonstrated the
Teasibility of processing zirconium-base fuels using fluoride volatility
technigues. In an INOR-8 hydrofluorination vessel, rejected fully en-
riched zirconium-uranium alloy or dummy Zircaloy-Z2 fuel elements are
dissolved at 500-600°C in NaF-LiF-ZrF, salts using an excess of anhy-
drous HF gas. Zirconium and uranium metal are converted to soluble
tetrafluorides which subsequently are transferred, along with the fluoride
bath, to a fluorination vessel. In the [lucrinator, which is constructed
of L nickel and operated at 500°C, elemental fluorine converts UF, to UFg
product which ie decontaminated and collected in cold traps. Figure 1
shows a simplified Tlowsheet of the volatility process,

Severe corrosion of the L nickel fluorinator occurs during processing.
Three fluorinators have been used to date in the pilot plant, and all three
have sustalned a maximum corrosion attack of approximately 1 mil/hr, based
on the fluorine exposure times.1»? Efforts to reduce the corrosive attack
on fluorination vessels have included minimizing the operating temperature,
careful exclusion of sulfur-containing compounds, and the search for a
more resistant construction material, Acceordingly, in the first two
pilot plant fluorinators, Mark T and II, corrosion tests were periormed

using many potential container materials, mostly nickel-bacse alloys.3

 

1A, P. Litman and A. E. Goldman, Corrosion Associated with Fluorina-
tion in the Oak Ridge National Laboratory Fluoride Volatility Process,
ORNL-2832, p 25 {June 5, 1961).

A, P, Litman, Corrosion of Volatility Pilot Plant Mark I INOR-8
Hydrofluorinator and Mark IIT L Nickel Fluorinator After Fourteen
Dissolution Rung, ORNL-3253, pp 1, 30 (Feb. 2, 1962).

*A. P. Litman and A. E. Goldman, op. cit., pp 108-23.

 

 

 
UNCLASSIFIED
ORNL-LR-DWG 81615

 

 

   
  
  
    
    

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Fa
DISPOSAL
I DESORPTION
/. IN, NaF
g "N d QUTLET UFg COLD | F2
AG. KOH
SPRAY
NGF -LiF-ZrFa ABSORPTION Fp TOWER
Ha OUTLET
! UFe
NEUTRALIZER MO;Q%FE COLLECTION l
(10% KOH ) =
I ARSORBER QUID WASTE
400 - o LI
LIQUID HF + Hp o-io07C
WASTE
"FUEL CHARGING :
Hp CHUTE F2
FREEZE VALVE
) :
— B
HF : ! 5 &GF"L%?"'“Z.FF%
RECYCLE k\ J
SYSTEM L /
ot/ NaF -Lif-ZrF4-UFy
\ ( ‘ WASTE SALT
Zru i

?v1 e q
SPENT PO 1
£ o

 

 

 

 

 

 

 

: |
1 | ! i
FUEL ~ . 1| 1 s00%c
| ! L
o ! | 1
850-50Q C ¢ P s/
] E PN
i e
HF FREEZE o -
HYDROFLUORINATOR

Fig. 1. Simplified Flowsheet — ORNL Fluoride Volatility Process,
-3 -

Those nickel binaries containing iron, cobalt, or manganese showed
improved corrosion resistance over L nickel and were thus selected for
additional testing in the current Mark IIT Tluorinator.

To date, 24 specimens have been exposed in the Mark III fluorinator.
This report covers the 12 specimens comprising Groups I and IT. Groups III
and TV will be discussed in a separate report. In addition, specimens have
been placed in the Tluorinator Tor exposure during current runs where

irradiated submarine fuel elements are being processed.

EXPERTMENTAL PROCEDURE
Specimen Description

Desceriptions of the Group I and IT test specimens, their location,
and chemical compositions are shown in Tables 1 and 2. Control specimens
contalning the materials used in the construction of the tTluorinator
were included in both groups. The control specimens consisted of Z-in.
lengths of £-in.-diam L nickel rod joined together with %-in. deposits
of INCO-tl weld metal. The control specimen Trom Group I and one of the
controls from Group II were fluorine conditioned for 3.2 hr at 600-645°C
before testing to ascertain the effsct of conditioning on corrosion.

The high-purity, vacuum-melted nickel specimen was obtained by re-
melting NiVac P nickel. Bubsequently, the high-purity nickel was cast
into a l-in.-diam bar, cold swaged and cold drawn down to an C.250-in.
rod, and annealed at 1500°F.

The other binary alloys used in these tests were melted from virgin
stock and cast into l-in.-diam bars, cold swaged and cold drawn down to
0.250-in. rods. Subsequently they were annealed at 1650°F and placed in

test.
Test Method

The specimen rods were located in nozzles attached to the lower
chamber of the Mark IIT Tluorination vessel, as shown in Fig. 2. Hach
rod was held in place by a fitting which gripped a tube prewelded to the
end of the rod (see Fig. 3). TFigure 4 shows a polar view of the fluorina-

tion chamber and the plan layout of the corrosion nozzles.
Table 1. Test Specimens Exposed in the Volatility
Pilot Plant Mark TIII Nickel Fluorinator

 

 

Specimen Nozzle
No. Location Description&
Group 1
51 0 L nickel, 3-in. lengths, Jjoined
by INCO-61 weld metal
32 L 98 NWi—-2 Mn
39 P High-purity, vacuum-melted nickel
24R R 95 Ni-5 Fe
27 M 90 Ni-10 Fe
29 N 80 Ni~20 Fe
Group II
52 P L nickel, 3-in. l@ngthg, Joined
by INCO-61 weld metal
55 N L nickel, 3-in. lengths, joined
by INCO-61 weld metal®
17 0 95 Ni~5 Co
21 R 90 Ni-10 Co
1R M 99 Ni—1 Al
5 L 97 Ni—-3 Al

 

a
All rods spproximately (0.250 in. diam X 36 in.
long.

DControi specimen — Tluorine conditioned for
5.3 hr at 560-670°C.

C . C o |
Contrcl specimen — not conditioned.
 

 

 

Table 2. Chemical Analyses of Test Specimens
Welght Percent {ppm)

Material Ni Mn Fe Co Al Sd Ti C S
98 Ni—Z2 Mn $7.00 2.18 0.057 40
95 Ni—5 Fe 95 4.9 0.019 < 10
90 Ni-10 Fe 88 11.8 0.0i6 < 10
80 Ni—20 Fe 79.6 20.1 0.017 < 10
95 Ni—5 Co 9. 6 5.9 0.020 < 10
90 Ni—-10 Co 90.0 9.4 0.026 20
99 Ni-1 Al < 0.04z2 < 10
97 Ni-3 Al 96.4 3. 0.027 < 10
INCO-61 weld 96+ 0.26 0.35 1. .36 1.44 0.0z27 30
metal deposit

NivVac P high- < 0.002 0,03 0.09  0.005 0. 007

purity Ni®
L nickel® 99.0° min 0.35  0.40 0.35 0.0z 100 max

 

f7race amounts of Cr, Ca, (u, Mg, and Op.

D . .
Noeminal analysis.

“Including cobalt.

R
UNCLASSIFIED
ORNL-LR-DWG 39150 -R

 

 

    

 

 

 

FURNAGE LINER--—|
| —FLUORINATION CHAMBER
(16-in.0D)
DRAFT TUBE —~—i_
WASTE SALT OUTLETMWig RINE INLET
o INCHES

 

 

 

 

 

 

FURNACE

 

 

 

Fig. 2. Mark III Volatility Pilot Plant Fluorinator Vessel
Showing Corrosion Specimen Nozzles.
MECHANICAL THREADED

Y/o-in. SCHED-40 PIPE

UNCLASSIFIED
CRNL-LR—DWG 70683

TUBE PRE-WELDED TO SPECIMEN
-7 770 FIT THREADED FITTING

FITTING

TOP OF FLUCRINATION

/ CHAMBER

(8 in. LONG)

   

o

  
 

SEAL WELD

SPEcaMEN/

,7///////////////////////\

Fig. 3. Method for Holding Specimen Rods in Fluorinator
Vessel.
UNCLASSIFIED
ORNL-LR-DWG 70690

FLUORINE DRAFT TUBE —_

0
O .~ SALT INLET

CONNECTING CYLINDER
BETWEEN SOLIDS

SETTLING CHAMBER AND

FLUORINATION CHAMBER —

 

SALT QUTLET | O . Q

Fo INLET

T~ SALT SAMPLER NOZZLE

Fig. 4. Polar View of the Top of the Fluorination Chamber
Showing Location of Corrosion Specimen Nozzles.
- 9 -

Test Conditions

The Group I corrosion specimens weres exposed during Volatility Pilot
Plant runs T-1 thrcough T-7, while the Group II specimens were cxposed in
rung TU-1 through TU-5. Test conditions Tor these runs are summarized in
Table 2. The T runs were made without uranium in the system, while the

TU runs were conducted with 0.3 wt % U in the starting fuel element.

Table 3. Process Conditions for Groups I and II Corrosion Specimens

 

 

Group Ea Group I1
Volatility Pilot Plant Runs T-1 through TU-1 through
T-7 TU-5
Thermal cycles, room tempera- 7 5
ture fo operating temperature
Salt composition, mole % LiF-NaF—2ZrF., LiF-NaF-ZrF,
(~ 30~27—43) (~ 29-29-42) +
0.2 wt % U
Molten salt exposure
Time 267 nr 205.5 hr
Temperature 485-605°C 490-575°C
. b
Filuorine exposure
Time 12.0 hr 10.5 hr
Temperature 535-570°C 500-515°C
Fluorine input 5760 liters 5385 liters
UFg exposure None 256 liters

 

a'L nickel and INCO-61 weld metal specimen 51 was fluorine conditioned
for 5.3 hr at 600°C (before exposure to Group I process conditions).

v

0 . .
Molten salt was also present during fluorine exposure.

RESULTS
Vigual Examination

Visual examination of the Group I specimens disclosed fluoride salts
had preferentially adhered to the specimens in the vapor and salt-vapor
interface regions. Figure 5 shows the Group T specimens after cleaning
with an ammonium oxalate solution. Burface roughening was apparent in all

the specimens, but no gross localized metal losses were evident,
Salt-vVapor

UNCL ASSIFIED
Y-38615

 

 

Fig., 5.
Reduced 25%,

Interface Level

Group I Corrosion Specimens from Mark

IIT Fluorinator.

el
Ixanmination of the Group II specimens showed flucride salts had
preferentially adhered to specimens in the lower vapor region. Some
loosely adherent deposits were alsco noted in the Interlace regilon.

Figure 6 shows the Group II specimens after an ammonium oxalate wash.
Dimensional Changes

Bulk metal losses from the specimens were determined from micrometer
measurements taken in the vapor, vapor-salt interflace, and salt-exposure
regions. Table 4 details the results. The Group II specimens generally

showed losses several times greater than the Group I specimens.
Metallographic Examination

Transverse and longitudinal sections taken from the vapcr, interface,
and salt regions of the corrosion specimens were examined using optical
microscopy. Photomicrographs of most of these gections are included in
the Appendix. Metallographic examination revealed that corrosion had
resulted in the production of one or more of the follewing: (1) surface
Tilms, (2) surface attack, {3) intergranular attack, and (4) grain-

boundary modilications.
Surface Films

Twe types of surface films were observed - a gray nonmetallic and a
bright semimetallic film. Usually the films were intermittent in coverage
rather than continuous. Figure 7 illustrates the types of fllms found.
Details regarding the surface films Tound on the specimens are summarized
in Tables 5 and ©. Except for the Group I specimens shewing a propensity
Tor formation of bright films in the salt-exposed region, no particular
pattern associating film Tormation with region of expcsure of specimen
composition was obvious.

Samples of the two types of surface Tilms were obtained from an L
nickel specimen using a microchisel® and submitted for x-ray diffraction

analyses. A quantitative analysis could not be cobtained, but the results,

 

“G. L. Kehl, H. Steinmetz, and W. J. McGonnagle, Metallurgia 55(329),
151 (1957). T
UNCL ASSIFIED
¥-40715

G e e et > M‘m‘

aasy e

P

MO, 55 LT MICKEL AND INCO 61 WELD METAL

 

B

LTOHICKEL  AND INCO &)

e B )
NGO, 52 'L
Froconditioned with Fq'
B A 1 o oo T en— m
" i

e

NO.WZ ONI-95 CO -5
o ho

M-S0 CO -1

SALT-VAPUR MITERFACE LEVELS !

WELD METAL

 

 

 

   
 

Wwo. LR M- 99 AL

 

 

 

R o

NO. 5 ™M .97 AL-3

. g
Rk ki

Fig. 6. Group II Corrosion Specimens from Mark ITII Fluorinator.
Reduced 22%.
- 13 -

 

 

 

 

Table 4. Bulk Metal Losses for Groups I and II Corrosion Specimens
Vapor Salt
Interface
Vapor Region Region Salt Region
Specimen _—
No. Composition Max Av  Max  Av Max Av
Group I
512 L nickel 1.4 0.9 2.0 1.7 2.2 1.5
INCO-61 weld metal 2.6 1.4 2.2 1.9 2.3 2.0
39 High-purity nickel 2.0 0.9 3.1 1.7 1.4 0.8
32 98 wt % Ni-2 wt % Mn 2.0 1.4 1.9 1.7 1.7 1.5
24R 95 wt % Ni—5 wt % Te 1.7 0.9 1.4 1.3 2.1 1.7
27 90 wt % Ni—-10 wt % Fe 1.9 1.1 1.8 1.5 1.7 1.4
29 80 wt % Ni—20 wt % Fe 2.9 1.4 1.4 1.0 1.9 1.6
Group TT
558 L nickel 2.9 1.75 9.1 8.4 7.1 5.9
INCO-61 weld metal 5.4 4.8 12.1 12.0 13.4 12.4
55b L nickel 2.7 2.4 11.4 8.9 7.1 6.3
INCO-61 weld metal 4,0 1.9 13.5 11.95 7.3 7.1
17 95 wt % Ni—5 wt % Co no change 13.4 10.5 11.9 9.2
21 20 wt % Ni~10 wt % Co 4.1 1.1 16.3 14.1 13.0 8.1
1R 99 wt % Ni—-1 wt % Al 2.3 1.2 11.5 10.6 7.8 6.3
5 97 wt % Ni—3 wt % Al 3.5 1.6 17.2 12.3 8.3 7.

 

%control specimen fluorine conditioned 5.3 hr at 560-670°C.

bControl specimen not conditioned.
- 14 -

 

 

 

N
W
T
L3
=
002
NON-ME TALLIC §
GRAY FILM
004
NICKEL SFPECIMEN
008
008
-
O
w-o...
«©)
(@)
UNCLASsIFIED 2%
. Y-39311 o
po Lo e
g
NICKEL PLATE ™
.06

 

007

 

.008

 

209

 

BRIGHT FILM - Moy BN e P Sty ¢ «\_‘fl_ Ao

&

 

/’ \ . 010
L 1 011

/ - =
\\, . ! .al2

NICKEL SPECIMEN

 

 

013

 

014

 

 

 

 

(b)

 

Fig. 7. Surface Films Found on Nickel Corrosion Specimens
Exposed in Volatility Pilot Plant Mark TTIT Fluorinator. (a) Gray
nonmetallic film found in vapor region of Group I L nickel specimen 51.
500X. (b) Semimetallic bright film found in salt region of Group I
high-purity nickel specimen 39. Note intergranular attack. BSurface
was nickel plated to preserve corrogion product, 250X.
- 15 -

Table 5, Surtace Films Found on Group I Volatility
Pilot Plant Fluorinator Test Specimens

 

Gray Nommetallic Film  Bright Semimetallic Film

 

 

specimen Maximum Thickness Maximum Thickness
No. Description Region (mils) (mils)
51B L nickel Vapor Intermittent, 3.5 Nil
Interface Nil Intermittent, 1.5
Salt Nil Intermittent, 1.0
51W INCO-6l Vapor Nil Nil
weld Interface Nil Intermittent, 0.5
Salt Nil Continuous, 1.5%
39 High-purity Vapor Intermittent, 2.7 Nil
nickel Interface Nil Intermittent, 1.0
Salt Nil Continuous, 1.2°
32 K nickel Vapor Intermittent, 1.2 Intermittent, 0.4
98 Ni—-2 Mn Interface Intermittent, 1.5 Intermittent, 0.2
Salt Nil Intermittent, 0.2
24R 95 Ni-5 Fe  Vapor Nil Intermittent, 0.3
Interface Intermittent, 0.3 Intermittent, 0.2
Salt Nil Intermittent, 1.0
27 90 Ni-1Q Fe Vapor Intermittent, 1.2 Intermittent, C.1
Interface Nil Intermittent, OC.1
Salt Nil Intermittent, 0.8
£9 80 Ni~20 Fe Vapor Intermittent, 0.5 Intermittent, 0.2
Interface Nil Intermittent, 0.7
Salt Nil Intermittent, 0.2

 

a , . g .  a . .
cemimetallic film was continuous only on one sgide of longitudinal
section.

b . R .
Semimetallic film was continucus over 60% of transverse section.
- 16 -

Table ©. Surface Films Found on Group II Volatility
Pilot Plant Fluorinator Test Specimens

 

Gray Nonmetallic Film Bright Semimetallic Film

 

 

Specimen Maximum Thickness Maximum Thickness
No. Description Region (mils) (mils)
52B L nickel Vapor Intermittent, 1.0 Intermittent, 0.1
conditioned Interface  Intermittent, 0.3 Intermittent, 0.2
Salt Intermittent, 0.7 Nil
52W  INCO-61 Vapor Intermittent, 1.3 Nil
conditioned Interface  Intermitient, 0.5 Intermittent, 0.2
Salt Nil Nil
55B L nickel Vapor Nil Intermittent, O.4
not condi~ Interface Nil Intermittent, 0.4
tioned Salt Nil Intermittent, 0.2
55W INCO-61 Vapor Intermittent, 0.4 Intermittent, 0.4
not condi- Interface  Intermittent, 0.2 Nil
tioned Salt Intermittent, O.Z Nil
17 95 Ni—5 Co Vapor Intermittent, 1.8 Intermittent, 0.7
Interface Nil Nil
Salt Nil Nil
21 90 Ni—10 Co Vapor Nil Nil
Interface  Intermittent, 0.5 Nil
Salt Nil Nil
1R 99 Ni-l1 Al Vapor Nil Intermittent, 0.1
Interface  Intermittent, 0.5 Intermittent, 0.3
Salt Intermittent, O Nil
5 97 Ni—3 Al Vapor Intermittent, 0.7 Intermittent, 0.9
Interface Nil Nil

Salt Nil Intermittent, 0.2

 
- 177 -

Table 7, indicated the gray nonmetallic {ilm was mostly NiFp, while the

bright semimetallic film was largely a mixture of NiC and nickel metal.

Table 7, X-Ray Diffraction Analysis of Surface
Films from L Nickel Specimen 51

 

 

 

Surface Pilm o Line
Type Location Tdentified Intensity
Gray, Vapor NiF» Strong
nonmetallic reglion NiO Weak
LiF Weak
Bright, Salt NiQ© Medium
semimetallic region Ni Medium

 

fnidenti fied extra lines also present in
both samples.

Surface Attack

Many of the corrosion specimens examined showed an attack of varying
character which generally could not be categorized under any heading
except surface attack. Occasionally tThis surface attack had the appearance
of pitting~-type corrosion. Some typical examples of the types of surface
attack found are shown in Fig. €. Additional photomicrographs showing

surface attack are presented in the Appendix.
Tntergranular Attack

Intergranular attack was found in many samples from the corrosion
specimens. Figure 7 illustrates this mode of corrosion as found on
L nickel. The amount of intergranular attack observed on all specimens is
recorded in Tables & and 9. In all cases corrosion resembling inter-
granular attack was designated as such only 1T the attack was observed in

the "ag-polished" metallographic condition.
Grain-Boundary Modifications

In some of the luorinator specimens, grain-boundary modifications
occurred which differed Irom Intergranular attack as previously delined,.
This form of grain-boundary attack was not apparent in the "as-polished"

metallographic sections as was the case for intergranular attack. but was
- 18 -

UNCL ASSIFIED
Y-44672

#

UNCL ASSIFIED
Y -44680

-

 

B UNCL ASSIFIED
Y-4484)

 
 

     
 

(¢)

 
 

f UNCL ASSIFIED
: Y-44642

 

(d)

008

008

 

 

Fig. &. Surface Attack Found on Volatility Pilot Plant Fluorinator

Test Specimens, Group II. (a) Vapor region of 99 Ni—L Al specimen 1R.
(b) Vapor region of 97 Ni~3 Al specimen 5. (c¢) Vapor region of
conditioned INCO-61 weld of specimen 52. {d) Interface region of
conditioned INCO-61 weld of specimen 52. 300X.
o e e o

Table 8.

Corrosion of Group I Volatility

Pilot Plant Fluorinator Test Specimens

 

 

Maximum Maximum Maximum

Bulk Metal Surface Intergranular Total
Specimen Attack Attack Attack Attack
No. Material Region (mils) (mils) (mils) (mils)
51 L nickel Vapor Q.7 0.5 1.2
conditioned Intervace 1.0 1.5 2.5

Salt 1.1 4.5 5.0

51 IBCO~-61 Vapor 1.3 1.3
weld conditioned Interface 1.1 0.2 1.3
Salt 1.2 2.0 3.2

39 High-purity Vapor 1.0 0.2 1.2
nickel Interface 1.6 5.0 6.6

Salt 0.7 6.5 7.2

32 E nickel Yapor 1.0 0.3 1.3
98 Ni—2 Mn Interface 1.0 1.0

Salt 0.9 .9

24R 95 Ni~5 Fe  Vapor 0.9 0.5 1.4
Interface 0.7 0.1 0.8

Salt 1.1 0.7 1.8

27 90 Ni-10 Fe Vapor 1.0 0.3 1.3
Interface 0.9 0.3 1.2

Salt 0.9 0.3 1.2

29 80 Ni—20 Fe Vapor 1.5 0.7 2.2
Interface 0.7 1.0 1.7

Salt 1.0 0.7 1.7

 
- 20 -

Table 9., Corrosion of Group II Volatility
Pilot Plant Fluorinator Test Specimens

 

 

Maximum Maximum Maximum

Bulk Metal OSurface Intergranular Total
Specimen Attack Attack Attack Attack
No. Material Region (mils) (mils) (mils) (mils)
52 L nickel Vapor 1.5 2.0 3.5
conditioned Interface 4.6 3.0 7.6

Salt 3.6 4.5 8.1

52 INCO-61 Vapor 2.7 1.0 3.7
weld conditioned TInterface 6.1 0.5 6.6
Salt 6.7 6.7

55 L nickel Vapor 1.4 3.0 A
not condi- Interface 5.7 6.0 11.7

tioned Salt 3.6 5.0 8.6

55 INCO-61 Vapor 2.0 0.2 2.2
weld not condi- Interface 6.8 6.8
tioned Salt 3.7 3.7

17 95 Ni~5 Co  Vapor 1.0 1.0
Interface 6.7 4.5 11.2

Salt 6.0 5.0 11.0

21 90 Ni—-10 Co  Vapor 2.1 2.1
Interface 8.2 8.2

Salt 6.5 0.3 6.8

1R 99 Ni—-1 Al Vapor 1.2 0.5 1.7
Interface 5.8 5.8

Salt 3.9 3.9

5 97 Ni—3 Al Vapor 1.8 0.9 2.7
Interface 8.6 0.5 9.1

Salt 4.2 4,2

 
- 21 -

visible when the sections were etched with 3 parts CH3;COOH and £ parts
HNO3. The modifications were found to be more clearly defined if the
etched surface was then ligntly repolished on a microcloth wheel using
0.1 ¢ alumina (see Fig. 9a). Another standard etchant for nickel,

92 HCl:5H,80,:3HNO4, revealed only the normal structure usually observed
on nickel (Fig. 9b).

The depth of grain-boundary modifications present in the Volatility
Pilot Plant specimens was determined using the nitric-acetic acid etch-
and-repolish technique described above.

The maximum depth of these grain-boundary modifications for each
corrosion specimen is recorded in Tables 10 and 11. The maximum amount of
grain-boundary modifications was usually observed in the sections taken
from the salt regions., For hnigh-purity nickel, the depth of the grain-
boundary modifications was iound to increase in proportion to the distance

from the top of the specimen (see Fig. 10).
Bend Tests

In order to gain preliminary information on how deleterious the grain-
boundary modifications were on the properties of the fluorination specimens,
a Tew bend tests were perlormed on the high-purity nickel samples. This
material was selected because samples had shown grain-boundary modifica-
tions with and without accompanying intergranular attack, Details of the
test and the results are shown in Table 12. Fracturing occurred in
specimens showing the modifications whether or not intergranular attack
accompanied the modifications. However, the depth of the modifications

did not seem to affect the depth of the 180-deg bend fractures.
Summary

The maximum total corrosion of the Volatility Pilot Plant specimens
was determined in two ways:

L. By summing the bulk metal losses, surface attack, and intergranu-
lar attack.

2. By summing the bulk metal losses and the grain-boundary modifica-

tions., Maximum values for each mode of attack were used in all cases.
- 22 -

  
 

UNCLASSIFIED
Y-44748

  
  
 

-
- ® "
* ¥ 9 . - * - .‘ * & *
. . LN .« '® . - . * . *
. * ¥ >
* . L s * v . -
*
. e -
. . . . . s " ' . * .
. * * . . - . . s
.. - - . ¥u ¥
s * " - .
0‘* . » ’o - -
; - . ' * . - . * s
* » 8 " . " ’ ot .
(@) g » . " :
- - » > -
- .m . -» . * . . -

UNCL ASSIFIED
Y-44645

  

(5)

Fig. 9. Development of Grain-Boundary Modifications in L Nickel

 

007

008

009

 

Q09

 

 

by Etching. Specimen 52B — vapor region. (a) Etched with 3CH;COOH:2HNO,

and repolished. (b) Btched with 92HCL:5H,S0,:3HNC ;.
Table 10.

- 23 -

Grain-Boundary Modifications in Group I

Volatility Pilot Plant Fluorinator Test Specimens

 

 

Grain-
Boundary a
Specimen Modifications
No. Material Region (mils)
51 L nickel Vapor 1.5
conditioned Interface 9.5
Salt 11.5
51 INCO-61 Vapor 0
weld conditioned Interface 0
Salt 0
39 High-purity Vapor 12
nickel Interface 28
Salt 125
32 B nickel Vapor O
98 Ni—-2 Mn TInterrtace 2
Salt 3.5
24R 95 Ni—-5 Fe  Vapor none
Interface apparent
Salt
27 90 Ni—-10 Fe Vapor O
Interface &
Salt 10
29 80 Ni-20 Fe Vapor 2
Interface 5
Salt 5

 

ol
Except where noted, measurements

transverse sections.

are for

b . R .
Etching behavior may have masked grain-
boundary modifications.

C * s s g
Measured in longitudinal section.
Table 11.

_ 24 -

Grain-Boundary Modifications in Group IT

Volatility Pilot Plant Fluorinator Test Specimens

 

 

Grain-
Boundary
Specimen Modifications
No. Material Region (mils)
52 L nickel Vapor 5.5
conditioned Interface 5.5
Salt 7
52 INCO-61 Vapor 0
weld conditioned Interface O
Salt O
55 L nickel Vapor 6
not condi- Interface 4.5
tioned Salt 7
55 INCO-61 Vapor 0
weld not condi- Interface 0
tioned Salt O
17 95 Ni-5 Co Vapor 3.5
Interface 30
Salt 39
21 S0 Ni—10 Co Vapor 4
Interface 3.5
Salt 5
1R 99 Ni—1 Al Vapor none
Interface apparent
Salt
5 97 Ni—-3 Al Vapor 0
Interface 15.5
Salt 14.5

 

aMeasurements are for

transverse sections.,

bEtching behavior may have masked grain-boundary

modifications.
  
 

  
   

 

 

 

 

  
      

 

 

 

 

 

UNCL ASSIFIED UNCL ASSIFIED
Y-44749 Y-44750
. T——— .. _ TTT—
- i N TN
. o ¢ \-)((\ (‘\\ . S s s
=z 3 . . . f
2 14 3. r i\ /y:;(,fi.«t Y
* Lo woe -
' s k“\ N Lo e v
. . 7 " .
. i\
~ -y
. - e .
. 0.02f !
™ - » v
- - ~ .
0.03] -~
. b . -
3
5 ' "
[0
TOP VAPOR
UNCLASSIFIED
@ Y+44752
Ly S
3 S -—
z ;
. .
| - ’
%
9.02 ‘1
L - \\,
| it Voo a
D b s 7
“ ) . \/‘j '.,/ . s . , { A 7
GO T f - i J z’“ >N 7 -
P . T K »4 . Py A ”'; “ X Q]’ ‘ ,
T O s |
L e N (T iy
SN e L /
‘ ~ -~ ’ v
. - [ | S« 7 -
f -~ - 7 ; Y
! \ - A - P
x i o
: ‘L T
z - ’ -
INTERFACE SALT

Fig. 10. Grain-Boundary Modifications in High-Purity Nickel
Specimen 39, FEtched with 3CH3CO0H: 2HNO; and repoclished lightly on
a microcloth wheel using O.1-u alumina.
- D6 -

Table 12. Grain-Boundary Modifications on
Bend-Test Fracture of High-Purity Nickel

 

 

Maximum Maximum Maximum
Depth of Depth of Depth of
Intergranular Grain-Boundary  Fracturing After
Attack Modifications 180~deg Bend

Location (mils) (mils) (mils)
Top O O Q
Vapor 0 12 15
Salt 6.5 125 9

 

Bulk losses based on specimen radlii were used since aggressive attack on
a process Tluorinator occurs essentially only on the inside diameter.
Total corrosion ncted for the specimens is detailed in Tables 8 and 9.
Corrosion rates for the fluorination specimens are shown in Figs. 11 and
12. The rates were determined on the basis of molten-salt residence

time as well as fluorine exposure time.

DISCUSSION OF RESULTS

The individual effects of fluorine, UFg, and fluoride salts on
container materials have been discussed previously.® The modes of attack
observed in this current series were similar to those previously described.

However, attempts were made to categerize better the corrosion modes.
Comparison Between Group I and Group II Specimens

The Group II corrosion specimens in general exhiblted higher corrosion
rates than did the Group I specimens, probably due to the presence of
uranium during the Group II rumns. Previous work has shown the accelerating
effect uranium has on corrosion during fluorination.?

Bulk metal losses, based on specimen radii, were about the same, 0.7

to 1.6 mils, for all the Group I specimens while the metal losses for the

 

SA. P. Litman and A. E. Goldman, Corrosion Associated with Fluori-
nation in the Oak Ridge National Laboratory Fluoride Volatility Process,

ORNL-2832, pp 25-31 (dune 5, 1961).
 

 

 

 

SPECIMEN
NUMBER DESCRIPTION
]
- | 'L'NICKEL |
| F CONDITIONED |
e
| 51-WELD INCO 61 i
METAL F CONDITIONED |
e
o 1 ]
i " HIGH PURITY |
L9 NICKEL
L A
| T !
E'NICKEL |
i 32 98 Ni—2 Mn
o *r .
24R | 95 N|—5Fe
27 ' 90 Ni-10Fe
P ]
29 80 Ni—20 Fe
|
o e

 

mil/mo BASED

ON MOLTEN SALT RESIDENCE TIME

UNCLASSIFIED
ORNL—LR—DWG 70631

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Fluorinator Test Specimens.

0 1.0 20 30 4.0 50 6.0
T T T } - . T T T T i B
b 3 I

| i i ; . | i '
71 \ 1 N i 1 ‘ ! '
N — | | | | I i
oy : 1 | | | . | | | S l
O | o | o
I | ‘ | ‘ | ! | |
! | | % i ; ;
| i i ‘ 1 | i ‘ j
: . | | ! | ; I
77T | 3 } ‘ i ; | : | : ;
! | | | | o
! | | | | | 3 |
! \ I | | | 1 ‘ ‘
. [ | | | | | -
=% | | I I L
5
o | L | : ‘ ‘ —= 240 mil/mo
! | . | : !
- : | | | } ]
| i ' : : i .
! ' i | ,
| | | . ‘ -
| T |
| | ? ; i LEGEND
| . | | B 5u K METAL LOSSES
! | INTERGRANULAR ATTACK
| ‘ ‘ ‘ EXEZ SURFACE ATTACK
1 i ‘ 3 ! 1 GRAIN BOUNDARY MODIFICATIONS i
| : _ ‘ : \
1 I |
. — | |
o T o | | 1
2R ! \ | ‘ ‘
E | | ! | |
= o o .
] o o | |
1 f l % i : ‘
0.5 10 15 2.0 2.5
mil/hr BASED ON FLUORINE TIME
Fig. 11. Corrosion Rates for Group I Volatility Pilot Plant

- LZ
 

 

 

 

 

 

 

SPECIMEN
NUMBER  DESCRIPTION
: 52 "L" NICKEL
| F, CONDITIONED
1
s2-wELD | mCO &1 |
METAL  F, CONDITIONED |
\
{77 - T
. ss "L" NICKEL, NOT l
L CONDITIONED |
55-WELD | INCO 61, NOT
METAL CONDITIONED
T
‘ 17 | 95Ni—5Ca
o
\

21 ¢ 90 Ni-10 Co
R
IR 99 Ni—1 Al
5 97 Ni-3 Al

 

 

 

 

Fluorinator Test Specimens.

mil/mo BASED ON

MOLTEN SALT RESIDENCE TIME

UNCLASSIFIED
ORNL-LR—DWG 70692

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

10 20 30 40 50 60 70 80 90 100 110 120
T 7 T T :
A Lo ! ; | | i
o | | i i
I ! '
| ‘ |
| | |
———_— P | ‘
\ P = \
| ‘ |
]
. 5 ;
| -
T !
| b E
! \
| i |
|
‘ | 124 mil/mo
T T T T 3
v I T T T T T T [ T T ] [ T [ [ T [ |
[ ! I 152 mit/mo
| | |
| | |
] \
i LEGEND &
Il cuL< METAL LOSSES
i INTERGRANULAR ATTACK ;
f EEER SURFACE ATTACK !
[ GRAIN BOUNDARY MODIFICATIONS
|
‘ I [ )
I N S O | f
= TTTTIITTT]]
LTI |
1.0 2.0 3.0
mil/hr BASED ON FLUORINE TIME
Fig. 12. Corrosion Rates for Group II Volatility Pilot Plant

- g2 -
- 29 -

Group II specimens varied from O to 8.6 mils. Group II interface sections
usually exhibited the greatest bulk losses, while sections taken in the
vapor region exhibited the least attack.

Intergranular attack was most prominent in the L nickel and high-
purity nickel specimens of Group I. The maximum depth of penetration by
this mode of attack was 6.5 mils for the high-purity nickel specimen.

In Group II, intergranular attack was found mainly in the L nickel
and 95 Ni—5 Co specimens. For the unconditioned L nickel specimen, inter-
granular attack to a depth of & mils was noted.

Grain~boundary modifications were found in all specimens of Group I
except INCO-6l weld metal and 95 Ni—5 Fe specimens. The L nickel and high-
purity nickel specimens showed thne greatest amount of grain-boundary
modifications — 11.5 and 125 mils, respectively.

All the Group II specimens except the INCO-61 weld metal and the
99 Ni-1 Al specimens exhibited grain-boundary modifications. The maximum
depth of attack by this mode of corrosion, 30 mils, was found in the

95 Ni—~5 Co specimen.
Comparison With Previous Studies

In general, the corrosion rates experienced by the Group I and
Group IT specimens were about the same as those experienced by speclnmens

in earlier tests.?’

Since many different alloys were tested 1n the
current and previocus serics, the best comparison can be made by examining
corrosion of the L nickel control specimens. Table 13 gives the maximum
corrosion rates experienced by all such nickel specimens.

As Table 13 indicates, during corrosion tests the L nickel specimens
were exposed in NaF-ZrF, salts (usually with UF, present), while the
Group I/Grouy IT tests were exposed to a LiF-NaF-ZrF, mixture. The
addition of LiF lowered the salt melting point so that the fluorination
could proceed at slightly lower temperatures. The lower operating temper-
atures would normally decrease corrosion rates. However, as has been
shown previously, the addition of lithium fluoride increases the corrosion

rates on nickel” and the total effect was one of averaging so that compos-

ite corrosion rates were about the same as in the early tests.
Table 13. Comparison Between Maximum Corrosion Rates
Experienced by L Nickel Specimens in Group I/Group IT
Tests and in Corrosion Tests

 

Maximum Corrosion Rate

 

 

Based on
Approximate Salt Based on
Temperature Initial Bath Residence Fluorine
Range Composition Time Time
Tests Runs (°C) (mole %) (mils/month)  (mils/hr)
Corrosion M 21-M 48  505-700 50 NaF—50 ZrF, > 1007 > 4.0%
teste C 9 15 500-650 48 NaF-—48 ZrF,—4 UF, 72 1.2 ,
E 3E 6 540—-660 48 NaF—49.5 ZrF,—2.5 UF, 45 0.8 3
L 1-L 4 560-710 54 NaF--4l1 7ZrF,—5 UF, T4 1.5 !
L 5L 9 540—700 52 NaF—45.5 ZrF,—2.5 UF, 27 0.7
Group I T 1-T 7 485-605 30 LiF-27 NaF—43 ZrF, llb O.5b
Group IT U 1-TU 7 490575 29 LiF—29 NaF—42 ZrF, + 40 1.1

0.3 wt % UC

 

aSpecimen was completely consumed.

b
Specimen was fluorine conditioned 3.2 hr at 600—645°C before test. All other
speclmens were in unconditioned state.

“Equivalent to 0.2 mole % U.
- 31 -

Effect of FPluorine Conditioning on L Nickel and INCO-61 Weld Metal

In Group II, one of the L nickel-INCO 61 specimens was fluorine
conditioned 3.2 hr at 600—645°C before corrosion testing. The conditioned
L nickel appeared to have sustained somewhat less attack than unconditioned
L nickel. On the other hand, conditioned INCO-61 weld metal exposed in
the vapor and salt regions exhibited greater attack than did unconditioned
INCO 6&1.

These observations are compatible with the theory thatl corrosion
resistance to fluorine is imparted by the formation oif a stable Iluoride
Tilm. The increased corrosion resistance ol the conditioned L nickel
presumably is due to the formation of a stable nickel Tluoride film. The
titanium present in INCO 61 possibly modifies and makes the NiF, ilm

less stable since titanium fluorides are highly volatile.

CONCLUSIONS

Several conclusions can be drawn based on the reported fluorination-
corrosion tests. These conclusions are in agreement with the previous
test series.

1. The combination of operating temperatures around 550°C with
lithium fluoride present in the salt baths produces about the same bulk
metal losses on nickel and nickel-base alloys as was found by operating
at 650°C without lithium in the salt baths.

2. 'The presence of uranium accelerates corrosion of nickel and
nickel-base alloys during the Volatility Process fluorination cycle.

3. Prior fluorine conditioning of L nickel decreases corrosion of
the material during subsequent fluorination.

4. Prior fluorine conditioning of INCO-61 weld metal increases the
attack on INCO 61 during subsequent Tluorination.

5. Bulk metal losses on L nickel and the nickel-binary alloys
containing manganese, iron, cobalt, or aluminum are about the same during

Tluorination at 550°C with lithium present in the fluoride salt baths.
- 32 -

6. The presence of the alloying elements, manganese, iron, or
aluminum, in nickel drastically reduces or eliminates intergranular attack
usually Tound in unalloyed nickel exposed to a fluorination environment.

7. In fluorination environments, the effect of adding cobalt to
nickel on subsequent corrosion by intergranular attack of trhe binary is
unclear. These reported tests showed that serious intergranular attack
of a 95 Ni—5 Co specimen occurred. On the other hand, this test series
and previocus series showed good resistance to this form of corrosion by
nickel containing 10 and 20 wt % Co.

8. Unalloyed nickel of greater than commercial purity shows less
resistance to bulk metal losses, intergranular attack, and grain-boundary
modifications when exposed to fluorination environments than L nickel

and all nickel alloys tested.

ACKNOWLEDGMENT

The authors wish to acknowledge the assistance given by L. A. Amburn,
Metallograpny Group, the X-Ray Difiraction Group, Metals and Ceramics
Division, and by personnel of the Analytical Chemistry Division,

Thanks are also due E. C. Moncrief, R. P. Milford, and others of the
Chemical Technology Division who alded in gathering process data or in
reviewing this report.

Special thanks are due D. A. Douglas, Jr., R. 3. Crouse, and
R. J. Gray for their constructive appraisal of this report, and to the
Metals and Ceramlics Division Reports Office and Graphic Arts Department

for preparation of the material for reproduction.
APPENDIX

Photomicrographs of metallographic sectlons taken from
Groups I and II, nickel and nickel-base, corrosion specimens
exposed in the Volatility Pilot Plant Mark ITI L nickel

Tluorinator.
- 34 -

UNCL ASSIFIED
Y-43351

{ o) VAPOR

UMCL ASSIFIED

NICKEL PLATE ¥-43353

(c) INTERFACE

UNCL ASSIFIED
Y-43354

NICKEL PLATE

.

 

(e) SALT

Fig. 13.

Volatility Pilot Plant Fluorinator Test Specimens.
right — as-etched with HNC3-CH3COOH-HCL.

 

 

 

 

007

NICKEL PLATE UNCLASSIFIED

¥-43352
001
- . L e
002
oy
o _
r
o
Z
005
006
007
008! () VAPOR
Gap e e o e g T 4SS CUNCLASSIEIED
NICKEL PLATE-* i Y-44714
002 ( ’
‘*Mwfigkflfiflwmemwfiwfidm%flwWf“* -
w #
o
|z \
008
006
oo7T
oos| {7} INTERFACE
S . UNCL ASSIFIED
oot | ANICKEL PLATE . Y-44715
o] o B , P 4

i3

 

 

 

008
ey

(F) SALT

Sections from L Nickel Specimen 51 from Group I,

Left — as-polished;
300%.
- 35 -

 

UNCL ASSIFIED
Y-43357 |

 
  
 

 

008

£07

{g) VAPOR

  
 

UNCLASSIFIED
Y-43355

  

 

(£) INTERFACE

NICKEL PLATE UNCLASSIFIED
Y“43356 L00i

UFY eran L SEMIMETALLIC g P T P
; 2 iy L M T e e i o

   
 

   
   

INCO ©f ‘

007

 

 

{c) SALT

Fig. l4. Sections from INCO-61 Weld Deposit of Specimen 51 from
Group I Volatility Pilot Plant Fluorinator Test Specimens. As-polished.
300X.
  
   
 

 

UNCL ASSIFIED
Y-43375

0086

07

{g) VAPOR

 

 

     

 

UNCLASSIFIED
Y-4335%
R |00t

() INTERFACE ]

 

 

   
 

B UNCLASSIFIED
_Y-43358

 

(¢) SALT

 

 

Fig. 15. Bections from High-Purity Nickel Specimen 39 from
Group I Volatility Pilot Plant Fluorinator Test Specimens. As-polished.
300X.
- 37 -

UNCL ASSIFIED
Y-43376

 
   
 

(g) VAPOR

 

 

! - » . * . UNCLASSIFIED [
, : +NICKEL PLATE . ¥-39320
‘ | - :‘ “f' ‘ : 220

< - |.o08

Lt0

 

. 011

 

 

 

01s

 

 

. -~ NICKEL PLATE o ¥-39319

o - W

 

 

 

 

(c) SALT

 

 

Fig., 16. Sections from 98 Ni—2 Mn Specimen 32 from Group I
Volatility Pilot Plant Fluorinator Test Specimens. (a) As-polished.
300X. (b) As-etched with HNO;-CH;COOH-HC1l. 250X. (c) As-etched
with HNO,-CH,COOH-HCL. 250X.
. 38 -

 

  
 

L UNCL ASSIFIED
Y-43363

 
 

L0

.006

007

UNCL ASSIFIED

NICKEL PLATE L ASSI

A T Py s I T It

 

(g} VAPOR

008

(p) VAPOR

 

UNCL ASSIFIED
Y+43364

UNCLASSIFIED

NICKEL PLATE L ASSIF

 

(¢) INTERFACE

  
 

UNCLASSIFIED
Y-43373

(e) SALT

 

006

e

 

 

  

UNCLASSIFIED
Y-44718

NICKEL PLATE

    

wn
| ¢
5 /
|z \\
S,
N /
Loos| N f}/
ol L[ -
~ .
oos| (F) SALT / -

 

Fig. 17.

Volatility Pilot Plant Fluorinator Test Specimens,
right — as-etched with HNO3-CH,COOH-HCL.

 

Sections from 95 Ni—5 Fe Specimen 24R from Group I

Left — as-polished;
300%.
- 39 -

  

UNCL ASSIFIED
Y-43365

{g) VAPOR

UNCL ASSIFIED
Y-43346

 
 

{¢) INTERFACE

  
 

BB UNCL ASSIFIED

(e} SALT

Flg. 18,

Volatility Pilot Plant Fluorinator Test Specimens,
right — as-etched with HNO3-CH3COOH-HCL.

   

 
 

 
 
 

 

Y-43367 |

 

 

 

D07

 

 

.008
e

 

UNCLASSIFIED

NICKEL PLATE Y-44719

   

008 () VAPOR

  
 

UNCL ASSIFIED
NICKEL PLATE Y-44720
LR Mgt age o i
| .002.
w
LD
x
[ &)
z
G008
008
007
008! () INTERFACE
UNCLASSIFIED

  

(F} SALT

Sections from 90 Ni—10 Fe Specimen 27 from Group I

Left — as~polished;
300%.
    
   

{a) VAPOR

(¢} INTERFACE

  
 

{e) SALT

Fig. 19.

 

. UNCLASSIFIED

NICKEL PLATE N

 

UNCLASSIFIED
Y.43370

 

 

ooz} " LN " T oY “C‘ v -~
LI T
om(6) VAPOR (¥ 3

F et SR T AR UNCL ASSIFIED
» NICKEL. PLATE Y y.44721

 

 

 

Q08
—

UNCLASSIFIED
Y-43369

 

.006

D07

 

17 Y

(o) INTERFACE -

 

    

 

 

Qo8
rmm—

Sections from 80 Ni—20

 
 

NICKEL PLATE

(£} SALT

Fe Specimen 29 from Group I

Volatility Pilot Plant Fluorinator Test Specimens. Left — as-polished;
right — as-etched with HNO3-CHsCOOH-HCL. 300X,
- 4] -

  
 

B UNCL ASSIFIED
Y-44644

  

{g) VAPOR

  
 

B UNCL ASSIFIED
Y~44646 B

  

(&) INTERFACE

UNCL ASSIFIED
Y-44648

 

(¢) SALT

Fig. 20. BSections from L Nickel Specimen 52 from Group II
Volatility Pilot Plant Fluorinator Test Specimens., As-polished.
300X.

008

O0T

.008

 

 

 

008

007

.co8

008

 

 
- 4D -

UMCIL.ASSIFIED
Y.44645

&

 
 

{g} VAPOR

UNCLASSIFIED
Y.44647
; v —

 
  

{p} INTERFACE

{ED

 

{c) SALT

Fig., 21. Sections from L Nickel Specimen 52 from Group II

£09

 

 

007

008

008

 

 

Volatility Pilot Plant Test Specimens. As-etched with 92HCLl:5H,804: 3HNO;.

300X,
 
 

UNCLASSIFIED
Y-44651

  

 

i % /‘ e fi\\ #
- e -
- : ’ ’ s ;
}' (\:? W n’:fi "t : w ‘»(‘
: M Cd .
(g) VAPOR
N T e S EEE AN 125?“ P AR Uy
B TR s T e R -, f L - o * & Loy oA 1* E‘ UNCL ASSIFIED
Bl S ead R NICKEL PLATE U “ B o T AR Ty 44653
- L o e 5. ST— e g g e e, gt R g WW% L e

 

{p) INTERFACE

 
 
 

&

(¢) SALT

Fig. 22.

Volatility Pilot Plant Fluorinator Test Specimens.
300X.

92HC1: 5H50,: 3HNOS.

*@ % UNCLASSIFIED
CLE Y-44656

Sections from L Nickel Specimen 55 from Group IT

As-etched with

007

.006

Q0T

.008

.006

007

008

 

 
 
 

IR UncUASSIFIED L
d  v.44641

   

 

(@) VAPOR 010

  
  

UNCL ASSIFIED
_ Y-44642

 

007

009

 

(H) INTERFACE

UNCLASSIFIED
Y-44643

 

07

008

£08

(¢) SALT

 

 

Fig. 23, Sections from INCO-61 Weld Deposits of Specimen 52 from
Group II Volatility Pilot Plant Fluorinator Test Specimens. As-polished.
300¥.
- 45 -

[ UNCLASSIFIED
Y- 44660

o
(=]
ra

 

INCHES

¥
L

o
<

003

0086

(g} VAPOR i : 008

UNCL ASSIFIED
Y-44662

 

oo v " e Lo 009

UNCLASSIFIED
Y-445665

0035

009

 

 

 

Fig. 24. Sections from 95 Ni—-5 Co Specimen 17 from Group IT
Volatility Pilot Plant Fluorinator Test Specimens. As-etched with
92HC1:5H,50,: 3HNO,. 300X,
- 4 -

UNCLASSIFIED
Y-44666

(g} VAPOR

UNCLASSIFIED
Y-44669

 
   

(6) INTERFACE

UNCL ASSIFIED
Y-44671

 
   
 

(¢) SALT

Fig. 25. Sections from 90 Ni—10 Co Specimen 21 from Croup IT
Volatility Pilot Plant Fluorinator Test Specimens. Vapor section is
as-polished. Interface and salt sections are as-etched with
92HCL: 5H,80,: 3HNO,.  300X.

 

.006

007

 

008
"

L09

 

.008

007

008

009

006

.007

08

 

 

 

man
- 47 -

UNCLASSIFIED
Y.44673

  
 

(@) VAPOR

UNCLASSIFIED
Y-44675

 
   
 

(b) INTERFACE

  
 

UNCL ASSIFIED
Y-444677

 
 

(¢} SALT

Mg, 26. 8ections from 99 Ni—1 Al Specimen 1R from Group II
Volatility Pilot Plant Fluorinagtor Test Specimens. As-etched with
92HCL: 5325@4: 3HNO3 . 300X,

 

008

007

008
fl—cey

008

gor

.00B

Kok

 

006

L0a7r

L8048
pr—

 

009
hod el

 

 
- 48 -

UNCIL_ASSIFIED

 

(o) VAPOR

UNCL ASSIFIED
Y-44682

———

 

(p) INTERFACE 1 o

  
 

UNCLASSIFIED
Y.44634

      

(¢) SALT

Fig. 27. Sections from 97 Ni-3 Al Specimen 5 from Group IT
Volatility Pilot Plant Fluorinator Test Specimens. As-etched with
92HCL: 5H80,: 3HNO,. 300X.

.006

007

 

008

0086

007

£08

008

L0t

L08

 

 
2=3.

o220,
21.
22.
23.

24—25.
26.
27.
28.
29,
30.
31.
32.
33.
34.
35.
36.
37.
38,
39.
40,
41,

43,
4bdi5,
47,
48.
49-51.,

- 49 -
DISTRIBUTION

Riology Library 52.
Central Research Library 53.
Reactor Divigion Library 5456,
ORNL — Y-1l2 Technical Library 57.

Document Reference Section 59,
Laboratory Records Department 59
Laboratory Records, ORNL R. C. 60.
ORNL Patent Office 6.
G. M. Adamson, dJr. 62
R. E. Blanco 63
J. C. Bresee 62,
B. 5. Borie 65
R. B. Briggs 66.
K. B. Brown 67
W, H. Carr 68.
G. I. Cathers 69.
R. 8. Crouse 70,
F. L. Culler 71
J. E. Cunningham 75_86 |
J. H. DeVan

D. A. Douglas, Jr. 87.
D. E. Ferguson
J. H Frye, Jr. 8.
H. E. Goeller 89,
C. E. Guthrie 90.
R. J. Gray 91 .
W. R. Grimes 90,
R. W. Horton 93,
M. R. Hill
FE. E. Hoffman

H. Tnouye

T. M. Kegley, Jr.

Lamb

Lindauer
Litman
Long, Jr.
MacPherson
Manly
McHargue
Milford

. Miller
Moncrief

Olsen

= 0 Q "oy g Q@ oot

. Patriarca
B. Ruch
H. Smiley
0. Smith
Taboada
C. Thurber
E. Whatley

S P 0P LT rEBE®QEEE D

=

Divigion of Technical
Information Extension (DTIE)

Research and Development
Division (ORO)

E. L. Anderson, AEC
Washington

0. E. Dwyer, BNL
5. Lawroski, ANL
P. D. Miller, BMI
J. W. Nehls, ORO

C. M. Slanksky
Phillips Petroleum
Company, Idaho Falls