CwmionSdmcc,1967, Vol. 7.p~. 39 to SO.PerpamonPrc*r Ltd.

Printui in Great Britain

THE ANODIC POLARIZATION BEHAVIOUR OF METALS

IN HYDROGEN FLUORIDE*
N. HACKERMAN
The University of Texas, Austin, Texas, U.S.A.
E. S. SNAVELY, Jr.j- and L. D. FIEL$
Tracer Inc., 6500 Tracer Lane, Austin, Texas, U.S.A.

Abetraet-The electrochemical behaviour of 23 materials as anodes in anhydrous hydrogen fluoride

(AI-IF) was investigated. These were grouped into three general classes according to their behaviour
in HF. Class I, high corrosion rate (Sb, Bi, Cd, MO, Ag, ZrB,, Ta, Tl, W. and pyrolytic carbon).
Class II, low corrosion rate with formation of a nonconducting film (Al, Cr. Co, Cu, Hastelloy-F,
Fe, Mg, Ti, Zn, and Zr), and Class III. low to moderate corrosion rate with a conducting surface
(Monel, Pt, and Ni). Class III materials represent the most promising group for use as anodes in HF.
Anodic dissolution rates on Class III materials were reduced by as much as 98 % by the addition of
trace amounts of water.
R&urn&On a etudie le comportement anodique de 23 metaux en presence d’acide fluorhydrique et
sur cette base, on les a classes en trois groupes: groupe I, haute corrodabilite (Sb, Bi,*Cd, MO, Ag
ZrB,, Ta. Tl, W, C pyrolytique); groupe II, faible corrodabilitt avec formation dune pellicule
non-conductrice (Al, Cr. Co, Cu. Hastelloy-F, Fe, Mg, Ti, Zn, Zr) et groupe III, corrodabilite faible
a mod&& avec une surface conductrice (Monel, Pt, Ni). Comme anodes dans HF. les metaux du,
groupe III sont les plus prometteurs. Des traces d’eau permettent d’en abaisser les vitesses de dis-
solution jusqu’il 98 %.
Zusammenfassung-Das elektrochemische Verhalten von 23 verschiedenen Anodenwerkstoffen in
wasserfreier FluDdure (AHF) wurde untersucht. Die Werkstoffe lieDen sich nach ihrem grundtitz-,
lichen Verhalten in 3 Gruppen einordnen: Gruppe 1: hohe Korrosionsgeschwindigkeit (Sb, Bi, Cd.
MO, Ag, ZrB1. Ta, Tl, W und pyrolytischer Kohlenstoff); Gruppe 2: geringe Korrosionsgeschwindig-
keit und Bildung eines nichtleitenden Films (Al, Cr, Co, Cu, Hastelloy F, Fe, Mg, Ti, Zn und Zr);
Gruppe 3: niedrige bis mlBige Korrosionsgeschwindigkeit bei guter Oberfllchenleitfiihigkeit
(Monel, Pt und Ni). Die Werkstoffe der Gruppe 3 scheinen als Anoden fur die Verwendung in
FluDsiiure besonders gee&net. Ihre anodische Aufldsungsgeschwindigkeit wird bis auf 2% des
Ausgangswertes vermindert, wenn Spuren von Wasser xugegen sind.
Pe@epZlT - ~CCJIeAOBaKO 'NIeHTPOXWMB'leCKOe nOBeAeHHe 23 BeqeCTB, HCIlOJIbElOBaHHbIX B
Kasecrse anonon, B 6eaBogHOM @T~~HCTOM nogopoge. ~TH semecrsa crpynnaposaiiar a rpn
OCHOBAble KJIWCa COrJIaCHO SIX IIOBeAeHHIo B HF. %IaCC 1 - BbICOKaR CKOPOCTb KOppOaHE
(SB, Bi, Cd, MO, Ag, ZnBa, Ta, Tl, W H nwponwrwrecmrg ymepon), unacc II - HW~KU
CKOPOCTb KOppO%iH C 06paaOBaHS¶eM HeIIpOBOAHQeft IlJIeHKK (Al,Cr,Co, Ctt,XaCTeJIJlOg -
F,Fe,Mg,Ti,Zn H zr) H KnaCC III- OT HHaKOi A0 CpeJJHei CKOpOCTH KOppOaHH C o6paao-
BaHHeM npOBOAX~etf UOBepXHOCTH (MoKenb, Pt H Hi). BemeCTBa 111 KJIaCCa RBJIRH)TCR
Haw6onee IIePCIleKTABHbIMA ~nii HCIIOJIbi3OBaHHfi HX B KaYeCTBe ~OAOB B HF. CKOPOCTH
~O~HO~O~aCTBO~eHAR:Be~eCTB~~~K~aCCaCHHHc~HCbH~98o/~~~ll~O6~~eHIiHC~eAOBBOAhI.

INTRODUCTION
THWE are several reasonably inert electrodes (e.g. Pt, Hg) available for use as anodes
in aqueous systems in the study of electrochemical reactions and electrode kinetics;
l Manuscript received 20 May 1966.
t Present address: Field Research Laboratory, Mobil Oil Corporation, Dallas, Texas.
$ Present address: Department of Physics, Colorado State College, Greeley, Colorado.
39
40 N. HACKERMAN, E. S. SNAVELY, Jr. and L. D. FIEL

however, no such electrode has been found for use in anhydrous hydrogen fluoride
(AHF) due to its extremely corrosive action on most materials.
Considerable work has been devoted to determination of the reactions of metals
with fluorine, HF, and aqueoussolutions of, HF becauseof the commercial importance
of these chemicals. From this work has evolved methods of passivating common
materials for construction for safe handling of HF and its aqueous so1utions.l
Electrodes for usein liquid HF, however, must be corrosion resistant under impressed
anodic bias and must remain electrically conductive. Conventional meansof passivating
metals, viz. exposure to gaseousfluorine, may result in the formation of a film having
a high electrical resistance.
Most cells for the electrochemical fluorination of organic compounds have
employed anodesof nickel, platinum, or carbon. 2 Simons proposed that copper, iron,
Monel metal, silicon carbide, and carbon may also be suitable anodes314All of the
foregoing materials have been usedas cathodes in HF although nickel and iron are the
most common. Numerous other studiescould be cited, but those of Nagae, et a1.j are
particularly pertinent here. For the electrochemical fluorination of propyl propionate,
they observed that the reaction proceeded smoothly with nickel and Monel electrodes;
however, high electrical resistanceor absenceoffluorination occurred when aluminium,
iron, cobalt, copper, zinc, silver, or lead anodes were used. Some fluorination. was
observed with stainlesssteel anodes, but corrosion rates were high.
In summation, an abundance of work has been performed on electrochemical
fluorinations in HF; however, little is known about the behaviour of electrode
materials because early handling methods allowed contamination of the HF, a
reference electrode was usually not employed, and only gross observations were made
on the reactions of the electrode materials. The effects of contamination are illustrated
by Donahue and Nevitt,6 who observed a high corrosion rate of nickel anodesin AHF
and a relatively low rate in HF containing 0.5 mole % water.
The purpose of this work was to observe the electrochemical behaviour of various
anode materials in high purity AHF under closely controlled conditions.

EXPERIMENTAL
The system developed for handling and storing the HF and the electrolytic cells
usedin this work have been previously discussed.‘,* All materials that contacted liquid
HF were Teflon or Kel-F. Other parts of the systemwere of Teflon or Monel.
The HF was prepared by a distillation and electrolysis procedure similar to that of
Rogers, Johnson, and Evans9and has beendescribed in detail elsewhere.7Conductivity
of the HF prepared in this manner was usually lO-5 Q-‘cm-l. The water concentration
was estimated from an empirical relation given by Ukaji and Kageyawa.‘O
The electrodes were in the form of 0.125 in. rods, except for pyrolytic carbon
(discussedbelow), thallium (0.063 in. wire), and platinum (0.050 in. wire). The samples
were prepared by mechanical sandingand buffing to a smooth surface if possible.Some
materials (e.g. thallium) were chemically cleaned to remove oxides. After treatment the
sampleswere rinsed in water and in benzene, and then dried under vacuum; they were
stored in a vacuum desiccator until needed.
The reference electrode used was the Hg/Hg,Fz electrode. Early work on this
 The anodic polarization behaviour of metals in hydrogen fluoride 41

electrode was reported by Koerber and DeVries; l1 details of construction and per-
formance have been discussedpreviously.7,1Z
All solutions usedwere AHF + 0.01 M NaF and all potentials were vs. Hg/Hg,F,
at - 20°C unlessotherwise specified.

RESULTS
The 23 materials investigated were grouped into three general classesaccording
to their anodic behaviour in HF as shown in Table 1.

TABLE 1. BEHAVIOUR OF VARIOUS MATERIALS AS ANODES IN HF

Class I Class 11 Class III

Rapid corrosion Low corrosion Passive
Antimony Aluminium Monel
Bismuth Chromium Platinum
Cadmium Cobalt Nickel
Molybdenum C%wer
Silver Hastelloy-F
Zirconium
diboride Iron
Thallium Magnesium
Tungsten Titanium
Pyrolytic carbon Zinc
Tantalum Zirconium

ClassI
Materials which exhibited very high dissolution rates in AHF at open circuit and/or
anodic bias are listed under ClassI in Table 1. The dissolution rates of thesematerials
in AHF are sufficiently high that they are probably uselessfor use as anodes. The
polarization curves are typical for active electrodes, viz. high currents at low anodic
bias. A typical polarization curve is shown in Fig. 1. Little evidence of protective film
formation is observed as the polarization curves are reproducible and the current for
anode dissolution does not decrease with time at constant applied potential. The
anodic polarization curves do not show evidence of appreciable fluorine evolution and
current efficienciesfor electrode dissolution are near 100 per cent even above 2.62 V,’
the fluorine evolution potential.
No correlation between electrode activity and solubility of the metal fluoride was
observed. For example, as shown in Table 2, the solubilities of ClassI materials range
from very low values (0.01 g/100 g for BiF,) to extremely high solubilities (305 g/100 g
for TlF), although dissolution rates roughly within the sameorder of magnitude are
observed. Confirmation of the oxidation state of the dissolved materials were obtained
by calculations of the current efficiencies for anodic dissolution. Attempts were made
to passivate thallium by the formation of slightly soluble TlF,; however, these were
unsuccessful.Thallium electrodes dissolved at extremely high rates even when inserted
in AHF under anodic bias of + 6.0 V or after impressing an anodic potential of
+ 6.0 V on an electrode corroding at open circuit.
Corrosion products accumulate on the surface of Class I materials which form
slightly soluble fluorides; however, theseare non-protective. For example, the corrosion
 N. IIACKERMAN, E. S. SNAVSLY, Jr. and L. D. Fn%

X-INITIAL RUN
O-2ND RUN
(30 MIN LATER)
-

POTENTIAL, VOLTS VS. WHg2F2

Fm. 1. Polarization curves for cadmium in AI-IF + 0,012 M NaF.

rate of cadmium at open circuit was observed to be essentially constant over a period
of 16 h, although a film of CdF, covered the specimens. As shown in Fig. 2, cadmium
specimens were coated with about 3 mg/cma of fluoride which caused no significant
stifling of the corrosion reaction. The fluoride was so loosely bound to the electrode
that some of the coating was lost in handling the electrode.
Pyrolytic carbon is an exception in the Class I materials in that it is inert to AHF
at open circuits but electrodes disintegrated under an anodic bias of 6.0 V. It is
possible that the damage was physical rather than chemical or electrochemical. The
pyrolytic carbon electrolytes were prepared by moulding discs of the material in
 The anodic polarization behaviour of metals in hydrogen fluoride 43

Fm. 2. Weight changes of cadmium in AHF at open circuit.

TABLE 2. DATA ON CLASS I MATERIALS AT - 24 j, 1°C

Solubility of metal Weight loss rate at Weight loss rate

Metal fluoride in AHF* anodic bias at open circuit
Metal fluoride cg/l~ g AI-IF) (mg cm-’ h-t) (mg cm-* h-l)

Exptl. Calc.
Sb SbF, 0.191 * 0~003 11.63$ 10.15 -
Bi BiF, 0.010 f 0.003 24.65 21.0 -
Cd CdF, 0.189 * Occ)l 76.57 62.5 0.3
MO MoF, O*OlSt 15.1 II 14.8 0.01
Ag A@ 27.2 & 0.7 - -
- 6.6
Ag AgFI 0.024 f 0.001 -
Ta TaF, - l . - -
Tl TlF 305 f 15 - -
- - 61.0
Tl -l-m 0.027 h OXI03
W m, - - 1836.0 -
ZrB, - - 0.969 1.80 -

*See Reference 13. 12.0 V vs. IQ/H&F,.

tCalculated value (see Ref. 7). 111.0 mA applied current.
$2.0 v vs. Ft. **Dissolved completely during polarization.
puring polarization.
44 N. HACKERMAN~ E. S. SNAVELY, Jr. and L. D. FIEL

Kel-F so that only one face of the lamella was exposed. Catastrophic failure of the
electrodes may have been due to the build-up of fluorine gas within the carbon.

ClassII
Materials in Class II are highly resistant to attack by AHF at open circuit and
under anodic bias. These materials exhibit anodic polarization behaviour analogousto
aluminium and titanium in dilute aqueous solutions, viz. high resistance to the
passageof electric current due to the formation of non-conductive protective oxidation
products. The polarization curves for iron (Fig. 3) are typical of the group. The anodic
current is controlled by impedance of the fluoride film as shown by comparison of
anodic polarization curves for iron in high-resistivity AHF and in conductive solutions
of NaHF, in AHF.
All the known solubilities of fluorides of Class II materials are low as shown in
Table 3. The dissolution rate for aluminium, 0.02 mg cm-2 h-l at 6.0 V, is not a steady-
state value but is the average rate measured after anodic polarization for 4.0 h.
Presumably, the anodic dissolution rate of aluminium would fall to a negligible value
on continued polarization in a manner similar to the behaviour of aluminium at open
circuit as shown in Fig. 4. This behaviour is analogous to anodic polarization of
titanium in aqueous systemswhere film thickness is proportional to applied voltage
up to the breakdown voltage. Evidence of fluorine evolution is observed on the

X AHF ONLY

I !-
A CPOIM HF2 -

2 4 6 8 IO
POTENTIAL, VOLTS VS. Hg / Hg;! F2

FIG. 3. Polarization curves for iron in AHF.

 The anodic polarization behaviour of metals in hydrogen fluoride 45

TABLE 3. DATA ON CLASS II MATERIALS AT -24 + 1°C

Solubility of metal Weight loss rate at

Metal fluoride in AHF* anodic bias
Metal fluoride k/l~ g AHF) (mg cm-* h-l)
Exptl. Calc.
Al MF3 I 0.004 0.02-f -
Cr CrF, - 0.17$ -
co CoF, 0.040 * 0.003 - -
co CoF, 0.272 + 0.016 0.05-$: 0.02
cu CuFz 0.010 * 0.004 0.131 -
Hastelloy-F - - Negligible
Fe FeF, 0~005 f 0.002 - -
Fe FeF, I 0.001 0.06t 0.07
Mg MS - 0.04$ < 0.01
Ti TiF, - - -
Ti TiF, - 0.07$ 0.05
Zn ZnF, 0.016 5 0.002 0.07g -
Zr ZrF, 0.023 * OX)02 0.487 0.20

*See Reference 13.

t5.0 V vs. Hg/Hg,&. 94.0 V vs. Hg/Hg,F,.
*During polarization. 7 10.0 V vs. Hg/H&F*.

polarization curves of Class II materials as shown by the inflection at 2.2 Y for iron
in Fig. 3. However, the limiting current for fluorine evolution was small in all cases.
Direct evidence of fluorine evolution was not obtained from calculations of anodic
current efficiencies for dissolution as the observed weight loss was usually higher

FIG. 4. Weight of 6lmed and de-filmed aluminium electrodes in AI-IF.

46 N. HACKERMAN, E. S. SNAVELY, Jr. and L. D. FIEL

than the loss calculated from the anodic current passed as shown in Table 3. This
discrepancy is presumably due to an open-circuit or rapid initial film-forming reaction
which accounts for a larger fraction of the total weight loss observed. For example,
aluminium at open circuit reaches a steady-state weight loss in 2 h as shown in Fig. 4.
Of a total weight loss of 90 pg/cm2 after 40 h, 74 pg/cm2 remained on the electrode as
AlF, to form a film 0.800 lo thick. Only 16 pg/cm2 of aluminium or 18 per cent of the
total weight loss was lost to solution in AHF.

ClassZZZ
Materials which resisted attack by HF and from which fluorine could be evolved
at high rates under anodic bias are grouped in Class III. This group is analogous to
those materials which exhibit passive behaviour in aqueous systems, i.e. anodic
treatment forms protective surfaces which remain electrically conductive. The analogy

POTENTIAL, VOLTS VS. Hg/HgZF2

FIG.5. Initial polarization curve for nickel in AHF + 0.01 M NaF.

 The anodic polarization behaviour of metals in hydrogen fluoride 47

TABLE 4. CURRENT EFFICIENCYFOR ANODE DISWLUTION

Current efficiency for Open circuit

Potential anodic dissolution weight loss
Metal U-W-W3 (per cent) (mg cm-* h-l)

Monel 8.0 V 3.6* 0.22

Platinum 5.0 v 14.3t 0.33
Nickel 6.0 V 75.6$ 0.05

*Assuming formation of NiF, and CuF,.

tAssuming formation of PtF,.
jAssuming formation of NiF,.

may not be strictly true in every aspect since the mechanism of conduction through
the conductive surface of materials in AHF is not known.
Polarization curves of this group are characterized by high polarizability below
2-O V and rapid increase in current above 2.0 V due to fluorine evolution. The polariza-
tion curve for nickel shown in Fig. 5 is typical of the Class III metals. The dissolution
rate of these materials at the 5uorine evolution potential in AHF is high compared to
rates observed for passive anodes in aqueous systems. Monel is the most resistant of
this group to anodic dissolution as shown in Table 4. Above the fluorine evolution
potential the current efficiency for anodic dissolution is 3.6 per cent for Monel,
14.3 per cent for platinum, and 75.6 per cent for nickel. Inspection of Fig. 5 shows that
anodic dissolution of nickel does not reach a limiting value at 2-O V but increases
markedly with fluorine evolution.
Pure AHF is more aggressive toward Monel and nickel than AHF contaminated

40

-. ____-.-- -------- -- --
.A. ._._ ._.-.-. -o.-----*-
__. L.
0
I50 200 CEUZ, 300 330 400 450 ! 0
ANWIC couu~

FE. 6. wei& lOSSeS of nickel in HF + 0.01 M NaF + H,O at + 6.0 V.

48 N. HACKERMAN, E. S. SNAVELY, Jr. and L. D. FIEL

with traces of water. Trace amounts of water inhibited anodic dissolution of nickel by
98 per cent and imparts a marked passive electrochemical behaviour to nickel
electrodes. This effect was reported previously6 and was studied extensively in this
laboratory.14 The rates of dissolution of nickel in AHF and in AHF containing
0.01 % and 0.10% H,O are given in Fig. 6. The weight loss in AHF increases linearly
with time at 6.0 V; however, the addition of 0.01 y0 water decreases the rate of dis-
solution by an order of magnitude. The inhibiting effect of H,O is apparently maximum
at a concentration of O.lO’? as concentrations greater than this appeared to have no
further beneficial effects. It is quite likely that the utility of nickel electrodes in AHF
can be increased greatly by the addition of small amounts of H,O.
Class III materials represent the most useful electrodes for AHF processes such as
electrochemical fluorinations. Of these Monel is the most resistant to anodic dissolution,
and this may be decreased even further through use of the inhibiting effect of H,O.

DISCUSSION
Anode materials grouped in Classes T and II are unsatisfactory for use in AHF
since they corrode rapidly under anodic bias or form a non-conducting film. Materials
in Class 111 are capable of fluorine evolution upon polarization even though some
corrosion occurs; the extent of the corrosion depends on electrolyte composition.
Therefore, these electrodes could be used as anodes in HF since they will sustain an
electrochemical reaction other than corrosion. Even though the Class II metals form
non-conductive films, they represent a potentially useful class of electrode materials
if means could be found to render the films conductive, e.g. by “doping” with a
charge carrying impurity such as arsenic.
Examination of Tables 2 and 3 shows no apparent correlation between electrode
reactivity and solubility of the respective metal fluorides. The two metals having the
most soluble fluorides13 (silver and thallium) of the metals studied are in Class I;
however, other Class I materials, as well as those in Class III, have solubilities of the
same magnitude as those in Class IT. This lack of correlation was also noticed by
Meutterties and CastleI in their studies of metals and metalloids in HF. Low fluoride
solubility is a necessary but not sufficient criterion for the utility of anode materials in
AHF. The fluorides must also be conductive and protect the substrate metal.
Pilling and Bedworth rulel’ calculations were made on all metal/metal fluoride
systems for which data were available. These results are tabulated in Table 5. All ratios
of the fluoride volume-to-metal volume (R) are greater than unity, indicating at least
complete coverage of the metal by its respective fluoride.
No correlation between reactivity and R is evident. It should be noted that a strict
correspondence to this rule could not be expected since the electrodes were in the
form of rods or wires with convex surfaces. This requires that the fluoride volume be
greater than the value of reacted metal for minimum coverage; however, the values of
R % 1, e.g. 2.5 to 3.0, which were obtained indicate that the fluoride films were under
high compression stresses which would tend to buckle the film and destroy its pro-
tective character. This effect was observed for nickel in AHF during experiments in
which the electrode was under anodic bias for long periods of time. In these experi-
ments the anodic current exhibited sudden increases, perhaps doubling in magnitude,
followed by a slow decrease. This is attributed to spalling of the NiF, film from the
 The anodic polarization behaviour of metals in hydrogen fluoride 49

TABLE 5. RATIO OF VOLUME OF METAL FLUORIDE TO VOLUME OF METAL

Class Metal Metal fluoride R

Sb SbF3 2.2
Sb SbF, 4.0
Bi BiF, 2.3
Cd CdFI 1.7
& AgF 2.1
Ta TaF, 5.4
TI TlF 1.57
II Al AIF, 2.9
II Cr CrF, 3.0
II Cr CrF, 3.9
II co CoF, 3.3
II co CoF, 4.5
II CU CuF, 3.4
II Fe FeF, 3.3
II Fe FeF, 5.7
II Mg MgF, 1.5
II Ti TiF3 2.9
II Ti TiFI 4.2
II Zn ZnFz 2.4
II Zr ZrF, 2.7
III Ni NiFz 3.2

nickel due to compressional stresses.Other metals having high ratios might exhibit
similar behaviour if held under anodic bias for long enough periods. The ratio R
appears to have no value in predicting behaviour in AHF since the samerange of
values of R are observed for all three classesof material. All of the metals in Class111
are transition elements or are composed of transition elements; however, not all
transition elementsare in this class.Generally, the metals having a high atomic number
(2) are in Class I and the metals with a low Z are in Class II. However, no definite
criteria for predicting the behaviour of a metal in AHF could be established.
ClassI metals (Table 1) are useful for the preparation of pure metal fluorides since
the dissolution rate of these materials is increased many times by impressedanodic
current. Class II metals are useful as materials of construction for handling AHF
or solutions in AHF. Class111metals are sufficiently inert and conductive to be used
for electrochemical anodes and/or materials of construction.
Ackno,v[erlge~nents-This work was supported in part by the United States Navy, Office of Naval
Research, under Contract Nonr-4054(00) with TRACOR, Inc., Austin, Texas. The authors also wish
to express appreciation to R. M. Hurd, L. G. Spears, and W. E. Harrell, Jr., for contributions to this
project. One of the authors (N.H.) takes this opportunity to express his thanks to The Robert A.
Welch Foundation, Houston, Texas, and to the Office of Naval Research for their support of the
work in his laboratory which led in part to this work.

REFERENCES
1. R. LANDAU and R. ROSEN, Id. Engng Chem. 37, 281 (1947).
2. M. STACEY, J. C. TATLOW and A. SHARPE, Adv. Fluor. Chem. 1, 133 (1960).
3. J. H:SIMONS, Fluorine Chemistry, Vol. 1, p. 225. Academic Press, New York (1950).
4. J. H. SIMONS, Fluorine Chemistry, Vol. 1, p. 414. Academic Press, New York (1950).
5. S. NAGAE, H. BABA and R. KOJIMA, Kogyo Kagaku 66 (9), 1287 (1963).
D
50 N. HACKERMAN, E. S. SNAVELY, Jr. and L. D. FUEL

6. J. A. DONOHUE and T. D. Nsvrrr, Oxygen-fluorine bond formation in electrolysis of wet

hydrogen fluoride, ARPA Propellant Contractors Synthesis Conference. IIT Research Institute,
Chicago, Illinois, 13-15 April 1964.
7. L. D. FIEL, Ph.D. Dissertation. The University of Texas (1966).
8. E. S. SNAVELY, JR., L. D. FIEL and N. HACKERMAN, Anodic polarization behaviour of some
metals in hydrogen fluoride. Third Int. Symp. Fluorine Chemistry. Munich, Germany, 30 August-
3 September 1965.
9. H. H. Rooms, S. EVANS and J. H. JOHNSON,J. electrochem. Sot. 111, 701 (1964).
10. R. UKAJI and I. KAGAYAMA, Bunseki Kagaku 9,604 (1960).
11. G. G. KOERBER and T. DEVFSES.J. Am. them. Sot. 74. 5008 (1952).
12. R. M. Huan and E. S. SNAV~LY, JR., Metal and metal/metal ‘fluoride electrode systems in
anhydrous hydrogen fluoride, ARPA Propellant Contractors Synthesis Conf. IIT Research
Institute, Chicago, Illinois, 13-15 April 1964.
13. A. W. JACHE and G. H. CADY, J. phys. Chem. 56, 1105 (1952).
14. L. D. FIEL, N. HACKERMAN, E. S. SNAVELY, JR., Anodic passivity of nickel in hydrogen fluoride.
(To be published.)
15. E. L. MEUT~ERT~E~ and J. E. CASTLE, J. inorg. nucl. Chem. 18, 148 (1961).
16. N. B. PILLING and R. E. BEDWOR~H, J. Inst. Metals 29, 534 (1923).