Reference

NBS

PUBLICATIONS

NBSIR 85-3282

AlllDk 0 3 1 k M 3

Survey of Alternate Stored

Chemical Energy Reactions

L. P. Cook

E. R. Plante

U.S. DEPARTMENT OF COMMERCE

National Bureau of Standards

Institute for Materials Science and Engineering

Ceramics Division

Gaithersburg, MD 20899

December 1985

Prepared for: Department of the Navy

~*fice of Naval Research

-QC- lington, VA 22217

100

NBSIR 85-3282

SURVEY OF ALTERNATE STORED

CHEMICAL ENERGY REACTIONS

L. P. Cook

E. R. Plante

U S. DEPARTMENT OF COMMERCE

National Bureau of Standards

Institute for Materials Science and Engineering

Ceramics Division

Gaithersburg, MD 20899

December 1985

Prepared for: Department of the Navy

Office of Naval Research

Arlington, VA 22217

U.S. DEPARTMENT OF COMMERCE, Malcolm Baldrige. Secretary

NATIONAL BUREAU OF STANDARDS. Ernest Ambler. Director

Survey of Alternate Stored Chemical Energy Reactions

Annual Report

For the Period May 25, 1984 May 25, 1985

L. P. Cook and E. R. Plante

Inorganic Materials Division

Institute for Materials Science and Engineering

National Bureau of Standards

Gaithersburg, MD 20899

September 15, 1985

Prepared for the Department of the Navy

Office of Naval Research

Arlington, VA 22217

APPROVED FOR PUBLIC RELEASE: DISTRIBUTION UNLIMITED

Under Contract Nos. N00014-83-F-0117 and N0014-84-F-0204

REPRODUCTION IN WHOLE OR IN PART IS PERMITTED FOR ANY PURPOSE OF THE

U. S. GOVERNMENT
-2 -

Survey of Alternate Stored Chemical Energy Reactions

Table of Contents

Page

Abstract 5

I. Introduction 6

II. Li/H

2 0; H2 /0

2 8

A. Starting Materials and Container Materials 8

B. Reaction Products 9

C. Kinetics 9

D. Enthalpy 10

E. Safety Considerations 11

III. Li/H

2 0; Na0

2 /H2 0; H

2 /02

11

A. Starting Materials 11

B. Reaction Products 12

C. Kinetics 12

D. Enthalpy 13

E. Safety Considerations 14

IV. MgAl/H

2 0; H

2 /0

2 14

A. Starting Materials 14

B. Reaction Products 15

C. Kinetics 15

D. Enthalpy 15

E. Safety Considerations 16
-3 -

V. LiAl/Cl0

3

F 17

A. Starting Materials 17

B. Reaction Products 18

C. Mass Spectrometry 19

i) Outline of Method 19

ii) Vaporization Considerations 20

iii) Experimental set-up 20

iv) Analysis of OlO^F 20

v) Reaction of Li-Al Alloy with ClO^F 21

vi) Al-CIO^F Interaction 22

D. Kinetics 23

E. Enthalpy 24

F. Safety Considerations ( 7 ) 25

VI. LiAlMg/C10

3

F 26

A. Enthalpy 26

B. Safety Considerations

VII. LiBe/C10

3

F 27

A. Enthalpy 27

B. Safety Considerations

VIII. Li/^^o

A. Starting Materials

B. Enthalpy

C. Safety Considerations 29
-4-

IX. LiB/NF

3 29

A. Starting Materials * 29

B. Enthalpy 29a

C. Safety Considerations 29a

X. Summary and Discussion 30

XI. Needs for Future Research 32

XII. References Cited 34

XIII. Appendix. Results of Literature Survey 35

XIV. Tables 63

XV. Figures 80

XVI. Distribution 103
-5-

Abs tract

A survey of eight alternative liquid metal stored chemical energy

reactions has been made for purposes of comparison with the lithiumaluminum/water, lithium/sulfur hexafluoride, and other reaction schemes.

The objective of the study was to survey the potential of these eight

reactions as alternate stored chemical energy systems and to develop

priorities for future study. Experimental data on the products of

reaction and kinetics of reaction are presented for: Li/t^O; H

2 /02 ),

(Li/H

2 0; Na02 /H2 0; H

2 /0

2 ), (MgAl/H2 0; H

2 /02

), and LiAl/CKXjF) . These

data have been collected using thermogravimetry and Knudsen effusion

mass spectrometry, with x-ray diffraction analysis of experimental

products. Among other results, the data show that the aluminum component of the fuels is relatively inert to oxidation up to 650 °C. Above

this temperature, materials limitations have hampered the collection of

experimental data.

Thermodynamic analysis has been used to extend the data on each of

the eight reaction schemes, and to predict the chemical reaction which

best represents the complete oxidation of each fuel by the indicated

oxidant at 1100 K. Enthalpies have been calculated for each fuel /oxidant combination. Safety considerations are also discussed for each.

Suggestions for future research are given, including suggestions for

overcoming the materials problems encountered in this study.
- 6-

I. Introduction

Recently there has been much interest in the use of light metals as

fuel for stored chemical energy devices. A system currently in usage

involves molten lithium metal and sulfur hexafluoride, according to the

reaction.

8Li + SF, -> Li0 S + 6LiF

6 2

[ 1 ]

Under development (1) is a system using lithium aluminum alloy as the

fuel and water as the oxidant, according to the reaction:

LiAl + 2H

2 0 -+ LiA102 + 2H

2 [2a]

The hydrogen liberated is combined with oxygen to yield water:

2H

2 + °2 H2° [2b]

The water produced in this way is returned to [2a] to complete the

cycle. In our laboratories investigation is continuing of reaction [2a],

which is potentially much more complex than as written (2).

In addition to reaction [2], there are other possible alternate

systems of interest and it is desirable to make a preliminary survey of

these, to determine if certain ones might emerge as clear choices for

further development, or at the least, if others might be eliminated from

further consideration. The fuel/oxidant combinations that have been

suggested are:
-7-

Li/H

2 0; H2 /0

2 [3]

Li/H

2 0; Na0

2 /H2 0; H

2 /02

MgAl/H

2 0; H2 /02

LiAl/C10

3

F

LiAlMg/C10

3 F

LiBe/C10

3

F

Ll/C

11

F

20

LiB/NF,

[ 4 ]

[5]

[ 6 ]

[7]

[ 8 ]

[9]

[ 10 ]

Combinations [3], [4], and [5] utilize a final stage of combustion in

which hydrogen is burned, in a reaction identical to reaction [2b]

above. Combinations [6] through [10], however, are envisioned as largely

single-stage energy release schemes. To fully evaluate all these candidates

it is desirable to have the following basic information:

(a) identity of the products of fuel/oxidant reaction

(b) an indication of the kinetics, especially the minimum temperature required for spontaneous combustion and self-sustaining

reaction

(c) an estimate of the enthalpy of reaction

(d) knowledge of toxicity of reaction products

Information collected to date for each of the fuel/oxidant combinations

is summarized in the paragraphs that follow. Most experiments were com-
- 8-

pleted using a Mettler 1 thermoanalysis system, except for reaction [6],

which was also investigated mass spectrometrically . Following a presentation of data for each of the above reaction schemes, a general discussion

and recommendations for follow-up research are given. Results of a

literature search are given in an Appendix (Section XIII).

II. Li/H

2 0; H

2 /0

2

A. Starting Materials and Container Materials

The starting material used for these experiments was finely powdered

lithium metal (-140 mesh, 99.95% pure on a metal basis). This material

had some surface oxidation upon receipt from the vendor, causing it to

have a slightly grayish cast; the contaminants were tentatively identified

as lithium carbide (Li

2 C2 ), lithium hydride, and lithium hydroxide, on

the basis of weak x-ray diffraction peaks. All materials handling

operations involving the lithium metal were completed in a glove box.

Quantitative study of the oxidation of metallic lithium poses

special materials problems. Any container must be capable of withstanding attack by both metallic lithium and the oxidant. Silica glass is

not a suitable container in the presence of both the lithium fuel and

the water oxidant. Graphite and molybdenum are mentioned in the literature (3, 4) as container materials for lithium alloys; however both are

attacked by oxidants at relatively low temperatures. A nickel-based

alloy would appear to offer promise; however, nickel could

l Certain commercial equipment, instruments, or materials are identified

in this paper in order to adequately specify the experimental procedure.

Such identification does not imply recommendation or endorsement by the

National Bureau of Standards, nor does it imply that the materials or equipment identified are necessarily the best available for the purpose.
-9-

be expected to undergo a certain degree of oxidation even at relatively

low temperatures, affecting the results of sensitive thermogravimetric

experiments, and possibly contaminating the sample. BN is a possible

material, but experiments with LiAl (see below) suggest lithium abosrption. Perhaps the strongest candidate crucible materials for future

work are BeO (5) and MgO; however, as these were not available, all

measurements to date were completed using readily available alumina

crucibles at temperatures below the melting point of lithium metal.

B . Reaction Products

Lithium metal was reacted with water-saturated flowing argon

(30,000 ppm H

2 O) in the thermoanalyzer. At 25 °C, slow reaction of

lithium metal with water produces LiOH.I^O. However the reaction probably proceeds sequentially, starting with LiOH, as evidenced by x-ray

analysis of samples from different zones within the reaction cell. Near

the bottom of the cell, products were largely LiOH; near the top, the

hydrate was dominant. At 100 °C, the reaction product is almost entirely

LiOH; small amounts of the hydrate are believed to have formed as the

experiment cooled.

C. Kinetics

The finely powdered lithium metal used in these expeiments is

highly reactive at room temperature in spite of the thin surface coating.

This is evidenced by rapid reaction when deliberately exposed to the

atmosphere. When placed in contact with water, violent reaction ensues,

and explosion occurs due to spontaneous ignition of the evolved hydrogen.
- 10-

In the thermoanalyzer experiments, the reaction was purposefully

set up to proceed in controlled fashion. Reaction curves at 25 and

100 °C are shown in Fig. 1. The 25 °C curve shows a nearly linear segment from 0 to 1500 min. of reaction time, implying that reaction control in the early stages is not associated with build-up of a product

layer, but rather may be linked to the rate of supply of the water

vapor. The second half of the 25 °C curve is nonlinear. This could be

due to the influence of the product layer of LiOH.l^O, but is more

likely to be due to the increased diffusion path required for vapor to

reach the powders in the bottom of the cell. The reaction was stopped

prior to completion. Theoretically completion would have occurred at a

fractional weight gain of 5.1 (compared with 3.7 at the termination of

the experiment). This number assumes complete conversion to LiCOlQ.l^OBy contrast, at 100 °C, the entire curve appears to be nonlinear.

This suggests influence of the product layer (in this case LiOH) . The

reaction appears to have terminated in spite of the fact that the theoretical fractional weight gain of 2.5 was not reached. This probably

indicates that the surface contamination of the Li powdered starting

material is more severe than the x-ray analysis suggested. Future

experiments will employ a much more nearly pure lithium powder.

D. Enthalpy

Thermodynamic data for calculation of the enthalpy of oxidation of

molten lithium metal by ^0 are available in the JANAF tables (6).

Enthalpy production in kcal per gram of fuel plus oxidant can be calculated, if the lithium oxidation reaction is combined with burning of

the evolved hydrogen and recycling of water thus produced:
- 11 -

Li + H

2 0 -> LiOH + (1/2)H2

[ 11 ]

(1/2)H

2 + (l/4)0

2 > (1/2)H

2 0 [ 12 ]

Li 4- (1/2)H

2 0 + (l/4)0

2 LiOH (combined reaction) [13]

The calculated value2 at 1100 K (827 °C) is 3.5 kcal/g. If LiOH did not

form, the combined reaction would be:

for which the enthalpy yield is 4.8 kcal/g. Clearly there is a heavy

energy penalty paid by loss of hydrogen in the cycle to form LiOH.

E. Safety Considerations (7 )

Lithium metal reacts exothermically with the moisture in human tissue, causing both thermal and chemical burns. An explosion hazard

exists when the metal is exposed to moisture of any form, or to any

other oxidizing material. When heated in air or burned it emits toxic

fumes of Li

2 0 and LiOH. It reacts with nitrogen at high temperatures.

III. Li/H

2 0; Na0

2 /H2 0; H

2 /0

2

A. Starting Materials

The Li/H

2 0 part of the reaction scheme has been discussed above.

The role of Na0

2 is to provide oxygen for the second stage burning of

hydrogen.

2A11 energy yield calculations in this report are listed in terms of

kcal per gram of fuel plus oxidant.

2Li + (l/2)0

2 + Li

2 0 [14]
- 12-

The Na0

2 used in these experiments was indicated by the vendor to

be 95% NaC^. X-ray powder diffraction analysis of the starting material

which consisted of pale yellow granules, yielded a very complex pattern

containing peaks for NaOH, NaO^Cl) and several unidentified peaks.

B. Reaction Products

NaC^ was placed in a platinum cell in the thermoanalyzer. The

sample was brought to temperature (25 or 100 °C) and then a stream of

flowing water-saturated argon (30,000 ppm l^O) was introduced. At the

conclusion of the 100 °C experiment the sample was x-rayed. This was

not possible for the 25 °C experiment, which produced liquid; apparently

the Na0

2 (or the NaOH produced from it) is deliquescent at 25 °C. The

100 °C experiment yielded predominantly NaOH; the lesser amount of

Na 0H.H20 present is thought to have formed as the experiment cooled.

C. Kinetics

Reaction curves for Na02/H20 at 25 and 100 °C are shown in Fig. 2.

The 25 °C curve consists of two linear weight gain portions. Interestingly the slope increases for the later segment. This is interpreted as

follows. During the early 25 °C segment, the reaction involves loss of

oxygen and gain of water:

2Na0

2 + 3H

2 0 + 2(Na0H.H

2 0) + (3/2)

0

2 [15]

The theoretical fractional weight gain for this reaction is 0.06, which

is near the change in slope for the 25 °C curve. During the later

segment of the 25 °C reaction curve in Fig. 2, the product is thought to

be the deliquescent liquid observed at the conclusion of the experiment,

produced according to the reaction:
-13-

Na0H.H

2 0 + H2 0 -> (NaOH, H2 0) (£) [16]

Possibly formation of the liquid results in increased accessibility by

the gas, explaining the increased slope.

At 100 °C, the reaction of Na0

2 with water vapor produces a nearly

linear weight loss as would be expected from the reaction:

2Na0

2 + H2 0 + 2NaOH + (3/2)

0

2 [17]

This reaction would yield a theoretical weight loss of 0.27. The 100 °C

reaction apparently terminates at less than this value, reflecting the

presence of the NaOH impurity noted in the x-ray analysis of the starting materials.

D. Enthalpy

If the sodium superoxide reaction is combined with the lithium/water

oxidization reactions, we have the following:

(l/3)Na0

2 + (1/6)H2 0 + (l/3)Na0H + (l/4)0

2 [18]

Li + (1/2)H

2 0 + (l/4)02

-> LiOH [19]

(l/3)Na0

2 + (2/3)H

2 0 + Li + (l/3)NaOH + LiOH [20]

(combined reaction)

An enthalpy of formation for Na0

2 at 298 K can be estimated as -62.7 k < . 1 1 .
- 14 -

Neglecting the heat required to bring the oxygen from the first stage up

to 1100 K, the total energy release in reaction [20] is -2.2 kcal/g.

This is significantly less than the -3.5 kcal/g calculated earlier for

the Li/l^O; H

2 /O

2 combination. However it may be that there are advantages

associated with use of a solid as the oxidant source rather than a

compressed gas.

E. Safety Considerations (7 )

Hazards associated with lithium are noted in the discussion of

Li/^O above. Sodium superoxide has much the same toxicity as NaOH,

which it forms upon contact with moisture. Contact with skin could be

expected to cause burns and ulceration; inhalation of the mist or powder

could cause damage to the upper respiratory tract and lungs. Heating

could cause violent decomposition. Contact with moisture or reducing

agents could result in explosion.

IV. MgAl/H

2 0; H2 /C>2

A. Starting Materials

Magnesium aluminum alloy of 50/50 atomic ratio was prepared in the

NBS metals processing lab by melting high purity magnesium and aluminum

together under a halide flux and casting the melt into a steel chill

mold. The resulting ingot was very brittle and was easily crushed in a

mortar and pestle in a glove box. A (-200, +400) sieve fraction was

then prepared for the experiment and stored in the glove box until use.

An x-ray diffraction pattern showed characteristic peaks for A^Mg^

with a few additional unidentified peaks of low intensity.
- 15 -

B. Reaction Products

The powdered alloy was placed in an alumina cell in a glove gox and

transferred to the thermoanalyzer system. Next the specimen was brought

to 650 °C in an argon atmosphere. At this temperature the specimen was

completely melted, according to the Mg-Al phase diagram (8). Next,

argon saturated with water at 25 °C (30,000 ppm l^O) was flowed continuously over the sample. At the conclusion of reaction the gray, porous

sample was cooled, removed and x-rayed. The x-ray powder pattern showed

strong peaks for aluminum metal and MgO (periclase). Apparently only

the magnesium component of the molten alloy was oxidized, as there were

no peaks for A^O^, MgA^O^ or any other aluminous phases.

C. Kinetics

Rate data for the oxidation of molten MgAl by water vapor are shown

in Fig. 3. The meaning of the step in the weight gain curve at about

100 minutes of reaction time is not clear. However the two segments of

this curve on either side of the break have substantially linear portions,

suggesting that diffusion through a product layer of increasing thickness

is not a controlling factor during most of the reaction. The reaction

appears to slow to a very low rate as the fraction reacted approaches

0.30. This is in agreement with the x-ray analysis, which indicates

essentially all the Mg has been oxidized; complete oxidation of the Mg

to periclase would correspond to a fractional weight gain of 0.31, very

close to that observed; on the other hand, complete oxidation of both

the magnesium and the aluminum would result in a fractional weight gain

of 0.62.

D. Enthalpy

Referring to the system Mg-Al- 0-H, at least three possible oxidation

reactions involving the 1:1 alloy and water could occurr. These nre
- 16 -

summarized below:

2MgAl + 5H

2 0 -> MgO + MgAl2 0

4 + 5H

2 [21a]

5H

2 + (5/2)0

2

-> 5H

2 0 [21b]

2MgAl + 5H

2 0 -> 2MgO + A1

2 0 + 5H

2 [22a]

5H

2 + (5/2)0

2 + 5H

2 0 [22b]

MgAl + H

2 0 -* MgO + A1 + H2 [23a]

H

2 0 + (l/2)0

2 + H2 0 [23b]

To complete enthalpy calculations for these reactions an estimate for

the enthalpy of formation of molten MgAl was made using the ideal solution approximation. Calculated enthalpy release values for the three

reaction pairs are respectively, -3.8, -3.8, and -2.2 kcal/g. Clearly,

formation of spinel (reaction [21a] vs. reaction [22a]) affects the

energy yield very little. Reaction [23a] has been included because it

is the one observed, and clearly its occurrence instead of [21a] or

[22a] results in substantially lower energy yield. Presumably at some

higher temperature the aluminum component will begin to react according

to reaction [21a] or [22a].

E. Safety Considerations (7 )

Hazards data are not available for MgAl alloy. Aluminum is not

regarded as a poison, although inhalation of finely divided powders can

damage the lungs. Magnesium on the other hand can cause chemical gas
- 17 -

gangrene if it enters the body, due to generation of hydrogen. Fine

magnesium powder readily ignites by exposure to spark or flame.

V. LiAl/C10

3 F

A. Starting Materials

The starting material for these experiments was powdered LiAl.

The material as received was packed under argon and visually showed no

signs of surface contamination—all surfaces were bright and shiny.

X-ray analysis showed only peaks of LiAl. All manipulations involving

this material were done in a glove gox through which a continuously

purified argon atmosphere was recirculated. The material used in these

experiments was a (-200, +400) sieve fraction. Transfer to the thermoanalyzer was accomplished in a glove bag, flushed repeatedly with purified

argon

.

The CIO^F (perchloryl fluoride) was obtained from the vendor in

cylinders containing either 100 g or 250 g. Principal impurities were

N

3

, 0

3

, CO

2

, ^0 and HF (see section on mass spectrometry).

Gas was run through a corrosive gas regulator and then through a

column containing NaOH pellets and molecular sieve, and finally through

a flowmeter and then into the thermoanalyzer. The CIO^F, a very dense

gas, was piped directly into the crucibles in the thermoanalyzer experiments. Provision was made for mixing the CIO^F with continuously variable amounts of argon. However, all thermoanalyzer experiments reported

were carried out using a flow of pure CIO^F since it was discovered that

the reactions proceeded in controlled fashion so that no argon dilution

was necessary. Although argon was used to flush the balance components
- 18 -

during the experiments, it is estimated that the effective partial

pressure of CIO^F over the specimens during these experiments was close

to 1 atmosphere.

B. Reaction Products

Initially, experiments were conducted in alumina crucibles; however

these were unsatisfactory above 700 °C, owing to the corrosiveness of the

molten alloy. Crucibles of LiA102 have been fabricated and these appear

to offer promise for application in higher temperature experiments.

Additionally MgO and BeO offer promise. Boron nitride crucibles were

fabricated and tested in contact with LiAl at 800 °C. They seem to hold

up to attack by the molten alloy well, except for a slight discoloration,

which may be associated with diffusion of Li. Also a steady and extensive

weight gain of the crucible occurred during preliminary tests under an

atmosphere of purified argon. As we have no explanation for or solution

to this problem, use of the BN crucibles was discontinued. Calciastabilized zirconia and silica glass crucibles were employed for the

mass spectrometric studies, with mixed results. All other experiments

reported employed alumina crucibles.

At the conclusion of the LiAl/ClO^F experiments, crucibles were

removed and placed in an inert atmosphere. X-ray mounts were prepared

in the glove box and x-rayed under flowing N

2

. Results of x-ray analysis

are indicated in Table 1, below.

As can be seen from Table 1, experimental results vary greatly

depending upon experimental conditions. The following generalizations

can be made, however, for the range of conditions investigated ( 350—

650 °C, Pcl0 F

= 1 atm; or, 900 °C, Pcl0 p

= 10~ 5 atm).
-19-

(1) Fluorides (Li.AlF, , A1F„ , LiF) appear to be by far the dom3 b 3

inant reaction products.

(2) Chlorides may form during initial stages of oxidation 3 (see

discussion of kinetics) but are relatively minor phases in the

end products.

(3) The lithium in the alloy is preferentially oxidized leaving

behind aluminum which behaves as though inert (see also discussion of MgAl oxidation).

(4) The occurrence of oxides as oxidation products is limited in

these experiments to low partial pressures of CIO^F and/or

high temperatures.

C. Mass Spectrometry

i) Outline of Method

In this technique, the Li-Al alloy contained in a Knudsen cell is

exposed to CIO^F introduced into the cell through a gas inlet system.

At appropriate temperatures, reaction products undergo vaporization into

the source of the mass spectrometer where the gaseous products are ionized and mass analyzed. The major advantage of this method is that it

can in principle detect gaseous reaction products. A second advantage

is that the number of collisions of reactant vapor with the condensed

phase may be controlled at a low value so that the kinetics of the

process can be substantially solved.

In the present measurements, however, it was found that reaction

rates are quite slow even up to temperatures as high as 1000 °C so that

modifications in the experimental arrangement to enhance reaction rates

will be advantageous.

3 0xidation is here used in the generic chemical sense.
- 20 -

ii) Vaporization Considerations

At low temperatures some of the reaction products may be relatively

non-volatile so that they will not be detected by mass spectrometric

analysis. On the basis of data in the literature, the metal chlorides

are more volatile than the metal fluorides while the metal oxides are

non-volatile up to temperatures of 1000 °C or so. Also, because the

halides will form a salt solution, complexing to form interhalide compounds may influence the volatity of the solution. For example, formation of LiAlCl^ would greatly reduce the pressure expected from formation of AlCl^.

iii) Experimental set-up

These measurements were made using a fused silica effusion sampler.

The Li-Al alloy was contained in a calcia-stabilized zirconia cup supported within the effusion sampler. The CIO^F was delivered to the gas

inlet tube through a small leak valve. The Li-Al alloy was loaded into

the zirconia cell in a dry-box then transferred to the mass spectrometer

under argon to reduce the reaction of the Li-Al alloy with ambient water

vapor

.

An effusion orifice of 1 mm diameter was used in the effusion

sampler. This proved to be too large as the CIO^F reacted much less

rapidly with the Li-Al alloy than expected.

The control valve was attached to the CIO^F cylinder in the dry box

so the CIO^F was diluted with Ar during the earlier parts of the experiment.

iv) Analysis of CIO^F

Mass spectrometric sampling of the commercial CIO^F gas showed

predominant peaks at m/e values of 104, 102, 85, 83, 69, 67, 53, and 51

37 35 +

corresponding to the Cl and Cl isotopes of the species CIO^F ,
- 21 -

C10^

+

, C102 +

, and C10+

. Except for C10^F+

, these peaks are due to fragmentation of the CIO^F during the ionization process using electrons at

30v. Besides the CIO^F, Ar which was introduced from the dry box installation of the regulator was also observed. By comparing the mass spectrum

with the CIO^F gas flow on or off, it was determined that the CIO^F also

contained a small amount (perhaps a percent or so) of air (N^, , CC^

,

and 1^0). The had apparently partially reacted with the steel

35 cylinder and produced slight traces of HF (mass 20), H Cl (36), and

37

H Cl (38). However, it is not likely that the contamination had significant effect on the reaction of CIO^F with the alloy.

v) Reaction of Li-Al Alloy with CIO^F

The first mass peaks due to reaction of CIO^F with the Li-Al alloy

were observed at 420 °C. These peaks were Li+from fragmentation of

LiCl(g), LiCl+ from ionization of the LiCl(g) and L^Cl"*", from ionization of the L±^Cl^(g) parent.

One might expect Al-Cl species in this temperature range but none

were observed, in spite of the fact that loss of volatile substances is

indicated by the analogous thermogravimetric experiment. It is clear

from the presence of both LiCl(g) and that a condensed halide

phase was formed on the sampler.

With time, the ratio of LiCl^/L^Cl"*" gradually increased. This

probably showed that LiF was also forming in the condensed phase and

reducing the activity of LiCl. At 600 °C, L^f"*" from the fragmentation

of Li

2 F2 was observed in the mass spectrum. Over the temperature range

from 600-900 °C ions corresponding to parent molecules LiCl, L^C^,

LiF, and L± 2^2 were observed. It did not appear that any A1 bearing

species were formed in the gas phase.
- 22 -

At the conclusion of the experiment, the Li-Al alloy still had a

• powdery appearance even through it had been heated several hundred

degrees above the melting point.

An x-ray diffraction pattern of the residue revealed the presence

of LiAlC^ with perhaps an equal amount of unreacted A1 (see Table 1).

vi) Al-CIO^F Interaction

Because A1 bearing species were not observed from the Li-Al alloy,

a mass spectrometric experiment was carried out using only powdered A1

in the effusion cell. The purpose of this experiment was to see if it

was possible to form A1 bearing species by reactions with CIO^F. Near

500 °C species corresponding to the halide ions A1F+

, A1C1+, A1F2+

,

A1C1F+

, Al^+

, AlF^Cl"*", AIC^f"*", and AlCl^"*" were observed. Because of

the number of complex species in the vapor phase, the existence of a

condensed phase at this temperature consisting of mainly AIF^ seems

likely. The duration of the experiment during which Al-halide species

was generated was quite short. All of the A1 bearing species decreased

with time and increasing the CIO^F flow rate and the temperature had no

effect on increasing their intensity. This seems to indicate that the

chlorination and fluoridation processes took place at only selected

sites in the A1 powder which were gradually depleted or lost, perhaps

because of oxidation.

At 760 °C, most of the A1 halide peaks had vanished except for

A1F2+

which is a major fragmentation product of AlF^Cg). The experiment

was terminated after a brief heating period at 800 °C. Visual examination of the residue at the conclusion of the experiment revealed that

most of the sample still had a powdery texture but a few small spheres

resulting from melting the sample were also present. Since the sample
-23-

was heated to about 150 °C above the melting point of Al, the powdery

texture of the sample must result from an oxide skeleton on the outside

surface of each grain in the powder. The sample initially weighed

118 mg and gained 2.2 mg during the experiment, despite loss of the

halides, indicating that a small amount of oxidation took place.

D. Kinetics

Thermogravimetric rate data for the reaction of LiAl with CIO^F are

shown in Fig. 4 at temperatures of 350, 450, 550 and 650 °C. It is

presumed on the basis of the Li-Al phase diagram (9) that the LiAl was

solid during these experiments. With the exception of the 350 °C experiment, rate curves all initially show a rapid weight gain at a nearly

steady rate. This continues until a weight fraction gain of between 0.5

and 0.7 has been reached. At this point the rate of weight gain decreases

for a short time and then increases again. This behavior is especially

pronounced in the 650 °C experiment, where a small weight loss with time

is apparent, followed by an increase in the rate of weight gain. This

weight loss (and possibly, as well, the temporary decrease in rate of

gain at all four temperatures) is best interpreted as due to formation

of a volatile reaction product, most probably AlCl^. Continued reaction

leads to a similar ultimate weight gain of between 0.9 and 1.1 for

experiments at all four temperatures, 350, 450, 550 and 560 °C (see

Table 1) . This is true in spite of the fact that the products are

somewhat different in each case. Table 2 lists hypothetical reactions

of LiAl with Cl, 0 and F and combinations thereof, together with theoretical weight gains. These reactions have been derived with the aid of

thermodynamically calculated equilibrium phase compatibilities shown in

Fig. 7. Calculated weight gains are highly variable, but the partial

fluorination reactions [26] and [27] of Table 2 best approximate the
-24-

experimental products observed (Table 1). The fractional weight gains

calculated for these reactions are 0.56 and 1.12, respectively, encompassing the range observed.

It seems likely from the curves in Fig. 4 that more than one reaction has occurred during the oxidation of LiAl by CIO^F. It also seems

likely that early stage condensed phase products undergo subsequent

reaction with time to yield a new generation of products. In future

experiments, reacion of LiAl with CIO^F will be completed at higher

temperatures, where hopefully a rapid approach to equilibrium will

eliminate many of these complications. It is hoped that mass spectrometer measurements will be carried out at higher pressures of CIO^F

using a transpiration system.

E. En thalpy

From Table 1 it can be seen that the reaction products at temperatures of 650 °C and below differ greatly, depending upon temperature.

Further, oxidation of the alloy is far from complete, and the majority

of the aluminum component of the alloy appears to have remained in the

metallic state. The reaction products suggest disequilibrium among

themselves; for example, Li_AlF, , A1F. and LiF are not in stable equili3 6 3 brium together. The principal difficulty then is in extrapolating these

limited results to a higher temperature such as 1100 K, at which oxidation could be expected to be much more complete, so that a meaningful

enthalpy yield calculation can be done.

The LiAl/ClO^F reaction can be described by the five component

chemical system Li-Al-Cl-O-F. Fortunately thermodynamic data are available for many of the end-member compounds in this system and so a preliminary thermodynamic analysis can be completed. This results in an
-25-

estimated equilibrium reaction for complete oxidation which can be used

to calculate enthalpy yield. The thermodynamic analysis was completed

as follows. Fig. 5 depicts graphically the compositional regions of

interest in the three principal quaternary subsystems contained within

the five component system. Fig. 6 shows calculated phase compatibilities

for important ternary reciprocal systems in Fig. 5. These compatibilities

are schematic and indicate major features of phase equilibria which are

consistent with known thermodynamic data, according to the reactions in

Table 3. On the basis of Fig. 6, Fig. 7 has been constructed. This

shows calculated equilibrium relations at 1100 K for the phase regions

shown in Fig. 5. Based on Fig. 6 and 7, Fig. 8 has been constructed,

showing calculated equilibrium relations at 1100 K among phases most

likely to form as products of complete reaction of LiAl and CIO^F. The

reaction suggested by Fig. 8 is:

2LiAl + C10

3 F -> A1

2 0

3 + LiF + LiCl [74x]

It should be emphasized that there is no direct experimental evidence

yet in support of this reaction: however on purely thermodynamic grounds

it is the favored reaction. To complete the enthalpy calculation, data

for LiAl were estimated using the ideal solution approximation. The

resulting value of enthalpy yield for this reaction is 3.8 kcal/g.

F. Safety Considerations (7 )

Safety hazards associated with LiAl are similar to those associated

with Li as noted above, although reaction with moisture is considerably

less vigorous at room temperature. Perchloryl fluoride is a highly

toxic gas which causes symptoms of asphyxiation and poisoning similar to
- 26 -

CO, although recovery is said to be rapid provided exposure has not been

prolonged. The gas has a sweet odor, but this cannot be relied upon to

indicate toxic concentrations. Perchloryl fluoride is readily absorbed

through the skin. Although nonflammable, it does support combustion, as

it is a powerful oxidizer. When heated to decomposition, it emits highly

toxic fumes of chlorides and fluorides.

VI. LiAlMg/C10

3 F

A. Enthalpy

At the time of writing, experiments have not yet been completed in

this system, owing to lack of available starting material. Therefore

enthalpy yield estimates must be made solely on the basis of preliminary

thermodynamic analysis. The fuel/oxidant reaction is represented by the

6-component system Li-Al-Mg-Cl-O-F. The phase equilibrium topology is

of course impossible to represent in three dimensions; nonetheless,

progress can be made by consideration of the six quaternary reciprocal

systems shown in Fig. 9. By calculation of the reactions in Table 4,

the schematic ternary phase compatibilities shown in Fig. 10 have been

derived. From additional reactions in Table 4 and compatibilities in

Fig. 10, construction of Figs. 11 and 12 was made possible. Fig. 11

pertains to progressive chlorination, fluorination or oxygenation of

fuel. Fig. 12 relates to the equilibrium products of complete reaction.

Table 5 gives some postulated equilibrium reactions involving progressive

reaction of LiAlMg fuel with Cl, F, 0 and combinations thereof.

Based on the above considerations, the following is thought to represent complete reaction of LiAlMg alloy (1:1:1 atomic) with ClO^F:
- 27 -

4LiAlMg + 3C10

3 F -* MgF

2 + LiF + 3LiCl + 2MgAl

2 0

4 + MgO [134]

The calculated enthalpy yield for this reaction at 1100 K is 3.6 kcal/g.

B. Safety Considerations (7 )

Safety hazards are similar to those noted for LiAlMg/ClO^F above.

VII. LiBe/C10

3 F

A. Enthalpy

Because of the toxicity of beryllium and beryllium compounds, experiments have not been conducted on the oxidation of lithium-beryllium

alloy by C10

3 F. Hence any estimate of enthalpy release must rely soley

upon thermodynamic estimates of the actual reaction. A thermodynamic

analysis of the five component system Li-Be-Cl-O-F was completed as

follows. Fig. 13 shows the three quaternary subsystems of interest.

Based on reactions in Table 6, the ternary phase compatibilities in

Fig. 14 have been constructed. Based on these compatibilities and

additional reactions in Table 6, the schematic quaternary phase compatibilities in Fig. 15 have been derived; these show the results of

progressive chlorination, f luorination, or oxygenation of LiBe fuel

(Table 7 lists equilibrium reactions involving LiBe fuel with various

combinations of Cl, 0 and F) . Fig. 16 indicates calculated compatibilities among likely reaction products. The reaction postulated on the

basis of thermodynamic data for complete oxidation of LiBe by PCF is:

8LiBe + 3C10

3

F -* 8BeO + Li

2 0 + 3LiF + 3LiCl [169]

The enthalpy relased by this reaction at 1100 K would be 4.6 kcal/;-.
= 28 -

B. Safety Considerations (7 )

Lithium and beryllium do not form stable intermetallic compounds

together (10) and would be expected to be present together in fuel as

the chemically uncombined metals. For a discussion of Li safety hazards,

see Li/l^O above. Beryllium is highly toxic both in metallic form and

in compound form. Many of the beryllium salts have high vapor pressures,

especially when heated. Symptoms of exposure usually involve respiratory

distress of varying severity; symptoms may be delayed for several years

after exposure. Chronic berylliosis can lead to death from respiratory

and cardiac failure. In addition to harm incurred by inhalation, beryllium and its compounds also act on the skin, causing lesions and tumors.

Beryllium by itself does not present an explosion hazard, however the

admixed lithium in the fuel obviously does. For a discussion of perchloryl fluoride safety refer to LiAl/ClO^F above.

VIII. Ll/C

11

F

20

A. Starting Materials

The fluorocarbon compound was not obtainable from commercial

suppliers; the closest molecular weight compound available was the

structurally similar double ring compound C-qF^, an apparently stable,

clear liquid. Experiments have not yet been completed due to the necessity of installing a special furnace with a boiling chamber for the

liquid oxidant on the thermoanalyzer. It is hoped that loan from another facility of a water vapor furnace (which would also provide 1 atm of

Pu for the Li/H o 0 and MgAl/Ho 0 experiments) will provide a solution

u z z to this experimental problem.
-29-

B. Enthalpy

In the absence of experimental data, it is again necessary to

utilize thermodynamic estimates in arriving at an oxidation reaction for

the enthalpy calculation. The system Li-F-C provides a compositional

representation of the Li/C^^F^Q reaction. By using calculated reactions

in Table 8, Fig. 17 can be constructed, showing schematic phase compatibilities at 1100 K. On this basis, the thermodynamically estimated oxidation reaction is:

C

11

F

20 + 20Li "* 11C + 20LiF [176]

As no enthalpy data have been located for it is necessary to

make an estimate. This can be done by extending the procedures used for

estimating properties of hydrocarbon molecules. A very approximate value

of 900 kcal/mole is obtained in this way for 298 K. The calculated enthalpy yield at 298 K is 3.1 kcal/g. Presumably the value at 1100 K

would be somewhat higher.

C. Safety Considerations (7 )

For a discussion of Li safety hazards, see Li/l^O above. Data are

not available for the obtained, but the related compound C-|

2 F 20

is a highly stable molecule which has been used to develop a synthetic

blood substitute.

IX. LiB/NF

3

A. Starting Materials

NF^ has been obtained from a commercial source in small cylinders.
-29aPrincipal impurities are stated by the vendor as N

3

> HF, NO and 1^0. A

source of LiB has been located but the material has not yet been procured,

and so there are not experimental data on the reaction at this point in time.

B. Enthalpy

In the absence of experimental data on the LiB/NF^ reaction, thermodynamic analysis of the system Li-B-N-F (Fig. 18) is essential. Using the

reactions in Table 9, the schematic 1100 K ternary phase relations in Fig. 19

have been calculated. Fig. 20 gives calculated compatibilities among product

phases at 1100 K. Table 10 gives reactions for progressive degrees of oxidation of LiB fuel by NF^. The suggested reaction for complete oxidation of

LiB by NF^ is

:

3LiB + 2NF

3

-* 3LiF + BN [185]

Boron trifluoride (BF^) is a gas even at relatively low temperatures, and

so this would not be a desirable reaction. However by simply adding excess

lithium to the fuel, in principle the following reaction could be obtained:

2Li + LiB + NF

3 + 3LiF + BN [186]

Depending upon the kinetics, BF

3 might still form as an intermediate product,

but the equilibrium final partial pressure would be very low. Although LiB

is known as a stable compound, thermochemical data were not available. It has

been assumed that at 1100 K it would be molten, and the ideal solution approximation has been applied to give an enthalpy of formation of 0.0 kcal. The enthalpy

yield of reaction [180] can then be calculated as 4.6 kcal/g.

C. Safety Considerations (7 )

Handling properties and toxicity of the compound LiB apparently
-30-

have not found their way into appropriate compendiums , but it is reasonable to assume that the comments made above under discussion of safety

for Li and LiAl fuels would also apply here. The compound is used in

pyr otechnical devices, and so there may be a potential explosion hazard.

With regard to NF^ , it is a colorless gas with a moldy odor and a high

toxicity similar to HF. It could therefore be expected to be extremely

corrosive to the respiratory tract and skin. Prolonged exposure may

cause skeletal changes.

X. Summary and Discussion

In terms of energy release/unit mass, ranking of various stored

energy reactions is as in Table 11, which includes for reference, two

schemes not otherwise discussed in this report:

Mg + H

2 0 -* MgO + H2 [187a]

H

2 + (l/2)0

2

-* H

2 0 [187b]

2A1 + 3H

2 0 -> A12

C> 3 + 3H

2 [188a]

3H

2 + (3/2)0

2

-* 3H

2 0 [188b]

Several points should be made regarding the ranking in Table 11. First,

direct experimental evidence for several of these reactions has not yet

been obtained, due in part to materials limitations. Although we are

optimistic that these will soon be overcome, in the meantime the ranking

-31-

in Table 11 may have only limited practical significance. An example is

<d the reaction Li/^O [14]. Theoretically it should be high on the list

at 4.8 kcal/g. However in practice this yield may not be achieved due

to formation of LiOH, which irreversibly ties up hydrogen in the water

cycle, and reaction [13], with an enthalpy yield of 3.5 could prevail

instead. Also there are presumably other factors such as safety to be

considered. The high toxicity of beryllium makes the practicality of

utilizing reaction [169] questionable. On the other hand, it could

probably be said that since fuel or oxidant or both are inherently

chemically unstable, all of the reaction schemes involve some degree of

toxicity to human tissue or other safety hazards, and suitable safeguards

must be employed with any reaction scheme to eliminate the possibility

of containment failure or runaway reaction. For example, lithium metal

exposed to moist air at room temperature rapidly generates hydrogen.

Perchloryl fluoride has a toxic effect similar to CO. NF^ is not only

toxic but extremely hazardous under pressure. When all such factors are

considered, undoubtedly the Mg/^O, MgAl/^O and Al/^O schemes pose the

least safety hazard; however the latter two fuels may require very high

temperature operation to overcome the kinetic barriers to oxidation of

the aluminum. In terms of safety the LiAl/H^O scheme is also high on

the list, as LiAl is much less reactive than lithium upon exposure to

air. Furthermore from a practical viewpoint, there may be other factors

to consider besides enthalpy yield. For example, although the Li/C.j

and Li/^O; NaC^/^O schemes rank low in Table 11, there may be certain

advantages associated with not having to store gaseous oxidizers.

Additional experimental work is necessary at higher temperature,

than attained to date in order to verify the reactions presented in
-32-

Table 11. Evidence to date suggests several of the reactions are kinetically hindered at temperatures below 650 °C. We are optimistic that

the materials limitations encoutered in this preliminary study will be

overcome, so that relevant experimental data on high temperature kinetics

and phase equilibria can be systematically gathered in the near future.

XI. Future Work

The highest priority involves finding suitable container materials

so that thermogravimetric experiments can be extended to higher temperatures. Rod stock of high density MgO has been obtained and is being

fabricated into crucibles. Also beryllia crucibles will be machined to

order by a vendor equipped to do this safely. Crucibles of LiA102 have

already been fabricated. We are optimistic that use of one or more of

these materials will allow us to extend the temperature range of experimentation into the 650-1000 °C region.

After the container problem is solved the first priority will be to

determine if the oxidation reactions can be made to go to completion,

and if so what the minimum temperature is at which this will occur.

Once optimum conditions for reaction are determined, an attempt will be

made to measure enthalpy of reaction directly using DTA.

Simultaneously with these experiments phase equilibrium measurements

will commence. The first experiments will involve heating the predicted

end products of the reactions together in sealed capsules, quenching and

examining to see if they really are in equilibrium as suggested by the

thermodynamically calculated reaction. This will give important information

on solubilities (both liquid and solid) as well.
- 33 -

It is hoped that mass spectrometric measurement of species vapor

pressures during these reactions can be completed using the NBS transpiration mass spectrometry system. This apparatus allows measurements

of species at pressures up to 10 atm, which would more closely simulate

actual reactor conditions. Top priority would be given to the investigation of the LiAl/ClO^F and LiAlMg/ClO^F systems. Also, the (Li + LiB)/NF^

and Li/C-^^F^Q systems might be amenable to investigation by this approach.
-34-

XII. References Cited

1. SCEPS II. A New High-energy Undersea Propulsion System, Garrett

Pneumatic Systems Division, Report No. 41-3675 (1982).

2. Cook, L. P. , Plante, E. R. , Roth, R. S., Hastie, J. W. , Phase

Equilibria of Stored Chemical Energy Reactants, National Bureau of

Standards, Report No. NBSIR 84-2490, 112 p. (1984).

3. Costas, L. P. and Marshall, R. P. , Trans. Met. Soc. AIME, 224, 971

(1962).

4. Kalakutskaya , N. A., Tepl. Vys. Temp., _6 436 (1968).

5. Levine, E. D. and Rapperport, E. J., Trans. Met. Soc. AIME, 224,

1204 (1963).

6. Stull, D. R. and Prophet, H. , JANAF Thermochemica

1

Tables, Second

Ed. : U. S. Govt. Printing Office, Washington, DC, NSRDS-NBS 37,

(1971). See also later supplements for 1971-1981 (J. PHys. Chem.

Ref. Data).

7. Sax, N. I., Dangerous Properties of Industrial Materials ( Sixth

Ed.): New York, Van Nostrand, 3124 p. (1984).

8. Murray, J. L. , Bull. Alloy Ph. Diag. _3 [1] 60 (1982).

9. McAlister, A. J., Bull. Alloy Ph. Diag. _3 [2] 177 (1982).

10. Moffatt, W. , The Hand Book of Binary Phase Diagrams , Vol . 1 : Schenectady, NY: General Electric Co. (1981 and updates).

11. Groff, E. G. , Characteristics of a steadily operating metal com- bustor: Penn. State Univ., Ph . D. thesis, 156 p. (1976).
-35-

XIII. Appendix: Results of Literature SurveyFollowing are bibliographic listings which have been selected from

a computerized literature search of the Chemical Abstracts Data Base

(1967-1984). References are not annotated, and low temperature as well

as high temperature studies have been included. References are loosely

grouped according to search categories that roughly correspond to the

various alternate stored chemical energy reaction fuels and oxidants.
-36-

A. Oxidation of Lithium metal, including kinetics and oxidation by water

Besson, J.and Pelloux, A., 1967, Oxidation kinetics of lithium by water

vapor: C. R. Hebd . Seances Acad. Sci. , Ser. C, V. 265, No. 15,

p. 816-19.

Cooper, J. F. ; Hosmer, P. K. and Homsy, R. V. , 1978, The anodic behavior

of lithium in aqueous lithium hydroxide solutions: J. Electrochem.

Soc. , V. 125, No. 1, p. 1-7.

Korovin, N. V. and Smirnov, S. E. , 1982, Anodic oxidation of lithium in

lithium hydroxide solutions. Structure of a lithium film: Elektrokhimiya, V. 18, No. 11, p. 1510-12.

Stone, H. E. N. , 1972, Oxidation of metals in relation to the periodic

classification: J. Mater. Sci., V. 7, No. 10, p. 1147-53.

Touzain, P. , 1967, Kinetic study of the oxidation of alkali metals by

dry oxygen: Commis. Energ. At. (Fr.). Rapp., No. CEA-R 3301, p. 1-93.
-37-

B. Oxidation of aluminum metal, including kinetics and oxidation by water

Agarwala, V. K. and Fort, T. Jr., 1974, Work function changes during

low pressure oxidation of aluminum at room temperature: Surf. Sci. , V. 45, No. 2, p. 470-82.

Agarwala, V. K and Fort, T. Jr., 1976, Nature of the stable oxide layer

formed on an aluminum surface by work function measurements: Surf.

Sci., V. 54, No. 1, p. 60-70.

Akimov, A. G. ; Rozenfel’d, I. L. and Dagurov, V. G. , 1980, X-ray electron spectroscopy study of oxidation of aluminum in oxygen and water

vapor: Zashch. Met., V. 16, No. 5, p. 573-6.

Andreev, L. A.; Gel'man, B. G. and Zhukhovitskii, A. A., 1974, Absorption of hydrogen by solid aluminum during high-temperature oxidation

in water vapors: Fiz-Khim. Issled. Metall. Protsessov, No. L., p. 90-

94.

Bachrach, R. Z.; Flodstrbm, S. A.; Bauer, R. S.; Hastrom, S. B. M. and

Chadi, D. J., 1978, Surface resonances and the oxidation of singlecrystal aluminum: J. Vac. Sci. Technol. , V. 15, No. 2, p. 488-93.

Baker, B. R. and Balser, J. D. , 1976, Formation of films on aluminum by

reaction with water: Aluminum (Duesseldorf ) , V. 52, No. 3, p. 197-200.

Bakulin, E. A.; Balabanova, L. A.; Bredov, M. M. and Stepin, E. V., 1973,

Characteristic electron energy losses during oxidation of aluminum films:

Fiz. Tverd. Tela (Leningrad), V. 15, No. 4, p. 1266-7.

Barycka, I. and Hejduk, A., 1974, Anodic oxidation of aluminum in a d.c.

oxygen discharge: Pr. Nauk. Inst. Technol. Elektron. Politech. Wroclaw.,

V. 11, p. 53-64.

Beck, A. F. ; Heine, M. A.; Caule, E. J. and Pryor, M. J., 1967, Kinetics

of the oxidation of A1 in oxygen at high temperature: Corros. Sci.,

V. 7, No. 1, p. 1-22.

Benndorf, C. ; Keller, G. ; Seidel, H. and Thieme , F. , 1977, High-resolution quartz oscillator microbalance and its application to the initial

oxidation of aluminum: J. Vac. Sci. Technol., V. 14, No. 3, p. 819-21.

Benninghoven , A. and Mueller, A., 1972, Investigation of the surface oxidation of metals in the submonolayer and monolayer range with the static

method of secondary ion mass spectrometry: Thin Solid Films, V. 12,

No. 2, p. 439-42.

Bhavani, K. and Vaidyan, V. K. , 1979, Asymptotic form of oxide growth for

aluminum thin films: Natl. Acad. Sci. Lett. (India), V. 2, No. 12,

p. 457-9.
-38-

Section 13, continued

Bradshaw, A. M. ; Hofmann, P. and Wyrobisch, W. , 1977, The interaction of

oxygen with aluminum (111): Surf. Sci. , V. 68, p. 269-76.

Breakspere, R. J. , 1970, High- temperature oxidation of aluminum in various

gases: J. Appl. Chem. , V. 20, No. 7. p. 208-12.

Bullett, D. W. , 1980, The bonding of oxygen to aluminum(lll) : Surf.

Sci., V. 93, No. 1, p. 213-22.

Cathcart, J. V.; Petersen, G. F. and Sparks, C. J. , 1967, Oxidation rate

and oxide structural defects: Surfaces Interfaces 1, Proc. Sagamore

13th Army Mater. Res. Conf . , Oak Ridge National Laboratory, Oak Ridge,

TN, (Burke, J. J., Ed.), p. 333-46.

Chang, C. C.; Fraser, D. B.; Grieco, M. J. ; Sheng. T. T.; Haszko, S. E.;

Kerwin, R. E.; Marcus, R. B. and Sinha, A. K. , 1978, Aluminum oxidation

in water: J. Electrochem. Soc. , V. 125, No. 5, p. 787-92.

Cox, B.,1974, Technique for studying the rate controlling processes during metal oxidation: Proc. 5th Int. Congr. Met. Corros. , At. Energy

Canada Ltd., Chalk River, Ont., (Sato, N. , Ed.), p. 682-9.

Dickens, P. G. ; Heckingbottom, R. and Linnett, J. W. , 1969, Oxidation of

metals and alloys. II. Oxidation of metals by atomic and molecular

oxygen: Trans. Faraday Soc., V. 65, No. 8, p. 2235-47.

Dong, D. , 1982, Anodic oxidation treatment of aluminum reactor vessel:

Huagong Jixie, No. 4, p. 59-62.

Eberhardt, W. and Kunz, C., 1978, Oxidation of aluminum single crystal

surfaces by exposure to oxygen and water: Surf. Sci., V. 75, No. 4,

p. 709-20.

Elyutin, V. P.; Mitin, B. S.; Samoteikin, V. V., 1971, Effect of oxygen

pressure on the oxidation of aluminum: Izv. Akad. Nauk SSSR, Metal,

V. 3, No.

Faeber, W. and Braun, P. , 1975, Investigations of the oxide formation

on metals with the Auger electron spectroscopy: Mikrochim. Acta, Suppl.

,

V. 6, p. 391-402.

Fehlner, F. P. and Mott, N. F. , 1971, Low-temperature oxidation. Reply

to discussion: Oxid. Metals, V. 3, No. 3, p. 275-7.

Flodstrom, S. A.; Bachrach, R. Z.; Bauer, R. S. and Hagstrom, S. B. M.

,

1977, Oxidation of aluminum single crystal faces: (100), (110), and

(111): Proc. 7th Int. Vac. Congr., Palo Alto Res. Cent., Xerox, Palo

Alto, CA, (Dobrozemsky , R. ; Ruedenauer, F. and Viehboeck, F. P., Eds.),

V. 2, p. 869-72.
-39-

Section _B, continued

Flodstrom, S. A.; Martinson, C. W. B.; Kalkoffen, B. and Kunz , C. , 1980,

Oxygen interaction with clean aluminum and magnesium films investigated

by synchrotron-radiation-induced photoeraission : Mater. Sci. Eng.,

V. 42, No. 1, p. 31-7.

Fontijn, A.; Felder, W. and Houghton, J. J., 1973, Kinetics of aluminum

atom oxidation: U. S. Nat. Tech. Inform. Serv. , AD Rep., No. 776673/6GA,

34 p.

Fontijn, A.; Kurzius, S. C. and Houghton, J. J., 1972, Kinetics of metal

atom oxidation reactions: U. S. Nat. Tech. Inform. Serv., AD Rep.,

No. 749380, 56 p.

Fridrich, J., 1971, Use of a quartz crystal microbalance to study the

oxidation of aluminum during vacuum deposition: Thin Solid Films, V. 7,

No. 3/4, p. 277-85.

Gerlach, J. and Weber, J. , 1974, Rate of oxidation of aluminum in fused

cryolite: Metall, V. 28, No. 3, p. 218-23.

Glukhov, V. I.; Fedoseev, V. A.; Grigorenko, I. N. and Kolpakova, T. I.,

1979, Chemical reactions of aluminum with water: Fiz. Aerodispersn.

Sistem, (Kiev), No. 19, p. 49-54.

Godard, H. P. , 1967, Oxide film growth over five years on some aluminum

sheet alloys in air of varying humidity at room temperature: J. Electrochem. Soc. , V. 114, No. 4, p. 354-6.

Goral'nik, A. S. , 1968, Kinetics of the anodic oxidation of aluminum and

its alloys: Elektrokhimiya, V. 4, No. 9, p. 1108-10.

Gorbunov, V. V.; Khromov, V. G. and Shidlovskii, A. A., 1971, Oxidative

activity of water vapor, carbon dioxide, and carbon monoxide toward

magnesium and aluminum powders: Zh. Prikl. Khim. (Leningrad), V. 44,

No. 4, p. 727-34.

Gray, T. J. and Pryor, J. M. , 1969, Oxidation kinetics: Mater. Sci. Res.,

Coll, of Ceram., State Univ. of New York, Alfred, NY, (Gray, T. J., Ed.),

V. 4, p 446-60.

Gremyachkin, V. M. ; Istratov, A. G. and Leipunskii, 0. I., 1974, Formation

of condensed oxide particles during combustion of fine metal drops: Zh.

Prikl. Mekh. Tekh. Fiz., No. 4, p. 70-8.

Grimblot, J. and Eldridge, J. M. , 1982, Oxidation of aluminum films: J.

Electrochem. Soc., V. 129, No. 10, p. 2369-72.

Grinbergs, M. , 1975, High- temperature oxidation of aluminum: Tezisy

Dokl. - 4th Konf . Molodykh Nauchn. Rab . Inst. Neorg. Khim., Akad. Nauk

Latv. SSR, Inst. Neorg. Khim., Riga, USSR, (Sokolov, Yu. N. , Ed.),

p. 24-5.
- 40 -

Section j3, continued

Hagstrom, S. B. M. ; Bachrach,

1977, Oxidation of aluminum

photoelectron spectroscopy:

R. Z. ; Bauer , R. S

.

surfaces studied by

Phys. Scr . , V. 16,

and Flodstrom, S. A.,

synchrotron radiation

No. 5-6, p. 414-19.

Hayden, B. E. ; Klemperer, D. F. ; Allen, G. C. and Tucker, P. M. , 1980,

The early stages of oxidation of magnesium, aluminum and magnesium/

aluminum alloys: Vide, Couches Minces, V. 201, Suppl., Proc. 4th, Int.

Conf. Solid Surf., VI, p. 453-7.

Hunt, G. L. and Ritchie, I. M. , 1972, Effect of pressure changes on the

oxidation rate of aluminum at 323-673 K: J. Chem. Soc. , Faraday Trans. 1,

V. 68, Pt. 8, p. 1413-22.

Hunt, G. L. and Ritchie, I. M. , 1972, Oxidation of aluminum by nitrous oxide

at 323-683 K: J. Chem., Faraday Trans. 1, V. 68, Pt. 8, p. 1423-34.

Kamel, K. H. M. ; Awad, S. A. and Kassab, A., 1979, Mechanism of electrochemical reactions at aluminum electrodes in sodium hydroxide solutions:

J. Elec.troanal . Chem. Interfacial Electrochem. , V. 99, No. 1, p. 121-5.

Khan, J. M. and Makowiecki, D. M. , 1978, Investigation of room-temperature

oxidation of aluminum thin films by scanning high-energy electron diffraction

Surf. Sci., V. 77, No. 1, p. L155-L161.

Kirk, C. T. , Jr. and Hueer , E. E., Jr., 1968, Oxidation of aluminum films

in low-pressure oxygen atmospheres: Surf. Sci., V. 9, No. 2, p. 217-45.

Kiselev, V. I. and Lepinskikh, B. M. , 1974, Kinetics of oxidation of

molten aluminum: Deposited Doc. , VINITI 542-74, 12 p.

Kiselev, V. I.; Lepinskikh, B. M. and Zhuchkov, V. I., 1974, Kinetics of

liquid metal oxidation by oxygen from the gaseous phase: Tr. Inst.

Me tall. , Akad. Nauk SSSR, Ural. Nauchn. Tsentr., V. 28, p. 117-20.

Klei, H. E. and Stutzman, L. F. , 1968, Effect of oxide thickness on the

oxidation of aluminum films: Mater. Sci. Eng., V. 3, No. 2, p. 71-5.

Krakauer, H. ; Posternak, M. ; Freeman, A. J. and Koelling, D. D. , 1981,

Initial oxidation of the aluminum(OOl) surface: Self-consistent electronic

structure of clean aluminum(OOl) and aluminum(001)-p(l x l)oxygen: Phys.

Rev. B: Condens. Matter, V. 23, No. 8, p. 3859-76.

Krueger, W. H. and Pollack. S. R. , 1972, Initial oxidation of aluminum

thin films at room temperature: Surface Sci., V. 30, No. 2, p. 263-79.

Labunov, V. A.; Parkhutik, V. P. and Gavrilov, I. G., 1977, Kinetics of

low temperature oxidation of metals in closed systems: Vestsi Akad.

Navuk BSSR, Ser. Fiz.-Tekh. Navuk, No. 4, p. 37-40.
- 41 -

Section _B , continued

Labunov, V. A.; Parkhutik, V. P. and Tkharev, E. E. , 1978, Model of the

low- temperature oxidation of metals: Zh. Fiz. Khim. , V. 52, No. 5,

p. 1168-71.

Labunov, V. A.; Smirnov, A. G. and Kazantsev, A. P. , 1976, Effect of con- ditions for carrying out plasma oxidation on the kinetics of oxide

growth on aluminum: v sb., Nitevid. Kristally i Tonkie Plenki.

,

Ch. 2, p. 487-93.

Leitenberger , H. ; Liebgott, H.; Schmidt, H. J. and Wuellenweber , H.

,

1973, Hydrogen from methanol and steam (Patent) : Germany Offen.

DE 2220617.

Lepinskikh, B. M. and Kiselev, V. I., 1974, Oxidation of liquid metals

and alloys by oxygen from the gas phase: Izv. Akad. Nauk SSSR, Met.,

No. 5, p. 51-4.

Levina, R. A. and Oleinikov, G. N., 1983, Contact potential difference

study of the oxidation of aluminum: Real. Struktura i Svoistva Tverd

.

Tel, Sverdlovsk, p. 23-8.

Lokenbach, A. K. ; Strods, V.; Lepins, L. ; Sulce, A.; Abrams, I. and

Zaporina, N. A. , 1981, Effect of the initial state of the surface on oxidation kinetics of highly dispersed aluminum powders: Latv. PSR

Zinat. Akad. Vestis, Kim. Ser., No. 1, p. 50-8.

Lokenbaha, A.; Strods, V.; Zaporina, N. A.; Abeltina, A.; Stodere, M.;

Lepins, L. and Abrams, I., 1983, Nonisothermal oxidation of highly

dispersed aluminum powders: Latv. PSR Zinat. Akad. Vestis, Kim. Ser.,

No. 3, p. 310-14.

Lokenbach, A. K. ; Zaporina, N. A. and Lepins, L., 1981, Phase composition

and structure of oxide films on particles of highly dispersed aluminum

powders: Latv. PSR Zinat. Akad. Vestis, Kim. Ser., No. 1, p. 45-9.

Maksimenko, V. I. and Maksimenko, L. S., 1973, Kinetics of oxidation of

aluminum and its alloys in the liquid state: Nov. Teor. Tekhnol.

Metall. Protsessov, p. 16-20.-

Meierhoefer, W. and Oswald, H. R. , 1972, Reaction of aluminum with molecular

oxygen and nitrogen at temperatures between 400 and 600 deg: Therm. Anal.,

Proc. 3rd Int. Conf., Inorg. Chem. Inst., Univ. Zurich, Zurich, Switz.,

(Wiedemann, H. G. , Ed.), V. 2, p. 409-21.

Michel, R. ; Jourdan, C. ; Castaldi, J. and Derrien, J., 1979, On the initial

interaction of oxygen with the (111) and (100) aluminum surfaces: Surf.

Sci., V. 84, No. 2, p. L509-L514.

Mitin, B. S. and Samoteikin, V. V., 1971, Oxidation of molten aluminum: Zh

.

Fiz. Khim., V. 45, No. 3, p. 730.
Section B, continued

Moskovits, M. , 1972, Kinetics of oxidation of molten aluminum in oxidant

streams: Oxid. Metals, V. 5, No. 1, p. 1-9.

Murata, Y. and Ohtani, S., 1972, Measurement of the growth of oxide layers

on metals by low-energy electron spectroscopy. Aluminum: J. Vac. Sci.

Technol . , V. 9, No. 2, p. 789-91.

Natanson, M. E., 1968, Spectral analysis of surface oxidation of different

metals: Dopov. Akad. Nauk Ukr. RSR, Ser. B, V. 30, No. 11, P. 1019-21.

Nevskii, 0. I.; Volkov, V. I.; Grishina, E. P. and Rumyantsev, E. M. , 1979,

Effect of surface films on the mechanism of the anodic dissolution of

aluminum: Progres. Elektrofiz. i Elektrokhim. Metody Obrab., Saratov,

p. 17-21.

Oblath, S. B. and Gole, J. L, 1980, On the continuum emissions observed

upon oxidation of aluminum and its compounds: Combust. Flame, V. 37,

No. 3, p. 293-312.

Pitts, J. R. ; Bischke, S. D.; Falconer, J. L and Czanderna, A. W., 1984,

Oxide formation on aluminum in the presence of keV electrons and carbon

dioxide: J. Vac. Sci. Technol., A, V. 2, No. 2, Pt. 2, p. 1000-3.

Pryor, M. J. , 1971, Low-temperature oxidation. Discussion: Oxid. Metals,

V. 3, No. 3, p. 271-3.

Radin, A. Ya., 1974, Oxidation of molten metals: Svoistva Rasplavl. Met.,

Tr. 16th Soveshch. Teor. Liteinykh Protsessov, USSR, (Gulyaev, B. B., Ed.),

p. 116-22.

Severdenko, V. P.; Labunov, V. A. and Stel'makh, V. T., 1971, Kinetics of

aluminum film oxidation in oxygen plasma: Khim.-Term. Obrab. Metal. Splavov,

p. 154-6.

Shinohara, K. ; Kyogoku, H.; Kumada, K. and Seo, T. , 1980, Oxidation kinetics

of aluminum single crystals in a transmission electron misroscope: Ehime

Daigaku Kiyo, Shizen Kagaku, B, V. 9, No. 3, p. 781-90.

Sinaiskii, N. A., 1971, Plasma-chemical process for preparing gamma-alumina:

Nizkotemp. Plazma Tekhnol. Neorg. Veshchestv, Tr, 2nd Vses. Semin., USSR,

(Zhukov, M. F. , Ed.)

.

Stolyarov, E. A. , 1968, Oxidation of aluminum with water by the action of

ultrasound: Zh. Prikl. Khim. (Leningrad), V. 41, No. 10, p. 2302-3.

Stone, H. E. N. , 1972, Oxidation of metals in relation to the periodic

classification: J. Mater. Sci., V. 7, No. 10, p. 1147-53.
-43-

Section J3, continued

Szalkowski, F. J. , 1982, Evidence for a molecular intermediate during the

oxidation of aluminum by water: J. Chem. Phys., V. 77, No. 10,

p. 5224-7.

Szczeklik, J. and Schabowska, E., 1980, Kinetics of the formation of thin

films of aluminum oxide in a low temperature plasma: Thin Solid Films,

V. 71, No. 1, p. L17-L19

.

Vernidub, I. I.; Makolkin, I. A.; Gusev, N. I. and Abramov, Yu. A., 1968,

Thermodynamic characteristics of the oxidation of aluminum and magnesium

by water and water vapor: Tr., Mosk. Inst. Nar. Khoz. , No. 46, p. 18-23.

Wahl, G. , 1983, Coating composition and the formation of protective oxide

layers at high temperatures: Thin Solid Films, V. 107, No. 4, P. 417-26.

Wiedmer, E. and Grauer, R. , 1974, Behavior of aluminum electrodes in fluoride

solutions: Aluminum (Duesseldorf ) , V. 50, No. 4, p. 268-70.

Yu, H. L.; Munoz, M. C. and Soria,. ,F. , 1980, On the initial stages of

oxidation of aluminum (111) by LEED analysis: Surf. Sci. , V. 94, No. 2-3,

p. L184-L190.

Zhuravlev, V. A. and Zakharov, A. P., 1980, Oxidation of aluminum in water

at different temperatures: Dokl. Akad. Nauk SSSR, V. 252, No. 5, p. 1162-6.

Zhuravlev, V. A. and Zakharov, A. P., 1980, Induction period at the initial

stages of aluminum oxidation in water: Dokl. Akad. Nauk SSSR, V. 254,

No. 5, p. 1155-8.
-44-

C. Reaction of LiAl alloy with water

Ichiki, M. and Ishii, M. , 1973, Electrolytic purification of waste water

(Patent): Germany Offen. DE 2225701.

Kanin, E. N. ; Gustareva, A. A.; Brazhnikova, G. I. and Zhukova, V. P.,

1978, Anodic oxidation of an aluminum-magnesium-lithium alloy: Zashchita

ot Korrozii Konstruktsion. Splavov. , Kuibyshev, p. 84-90.

Oda, N. ; Yoshida, T.; Nakanishi, T.; Yoshikawa, K. ; Adachi, A.; Ueda, J. and Mizota, A., 1974, Production of high pressure gas (Patent): Japan

Kokai Tokkyo Koho JP 7447282.

Oda, T. ; Yoshida, T. ; Nakanishi, T. ; Yoshikawa, K.; Adachi, A.; Ueda, S.

and Mizota, A., 1977, Generation of a high-pressure gas propellant for

self-propelled underwater vessels (Patent): Japan Tokkyo Koho JP 7727626.

Urbach, H. B. ; Icenhower, D. E. ; Cervi, M. C. and Bowen, R. J., 1974, Fuel

cell using lithium-aluminum alloy anode and aqueous electrolyte (Patent):

United States US 482980.
-45-

D. Oxidation of LiAl alloy

Carpio, R. A. and King, L. A., 1981, Deposition and dissolution of lithiumaluminum alloy and aluminum from chloride-saturated lithium chloride-aluminum

chloride and sodium chloride-aluminum chloride melts: J. Electrochem.

Soc. , V. 128, No. 7, p. 1510-17.

Field, D. J. ; Butler, E. P. and Seamans, G. M. , 1981, High- temperature oxidation

studies of aluminum-3 wt . % lithium, aluminum-4.2 wt . % magnesium and

aluminum-3 wt. % lithium-2 wt . % magnesium alloys: Alum. -Lithium Alloys,

Proc. 1st Int. Alum. -Lithium Conf . , Dep. Metall. Mater. Sci., Imp. Coll.,

London, Engl., (Starke, E. A., Jr., Ed.), p. 325-46.

Fridlyander, I. N.; Litvintsev, A. I.; Gabidullin, R. M. ; Dudkina, S. I.;

Klimova, L. N. and Shiryaeva, N. V., 1968, Oxidation of alloys of an aluminum-magnesium-lithium system with a beryllium additive: Alyum.

Splavy, V. 5, p. 335-41.

Fridlyander, I. N. ; Sandler, V. S.; Nikol’skaya, T. I.; Savinkov, R. A. and

Roshchina, I. N., 1978, Study of the near-surface layer of the aluminum

alloy 01420: Izv. Akad. Nauk SSSR, Met., No. 2, p. 220-2.

Goncharov, V. I. and Breslavets, V. P. , 1979, Mechanism of lithium-aluminum

electrode performance: Fiz. Khim. Elektrokhim. Rasplavl. Tverd. Elektrolitov

,

Tezisy Dokl. Vses. 7th Konf . Fiz. Khim. Ionnykh Rasplavov Tverd. Elektrolitov,

USSR, V. 2, p. 125-7.

Horski, J., 1970, Method for obtaining tritiated water from a lithium-aluminum

alloy irradiated in a reactor: Nov. Metody Poluch. Radioaktiv. Prep., Sb.

Dokl. Simp., Cent. Prod. Distrib. Isot. , Inst. Nucl. Res., Swierk, Pol.,

p. 311-18.

Kanin, E. N.; Gustareva, A. A.; Brazhnikova, G. I. and Zhukova, V. P. , 1978,

Anodic oxidation of an aluminum-magnesium-lithium alloy: Zashchita ot

Korrozii Konstruktsion. Splavov. , Kuibyshev, p. 84-90.

Kuz'michev, L. V.; Maizlin, L. Ya. ; Radin, A. Ya. and Gureev, B. D., 1976,

Oxidation of aluminum- lithium alloys and methods of protection: Tekhnol.

Legkikh Splavov. Nauch.-tekhn. Byul. VILSa, No. 8, p. 18-22.

L'vov, A. L. ; Gnilomedov, A. A. and Protasov, E. N. , 1979, Anodic oxidation

of lithium-aluminum alloys in fused chlorides: Elektrokhim. Ionnykh

Rasplavov, Saratov. Gos. Univ. , Saratov, USSR, (Delimarskii, Yu. K., Ed.),

p. 135-9.

L'vov, A. L. ; Gnilomedov, A. A. and Protasov, E. N., 1979, Electrochemical

behavior of lithium-magnesium, lithium-magnesium-aluminum, and lithiumsilicon alloys in a lithium chloride-potassium chloride molten eutectic:

Issled. v Obi. Khim. Istochnikov Toka, (Saratov), No. 6, p. 3-6.

l.'vov, A. L; Gnilomedov, A. A.; Selemenev, A. P. and Protasov, E. N., 197 rj,

Anodic dissolution of lithium-aluminum alloys in a lithium chloride-pot ns . i urn chloride melt: Elektrokhimiya , V. 11, No. 9, p. 1322-4.
-46-

E. Oxidation of Magnesium metal, including kinetics and oxidation by water

Andreev, L. A.; Lunskii, M. Kh. ; Gel'man, B. G. and Zhukhovitskii , A. A.,

1973, Kinetics of exoelectron emission during the oxidation of magnesium:

Zh. Fiz. Khim., V. 47, No. 4, p. 852-5.

Bellobono, I. R. ; Mazza, F. and Cataldi, M. T., 1976, Spontaneous dissolution

of metals in aqueous electrolytes. II. Kinetics of the reaction of magnesium

and zinc with hydrochloric acid solutions: Gazz. Chim. Ital. , V. 106, No. 3-6,

p. 259-65.

Benninghoven, A. and Wiedmann, L. , 1974, Investigation of surface reactions by

the static method of secondary ion mass spectrometry. IV. Oxidation of

magnesium, strontium, and barium in the monolayer range: Surface Sci.,

V. 40, No. 2, p. 483-92.

Bloshenko, V. N. ; Merzhanov, A. G. and Khaikin, B. I, 1976, Determination of

the kinetic parameters of the high- temperature oxidation of magnesium: Fiz.

Goreniya Vzryva, V. 12, No. 5, p. 682-8.

Cismaru, D. and Simon, Z. , 1969, Kinetics of the formation of oxide layers

on metals: Rev. Roum. Chim., V. 14, No. 7, p. 837-43.

Faeber, W. and Braun, P., 1975, Investigations of the oxide formation on metals with the Auger electron spectroscopy: Mikrochim. Acta, Suppl. , V. 6,

p. 391-402.

Felder, W. , 1981, Kinetics of some metal atom and metal fluoride oxidation

reactions relevant to Air Force technology development: AeroChem Res. Lab.

Inc., Princeton, NJ, Report No. AER0CHEM-TP-411, AFOSR-TR-81-0599, 20 p.

Flodstrom, S. A.; Martinson, C. W. B.; Kalkoffen, G. and Kunz, C., 1980,

Oxygen interaction with clean aluminum and magnesium films investigated

by synchrotron-radiation- induced photoemission: Mater. Sci. Eng., V. 42,

No. 1, p. 31-7.

Frishberg, I. V. and Mikulinskii, A. S., 1966, Comparison of oxidizability

of metallic powders prepared by condensation and mechanically: Tr. Inst.

Metall. , Sverdlovsk, V. 11, p. 49-53.

Fuggle, J. C. ; Watson, L. M. ; Fabian, D. J. and Affrossman, S., 1975, X-ray

photoelectron studies of the reaction of clean metals (magnesium, aluminum,

chromium, manganese) with oxygen and water vapor: Surf. Sci., V. 49, No. 1, p. 61-76.

Gorbunov, V. V.; Khromov, V. G. and Shidlovskii, A. A., 1971, Oxidative

activity of water vapor, carbon dioxide, and carbon monoxide toward magnesium

and aluminum powders: Zh. Prikl. Khim. (Leningrad), V. 44, No. 4, p. 727-34.

Glushkov, V. E. and Fedoseeva, N. V., 1966, Ignition of magnesium particles in

steam: Fiz. Goreniya, I. I. Mechnikov Odessk. Gos. Univ. , Odessa, USSR,

p. 37-41.
-47-

Section JE , continued

Grasselli, R. K. ; Suresh, D. D. and Hardman, H. F. , 1976, Oxidation catalyst

(Patent): Germany Offen. DE 2530959.

Hayashi, S. and Saito, H., 1972, Growth of fibrous magnesia via the vapor phase:

Yogyo Kyokai Shi, V. 80, No. 8, p. 319-23.

Hayden, B. E. ; Klemperer, D. F. ; Allen, G. C. and Tucker, P. M. , 1980, The

early stages of oxidation of magnesium, aluminum and magnesium/aluminum

alloys: Vide, Couches Minces, V. 201, Suppl. , Proc. 4th Int. Conf. Solid

Surf., VI, p. 453-7.

Hayden, B. E. ; Schweizer, E. ; Koetz, R. and Bradshaw, A. M., 1981, The early

stages of oxidation of magnesium single crystal surfaces: Surf. Sci., V. Ill,

No. 1, p. 26-38.

Hodgson, A. and Machie, J. C., 1979, A shock-tube study of the kinetics of

evaporation and oxidation of magnesium: Combust. Flame, V. 35, No. 3, p. 323-34.

Kashireninov , 0. E. ; Kuznetsov, V. A. and Manelis, G. B. , 1974, Kinetics of

the gas-phase reaction of magnesium with oxygen: AIAA Pap., V. 74-145, 8 p.

Kashireninov, 0. E. ; Manelis, G. B. and Repka, L. F., 1982, Refinement of

kinetic constants for the oxidation of alkaline earth metal vapors: Zh. Fiz.

Khim., V. 56, No. 4, p. 1030-1.

Kashireninov, 0. E. and Osherov, V. I., 1981, Polanyi-Semenov rule in gas-phase

reactions of alkaline earth metals: Dokl. Akad. Nauk SSSR, V. 257, No. 3,

p. 636-40.

Koetz, R. ; Hayden, B. ; Schweizer, E. and Bradshaw, A. M. , 1981, The application

of spectroscopic ellipsometry to the oxidation of magnesium: Surf. Sci.,

V. 112, No. 3, p. 229-40.

Kovalev, G. I.; Gogitidze, L. D. ; Kuranova, V. I. and Denisov, E. T., 1979,

Kinetics of the oxidation of fuels in the presence of structural materials:

Nef tekhimiya, V. 19, No. 2, p. 237-43.

Lea, C. and Molinari, C. , 1984, Magnesium diffusion, surface segregation and

oxidation in aluminum-magnesium alloys: J. Mater. Sci., V. 19, No. 7,

p. 2336-52.

Markstein, G. H. , 1968, Study of the reaction of magnesium vapor and oxygen at

the surface of magnesia deposits by atomic-absorption spectrophotometry:

Purdue Univ., Lafayette, IN, U. S. Clearinghouse Fed. Sci. Tech. Inform., AD,

No. AD-672575, 34 p.

Namba, H. ; Darville, J. and Gilles, J. M., 1980, Oxidation of single crystalline magnesium (0001) studied by ELS, AES, LEED and work function measurement.'

Vide, Couches Minces, V. 201, Suppl., Proc. 4th Int. Conf. Solid Surf., VI,

p. 470-3.
-48-

Section _E, continued

Namba, H. ; Darville, J. and Gilles, J. M. , 1981, A model for the oxidation of

magnesium (0001) based upon LEED, AES, ELS and work function measurements:

Surf. Sci., V. 108, No. 3, p. 446-82.

Natanson, H. E. , 1968, Spectral analysis of surface oxidation of different

metals: Dopov. Akad . Nauk Ukr. RSR, Ser. B, V. 30, No. 11, p. 1019-21.

Ponomarenko, A. M. ; Bondarev, B. I. Ivanov, V. S., 1978, Kinetics of liquid

magnesium oxidation in an atmosphere of air and argon with sulfur dioxide

and sulfur hexafluoride additives: Tekhnol. Legk. Splavov, No. 8, p. 3-8.

Sarrazin, P. and Besson, J., 1966, Kinetics of magnesium oxidation by dry

oxygen at 350-450 degrees. Pressure dependence: Metallurgie (Mons, Belg.),

V. 6, No. 1, p. 11-15.

Selivanov, S. E., 1971, Oxidation of magnesium in nitrous oxide: Fiz.

Aerodispersnykh Sist., No. 4, p. 62-6.

Sergeev, G. B.; Smirnov, V. V.; Zagorskaya, 0. V.; Zagorskii, V. V. and

Popov, A. V. , 1982, Low- temperature reaction of magnesium atoms and carbon

dioxide: Vestn. Mosk. Univ. , Ser. 2: Khim. , V. 23, No. 3, p. 232-6.

Shevtsov, V. I. and Fursov, V. P. , 1983, Study of the mechanism of oxidation of magnesium: Fiz. Goreniya Vzryva, V. 19, No. 4, p. 99-102.

Stone, H. E. N., 1972, Oxidation of metals in relation to the periodic classification: J. Mater. Sci., V. 7, No. 10, p. 1147-53.

Svettsov, V. I. and Labirev, V. L. , 1981, Calculation of process rates

during the plasma reaction-thermal deposition of oxide films: USSR,

Deposited Doc., Report No. SPSTL 61 khp-D81, 21 p.

Tetere, A.; Steina, D. ; Lokenbah, A.; Lepins, L. and Abrams, I., 1976,

Oxidation of magnesium hydrosol: Latv. PSR Zinat. Akad. Vestis, Kim.

Ser., No. 5, p. 564-8.

Tiunov, V. S. ; Mamaev, V. I. and Morachevskii, A. G., 1979, Study of the

electrochemical behavior of lithium-magnesium alloys in a lithium chloridepotassium chloride molten electrolyte: Fiz. Khim. Elektrokhim. Rasplavl.

Tverd. Elektrolitov, Tezisy Dokl. Vses. 7th Konf. Fiz. Khim. Ionnykh Rasplavov

Tverd . Elektrolitov, V. 2, 122 p.

Tseluikina, G. V. and Abakhaev, M. G., 1981, Electrochemical behavior of

magnesium in liquid ammonia media: Khim. Istochniki Toka, Novocherkassk,

p. 50-6.

Vale, R. and Smallman, R. E. , 1977, An x-ray topographic study of the behavior of vacancy loops formed during the high-temperature oxidation of

magnesium crystals: Philos. Mag., V. 36, No. 1, p. 209-23.
-49-

Section Ii, continued

Vernidub, I. I.; Makolkin, I. A.; Busev, N. I. and Abramov, Yu. A., 1968,

Thermodynamic characteristics of the oxidation of aluminum and magnesium

by water and water vapor: Tr., Mosk. Inst. Nar. Khoz., No. 46, p. 18-22.

Williams, R. E. and Kottenstette, J. P., 1967, Approach to combustion kinetics

new technique: West. States Sect., Combust. Inst. (Pap.), No. 67-27, 14 p.
-50-

F. Oxidation of aluminum-magnesium alloy, including kinetics and oxidation

by water

Anthony, W. H. and Rasmussen, T. S. , 1976, Corrosion-resistant aluminum com- posite material (Patent): Germany Offen. DE 2458201.

Baranov, N. S. ; Lotsmanov, S. N. ; Stepanov, G. A.; Getalov, S. P. ; Red 'kin, L. A. Lokhmatov, B. V. ; Egorov, V. M. and Shlyamneva, I. A., 1970, Alloy for dehydration of molten salts (Patent): USSR SU 270462.

Boehmer, M. and Munz, D. , 1975, Fatigue of an aluminum-magnesium alloy (AlMg 3 ) in gases of different pressures. I. Fatigue life measurements: Z. Metallkd.,

V. 66, No. 6, p. 329-33.

Boehmer, M. and Munz, D. , 1975, Fatigue of an aluminum-magnesium (AlMg 3 ) in gases of different pressures. II. Surface studies and f ractography

:

Z. Metallkd., V. 66, No. 6, p. 333-7.

Boehmer, M. and Munz, D. , 1975, Fatigue of the aluminum alloy AlMg 3 in gases of

different pressures. III. Gas-metal interaction during fatigue: Z. Metallkd.

V. 66, No. 7, p. 416-21.

Case, B. ; Bradford, P. M. and Garbett, K., 1977, Silicate and the aqueous

corrosion of a high-magnesium alloy: Nature (London), V. 268, No. 5617,

p. 223-5.

Cherepakhova, G. L. and Shreider, A. V. , 1972, Effect of the ions of cooling

waters on the pitting corrosion of an aluminum-magnesium alloy: Zh.

Prikl. Khim. (Leningrad), V. 45, No. 9, p. 1958-63.

Cochran, C. N.; Belitskus, D. L. and Kinosz, D. L., 1976, Oxidation of

aluminum-magnesium melts in air, oxygen, flue gas, and carbon dioxide:

Light Met., Proc. Sess., AIME Ann. Meet., V. 2, p. 203-27.

Ford, F. P. , 1972, Stress corrosion-resistant aluminum-magnesium alloy (Patent):

Germany Offen. DE 2114209.

Gavra, Z. ; Hadari, Z. and Mintz, M. H., 1981, Effects of nickel and indium

ternary additions on the hydrogenation of magnesium-aluminum intermetallic

compounds: J. Inorg. Nucl. Chem. , V. 43, No. 8, p. 1763-8.

Gorbunov, V. V.; Vasil'ev, A. V. and Shidlovskii, A. A., 1959, Combustion

of mixtures of high-energy metal powders with water: Izv. Vyssh. Ucheb.

Zaved., Khim. Khim. Tekhnol. , V. 12, No. 9, p. 1171-4.

Grauer, R. and Schmoker, P. , 1976, The oxidation of aluminum-magnesium alloys

in oxygen at elevated temperatures: Werkst. Korros., V. 27, No. 11, p. 769-74.

Haginoya, I. and Fukusako, T. , 1984, Influence of water vapor on the oxidation of molten aluminum-magnesium alloys: Imono, V. 56, No. 5, p. 264-8.
- 51 -

Section _F, continued

Hayden, B. E. ; Klemperer, D. F. ; Allen, G. C. and Tucker, P. M. , 1980, The

early stages of oxidation of magnesium, aluminum and magnesium/aluminum

alloys: Vide, Couches Minces, V. 201, Suppl. , Proc. 4th Int . Conf. Solid

Surf., VI, p. 453-7.

Kovalenko, A. I., 1979, Electrochemical characteristics of anode alloys in

stratal water: Korroz. Zashch. Neftegazov. Prom-sti. , No. 7, p. 16-19.

Kuznetsov, D. A.; Notkin, E. B. and Malakhov, A. I., 1969, Effect of some

factors on the quantity and chemical composition of evolving gases during

sand mold casting of aluminum-magnesium alloys: Tr. Mosk. Khim. -Tekhnol

.

Inst., No. 60, p. 254-6.

Lepinskikh, B. M. and Belousov, A. A., 1975, Study of the kinetics of

oxidation of magnesium-aluminum alloys in a molten state: Deposited Doc.,

VINITI 554-76, 12 p.

Maischak, K. D. and Feige, W. , 1970, Causes and prevention of aluminum-water

explosions: Neue Huette, V. 15, No. 11, p. 662-5.

Makovichuk, Yu. I. and Psarev, V. I., 1976, Agglomeration kinetics of betaphase particles in aluminum-magnesium alloys: Nekotor. Vopr. Fiz. Kinet.

Tverd. Tel, No. 2, p. 35-63.

Mima, G. and Yamaguchi, M. , 1964, Isothermal softening spectrum of cold drawn

aluminum alloys with 2 weight % magnesium. Optical microscopic observations

and kinetics of isothermal softening: Nippon Kinzoku Gakkaishi, V. 28,

p. 710-16.

Mintz, M. H. ; Malkiely, S.; Gavra, Z. and Hadari, Z., 1978, Effect of Group

IIIA metal additives on the kinetics of magnesium hydride formation: J. Inorg. Nucl. Chem., V. 40, No. 11, p. 1949-51.

Nair, C. G. K., 1983, Kinetics of magnesium loss during melting/holding of

aluminum-magnesium alloys: Trans. Indian Inst. Met., V. 36, No. 4-5, p. 351-3.

Nikitina, M. F. ; Fadeeva, G. N. and Romashin, V. M. , 1966, Oxidation kinetics

of aluminum-magnesium alloys: Tr., Mosk. Aviats. Tekhnol. Inst., No. 67,

p. 65-78.

Pagetti, J., 1972, New device for studying passivation of metals and alloys:

AVIRES 2, Colloq. 2nd Int. Appl. Sci. Tech. Vide Revetements Etats Surface,

C. R. , Lab. Genie Chim. , Ec. Natl. Super. Chim. Paris, Fr. , p. 174-88.

Psarev, V. I. and Kulikov, A. F. , 1977, Kinetics of the coalescence of

disperse beta-phase of aluminum-magnesium alloys. I: Izv. Vyssh.

Uchebn. Zaved . , Fiz., V. 20, No. 12, p. 46-51.

Radin, A. Ya., 1974, Oxidation of molten metals: Svoistva Rasplavl. Met.,

16rh Tr. Soveshch. Teor. Liteinykh Protsessov, USSR (Gulyaev, B. B. , F.d.),

p. 116-22.
-52-

Section _F , continued

Ryum, N. and Embury, J. D. , 1982, A comment on the recrystallization behavior

of aluminum-magnesium: Scand. J. Metall. , V. 11, No. 2, p. 51-4.

Shimogori, K. ; Fujiwara, K. and Komura, M. , 1974, Corrosion-resistant aluminum

alloy useful as heat exchanger tube material (Patent) : Japan Kokai Tokkyo

Koho JP 7458013.

Shrieder, A. V. and Cherepakhova, G. L. , 1972, Reversal of polarity during

the contact corrosion of aluminum-magnesium alloys: Zh. Prikl. Khim.

(Leningrad), V. 45, No. 7, p. 1603-4.

Tuck, C. D. S. and Seamans, G. M. , 1982, Hydrogen embrittlement of aluminumzinc-magnesium and aluminum-magnesium alloys: Hydrogene Mater., 3rd Congr.

Int., Alcan Int. Ltd., Banbury, UK (Azou, P., Ed.), V. 2, p. 665-70.
h

-53-

G. Lithium-beryllium alloys

Alekseevskii , N. E. and Zakosarenko, V. M. , 1973, Superconductivity of

beryllium alloys: Dokl. Akad Nauk SSSR, V. 208, No. 2, p. 303-6.

Fridlyander, I. N.; Gulin, A. N. ; Sandler, V. S.; Yatsenko, K. P. ; Kolesnikova,

V. I.; Polyakov, E. S. and Yudin, A. F. , 1971, Deformable alloy based

on aluminum (Patent) : USSR SU 310946.

Griffiths, L. B. , 1969, Fine-grained, ductile beryllium-aluminum-magnesiumsilicon composites obtained by chill-mold casting under argon using lithium

chloride and fluoride as flux (Patent): France FR 1567093, 9 p.

Krock, R. H.; Larsen, E. I. and Jones, C. R. , 1967, Alloys of beryllium with

aluminum magnesium (Patent): United States US 3323880, 5 p.

Krock, R. H. ; Larsen, E. I. and Jones, C. R. , 1967, Alloys of beryllium with

silver and aluminum (Patent): United States US 3322512, 5 p.

Nishimura, M. , 1971, Beryllium-containing metal filler for welding aluminum

(Patent): Japan Tokkyo Koho JP 7139452, 2 p.

TRW Inc., 1968, Controlled heat production by the reaction of sulfur hexafluoride with lithium (Patent): France FR 1526940, 3 p.

Pauliukonis, R. S. , 1967, Sulfur hexafluoride-lithium fuel (Patent): United

States US 3325318, 2 p.
-54-

H. Lithium-boron aiioys

Bischof, J. ; Dlouhy, Z,; Kvitek, V. and Vobecky, M. , 1972, Determination

of boron and lithium in materials by an (n, alpha) nuclear reaction:

Jad. Energ., V. 18, No. 9, p. 269-8.

Bom, E. and Loewedey, R. , 1975, Diffusion of the products of the nuclear

reaction 10B(n, alpha) 7Li and hydrogen in single crystals of betarhombohedral boron: Atomkernenergie , V. 26, No. 4, p. 283-4.

Born, E. ; Krahl, J. and Loewedey, R. , 1975, Distribution of lithium in

surface layers of neutron irradiated boron crystals and its change following heat treatment: Atomkernenergie, V. 26, No. 1, p. 58-60.

Dallek, S., Ernst, D. W. and Larrick, B. F., 1979, Thermal analysis of

lithium-boron alloys: J. Electrochem. Soc. , V. 126, No. 5, p. 866-70.

Dallek, S. ; Larrick, B. F. and Szwarc, R. , 1982, Lithium-boron alloy anodes

for thermally activated batteries: Proc. Power Sources Symp., V. 30,

p. 42-5.

De Vries, R. C. and Fleischer, J. F. , 1972, Cubic boron nitride preparation

from lithium-boron-nitrogen mixtures (Patent): United States US 3701826.-

DeVries, L. E. and Gubner, E., 1978, Determination of main components and

impurities in lithium-boron alloys: Anal. Chem. , V. 50, No. 6 , p. 694-8.

Dzhakhandarov , Sh. D. ; Rza-Zade, P. F. ; Samedov, F. R. and Eyubova, N. A.

,

1975, Phase diagram of the lithium oxide-boron oxide-cobalt(II) oxide

(Li 20 .

B

2 O 3 -C0 O) system: Azerb. Khim. Zh., No. 4, p. 116-18.

Ernst, D. , 1982, DSC study of two reactions in the lithium-boron alloy system

J. Electrochem. Soc. , V. 129, No. 7, p. 1513-15.

Ferguson, I. F. ; Masters, D. R. and Turek, M., 1983, The Auger spectra of

lithium metal and "oxidized lithium": Salwick/Preston, UK, North, Div.

Rep. ND-R - U. K. At. Energy Auth. , Report No. ND-R-463(S), 26 p.

Itoh, M. ; Sato, S. and Yokokawa, T., 1976, E.m.f. measurements of molten

mixtures of lithium oxide +, sodium oxide +, and potassium oxide + boron

oxide: J. Chem. Thermodyn. , V. 8 , No. 4, p. 339-52.

James, S. D. , 1981, Comparison of anodic dischargability of lithium-boron

alloy with pure lithium in lithium carbide (LiCIO) 4-propylene carbonate:

Naval Surface Weapons Cent., Silver Spring, MD, Report No. NSWC/TR-8 1-155

,

SBI-AD-F500015, 27 p.

James, S. D. , 1982, Comparison of anodic dischargeability of lithium-boron

alloy with pure lithium in lithium perchlorate-propylene carbonate:

J. Appl. Electrochem., V. 12, No. 3, p. 317-21.
Section H, continued

James, S. D. and De Vries, L. E. , 1976, Structure and anodic discharge

behavior of lithium-boron alloys in the lighium chloride-potassium chloride

eutectic melt: J. Electrochem Soc., V. 123, No. 3, p. 321-7.

Kezuka, H. and Iwamura, K. , 1982, Studies of thin films of lithium-boron

alloys: Appl. Surf. Sci. , V. 11-12, No. 1-3, p. 144-8.

Kilroy, W. P. and Angres, I., 1979, The extraction and determination of

free lithium in lithium-boron alloys: J. Less-Common Met., V. 63, No. 1,

p. 123-8.

Larrick, B. F. ; James, S. D. and Szwarc, R. , 1978, Lithium-boron alloy - a new battery anode material: Proc. - Power Sources Symp. , V. 28th, p. 95-8.

Lewis, H. L, 1980, Exothermic IR source materials. Lithium-boron alloy

materials: Nav. Weapons Support Cent., Crane, IN, Report No. NWSC/CR/RDTR-134

,

18 p

.

Lewis, H. L. , 1982, Thermogravimetric analysis of reactivity of an air-reactive

alloy of lithium and boron: Proc. Int. Pyrotech. Semin., V. 8, p. 446-65.

McManis, G. E. ; Miles, M. H. and Fletcher, A. N. , 1984, The lithium-boron

alloy anode in molten nitrate electrolytes: J. Electrochem. Soc., V. 131,

No. 2, p. 286-9.

Mestwerdt, R. and Selzer, H. , 1976, Experimental investigation of boron/lithium

combustion: ALAA J. , V. 14, No. 1, p. 100-2.

Mitchell, M. A. and Sutula, R. A., 1978, The density, electrical resistivity

and Hall coefficient of lithium-boron alloys: J. Less-Common Met., V. 57,

No. 2, p. 161-75.

Nakamura, S. and Hayashi, H. , 1975, Compounds in a lithium oxide-boron

oxide-water system: Yogyo Kyokai Shi, V. 83, No. 1, p. 38-45.

Schleyer, P. v. R. , 1983, Are lithium carbide (CLie), lithium nitride (NLis),

lithium oxide (0Lii+), etc., hypervalent ? : New Horiz. Quantum Chem. , Proc.

4th Int. Congr. Quantum Chem., Fr iedr ich-Alexander-Univ . Erlangen-Nurnberg

,

Erlangen, Germany (Loewdin, P.-O. and Pullman, B., Ed.), p. 95-109.

Samedov, F. R. ; Rzazade, P. F. and Abdullaev, G. K. , 1970, The Li 20 .B 203 ~ Ga20a system: Izv. Akad . Nauk SSSR, Neorg. Mater., V. 6, No. 5, P. 1030-1.

Secrist, D. R. , 1967, Compound formation in the systems lithium-carbon and

lithium boron: J. Am. Ceram. Soc., V. 50, No. 10, p. 520-3.

Selzer, H. , 1975, Use of lithium boride (LiB 2 ) in pyrotechnic fires: Pyrotech.:

Grundlagen, Technol. Anwend . , Jahrestag. , Inst. Chem. Treib-Explosiv st

.

Fraunhof er-Ges. , Bremen, Germany, p. 99-107.
-56-

Section H, cont inued

Simons, D. G. ; Land, D. J. ; Brown, M. D. and Brennan, J. G. , 1980, Ion Beam

analysis of lithium-boron alloys: White Oak Lab., Nav. Surf. Weapons Cent.,

Silver Spring, MD, Report No. NSWC/TR-79-95, 18 p.

Sutula, R. A. and Wang, F. E. , 1979, Battery with boron-lithium alloy anode

(Patent): United States US 4162352.

Szwarc, R. and Dallek, S., 1982, Lithium-boron (Li(B)) ingot preparation

scale-up study: Gen. Electr. Co., St. Petersburg, FL, Report No. GEPPTM-645, 44 p.

Szwarc, R. ; Walton, R. D. ; Dallek, S. and Larrick, B. F. , 1982, Discharge

characteristics of lithium-boron alloy anode in molten salt thermal cells:

J. Electrochem. Soc. , V. 129, No. 6, p. 1168-73.

Vakhtin, B. S. and Filippov, E. M. , 1972, Differential determination of

boron and lithium by the neutron-resonance method: Zh. Anal. Khim.

,

V. 27, No. 3, p. 595-7.

Wang, F. E. , 1978, Ductile lithium-boron alloys (Patent): United States

US 4110111, 4 p.

Wang, F. E. , 1979, An unusual phenomenon in the formation of lithium-boron

(LisBi*) compound-alloy: Metall. Trans., A, V. 10A, No. 3, p. 343-8.
-57 -

1. Perchloryl fluoride and nitrogen trifluoride

Adcock, W. and Khor, T. C. , 1975, Perchloryl fluoride. Further warning:

J. Organomet. Chem. , V. 91, No. 1, p. C20.

Alekseev, V. I.; Fedorova, L. I. and Baluev, A. V. , 1983, Mass-spectrometric study of thermochemical characteristics of perchloryl fluoride

and its decomposition product chlorosyl fluoride: Izv. Akad . Nauk SSSR,

Ser. Khim. , No. 5, p. 1084-90.

Anderson, D. G. ; England, D. C. and Milian, A. D. , Jr., 1981, Fluorinated

carbonyl compounds (Patent): Germany Offen. DE 3032471.

Aubert, J.; Bougon, R. and Carles, M. , 1967 , Hydrolysis of chlorine trifluoride, chlorine monofluoride, and chloryl fluoride. Study of the formation of perchloryl fluoride: Commis. Energ. At. (Fr.), Rapp., V. CEA-R

3282, 19 p.

Barberi, P. , 1973, Enthalpy of combustion and formation of oxychlorof luor ide

compounds: Bull. Inform. Sci. Tech., Commis. Energ. At. (Fr.), V. No. 180,

p. 55-60.

Barberi, P., 1977, Contribution to the study of chlorine, fluorine and oxygen

compounds: CEN Saclay, CEA, Gif-sur-Yvett , Fr. , Report No. CEA-R-4771, 157

Beardell, A. J. and Grelecki, C. J. , 1968, Perchloryl fluoride (Patent):

United States US 3404958.

Beresneva, I. V.; Mamynov , V. V. and Tukhvatullin , A. M. , 1983, Logarithmic

dependence of the heat capacity of individual substances on temperature:

Zh. Fiz. Khim., V. 57, No. 2, p. 285-8.

Blackburn, G. M. ; England, D. A. and Kolkmann, F. , 1981, Monofluoro- and

dif luoromethylenebisphosphonic acids: isopolar analogs of pyrophosphor ic

acid: J. Chem. Soc., Chem. Commun. , No. 17, p. 930-2.

Bougon, R. ; Carles, M. and Aubert, J. , 1967, Reaction between chlorine trifluoride and water: C. R. Hebd . Seances Acad. Sci., Ser. C, V. 265, No. 3,

p. 179-82.

Britton, D. ; Farooq, S. and Keese, R. , 1977, Synthesis and structure of

f luorotricyanomethane : Helv. Chim. Acta, V. 60, No. 4, p. 1393-7.

Cady, G. H. , 1978, Solubility and reactions of perchloryl fluoride in water:

J. Fluorine Chem., V. 11, No. 3-4, p. 225-41.

Cartwright, M. and Woolf, A. A., 1979, A redetermination of the heat of forma

tion of perchloryl fluoride: J. Fluorine Chem., V. 13, No. 4, p. 353-64.

Christe, K. 0.; Curtis, E. C. ; Sawodny, W. ; Hartner, H. and Fogarasi, ., i The general valence force field of perchloryl fluoride: Spe> trochim. t ,, Part A, V. 37A, No. 7, p. 549-56.
-58-

Section I., continued

Claassen, H. H. and Appelman, E. H. , 1970, Vibrational spectra and structures

of perbromyl and perchloryl fluorides: Inorg. Chem. , V. 9, No. 3, p. 622-4.

Clark, A. H. ; Beagley, B. and Cruickshank, D. W. J. , 1968, Structural parameters of perchloryl fluoride and perchloric acid: Chem. Commun. , No. 1,

p. 14-15.

Clark, A. H. ; Beagley, B. ; Cruickshank, D. W. J. and Hewitt, T. G. , 1970,

Electron diffraction investigation of gaseous perchloryl fluoride and

calculation of its force field and amplitudes of vibration: J. Chem. Soc.

A, No. 6 , p. 872-5.

Clark, R. J. H. and Rippon, D. M. , 1974, Vapor phase Raman spectra, Raman

band contour analyses, Coriolis constants, force constants, and thermodynamic

functions of symmetric top molecules phosphoryl fluoride, phosphoryl chloride,

trif luorooxovanadium, tr ichlorooxovanadium, thiophosphoryl chloride, and

fluorine chlorate: Mol. Phys., V. 28, No. 2, p. 305-19.

DeLeon, R. L. and Muenter, J. S., 1980, Stark effect and dipole moment of

perchloryl fluoride: J. Mol. Spectrosc., V. 83, No. 2, p. 469-70.

DeKock, R. L. ; Lloyd, D. R. ; Hillier, I. H. and Saunders, V. R. , 1972, Experimental and theoretical study of the electronic structures of sulfuryl

fluoride and perchloryl fluoride: Proc. Roy. Soc., Ser. A, V. 328, No. 1574,

p. 401-11.

Dersch, R. and Reichardt, C. , 1982, Syntheses with aliphatic dialdehydes.

XXXIII. Attempts to synthesize dif luoromalonaldhyde : Liebigs Ann.

Chem., No. 7, p. 1330-47.

Dersch, R. and Reichardt, C. , 1982, Syntheses with aliphatic dialdehydes.

XXXIV. Attempts to synthesize bromo- or chlorof luoromalonaldehyde and

f luoro (methyl) - or f luoro (phenyl)malonaldehyde : Liebigs Ann. Chem.,

No. 7, p. 1348-58.

Farrar, T. C. ; Maryott, A. A. and Malmberg, M. S., 1971, Pulsed NMR study of

rotational diffusion in perchloryl fluoride: Ber. Bunsenges. Phys. Chem.,

V. 75, No. 3/4, p. 246-7.

Green, J. ; Levine, N. B. and Sheehan, W. , 1966, Elastomers resistant to rocket

propellants: Rubber Chem. Technol., V. 39, No. 4, p. 1222-32.

Guest, M. F. and Hillier, I. H. , 1972, Localized orbital calculations of the

bonding in SC> 2 _ 4 , SO2 F 2 , CIO 3 F and SOCI 2 : Int. J. Quantum Chem., V. 6 , No. 5, p. 967-73.

Kamley, M. J. , 1971, Explosive and/or propellant compounds containing a

f luorodinitromethyl group (Patent): United States US 3624129.
-59-

Section _I, continued

Khutoretskii , V. M. ; Okhlobystina , L. V. and Fainz il ' berg , A. A., 1967,

Perchloryl fluoride (production, physical properties, reactions): Usp.

Khim. , V. 36, No. 3, p. 377-98.

Kliegel, J. R. ; Gold, P. I. and Weekley, C. T. , 1969, Chemical species and

chemical reactions of importance in nonequilibrium rocket engine performance calculations: Pyrodynamics , V. 6, No. 3-4, p. 257-73.

Mohan, S.; Ravikumar, K. G. ; Boopathy, T. J. and Chandraprakash, N. , 1984,

Normal coordinate analysis of some axially symmetric XYZ3 type molecules:

Indian J. Phys., B, V. 58B, No. 1, p. 56-60.

Mountfield, K. R. and Weir, R. D. , 1977, Low temperature heat capacity,

dielectric constant, and thermodynamic properties of solid perchloryl

fluoride: J. Chem. Phys., V. 66, No. 2, p. 736-42.

Nagarajan, G. and Redmon , M. J. , 1972, Quantum mechanical studies of atomic,

bond, and molecular polarizabilities, spectroscopic studies of vibrational

constants, and statistical thermodynamics. Perchloryl and perbromyl

fluorides: Monatsh. Chem., V. 103, No. 5, p. 1406-26.

Ostorero, J. , 1970, Measurements of the viscosity of some gaseous fluorine

compounds: Coramis. Energ. At., Saclay, Fr . , Report No. CEA-N-1293, 36 p.

Pilipovich. D.; Rogers, H. H. and Wilson, R. D. , 1972, Chlorine trifluoride

oxide. II. Photochemical synthesis: Inorg. Chem., V. 11, No. 9, p. 2192-5.

Ripmeester, J. A.; Garg, S. K. and Davidson, D. W. , 1978, Molecular reorientation in solid perchloryl fluoride: J. Chem. Phys., V. 69, No. 5, p. 2265-7.

Rips, S. M. ; Zercheninov, A. N. and Pankratov, A. V. , 1969, Detection of the

thermodynamic properties of some fluorine and chlorine compounds: Zh. Fiz.

Khim., V. 43, No. 2, p. 386-9.

Rogers, H. H. and Pilipovich, D. , 1973, Oxychlorine trifluoride (Patent):

United States US 3718557.

Rosolovskii, V. Ya. and Nikitin, I. V. , 1972, Nitrogen oxyf luorides . Chlorine

oxyf luorides . (Collection of reviews): Inst. Nov. Khim. Probl., Chernogolovka, USSR, Report No. VINITI 5437-73, Deposited Publ., 70 p.

Rutt, H. N. , 1980, Optically pumped laser action in perchloryl fluoride: Opt.

Commun., V. 34, No. 3, p. 434-8.

Sheppard, W. A., 1969, Mechanism of fluorination by perchloryl fluoride:

Tetrahedron Lett., No. 2, p. 83-4.

So, S. P. and Chau, F. T. , 1973, Urey-Bradley force field of perhalyl fluorides

Z. Phys. Chem. (Frankfurt am Main), V. 85, No. 1-4, p. 69-75.
- 60 -

Section j[ , continued

Streng, A. G. , 1971, Miscibility and compatibility of some liquefied and solidz ified gases at low temperatures: J. Chem. Eng. Data, V. 16, No. 3, p. 357-9.

Sunder, S. ; Hallin, K. E. and McClung, R. E. D. , 1974, Raman studies of

molecular reorientation in liquid perchloryl fluoride: J. Chem. Phys.,

V. 61, No. 7, p. 2920-4.

Sunder, S. and McClung, R. E. D. , 1974, Raman spectra of polycrystalline

perchloryl fluoride: Can. J. Phys., V. 52, No. 22, p. 2299-302.

Takano, K. ; Hosoya, H. and Iwata, S., 1982, Analysis of the oxidation state

and oxidation number by ab initio molecular orbital calculations: chlorine

and sulfur compounds: J. Am. Chem. Soc., V. 104, No. 14, p. 3998-4005.

Tantot, G. , 1976, Structural study of some halogen oxyf luorides : CEN Saclay,

CEA, Gif-sur-Yvette, Fr. , Report No. CEA-R-4770, 237 p.

Vereshchagin, A. N. ; Vigalok, I. V.; Aliksandrova, L. K. and Petrova, G. G.

,

1981, Polarity and polarizability of some perchloryl compounds: Izv. Akad

.

Naul SSSR, Ser. Khim., No. 2, p. 257-61.

Vigalok, A. A.; Petrova, G. G. ; Lukashina, S. G. and Vigalok, I. V., 1982,

Study of the reaction of perchloryl fluoride with halide ions: Zh. Neorg.

Khim., V. 27, No. 8, p. 1931-4.

Vigalok, I. V.; Petrova, G. G. and Lukashina, S. G. , 1983, Salts of the

organic f luoronitrogen cation - 1-f luoro-l-alkyl-2 , 2 , 6 , 6-te-tramethylz piper idinium : Zh. Org. Khim., V. 19, No. 6, p. 1347-8.

Wamser , C. A.; Fox, W. B.; Gould, D. and Sukornick, B. , 1968, Preparation of

perchloryl fluoride by acid solvolysis of perchlorates in fluorinated solvents

Inorg. Chem., V. 7, No. 9, p. 1933-5.

Wamser, C. A.; Sukornick, B. ; Fox, W. B. and Gould, D. , 1973, Nontransitionz metal compounds. Perchloryl fluoride: Inorg. Syn. , V. 14, p. 29-33.

Yodis, A. W. and Cunningham, W. J. , 1968, Production of perchloryl fluoride

(Patent) : United States US 3375072.

Ziebell, G. and Gross, H. , 1978, Aromatic perchloryl compounds (Patent):

Patent No. Germany (East) DD 132391.
- 61 -

J. Fluorocarbon (C 11 F 20 )

Chambers, R. D. ; Taylor, G. and Powell, R. L, 1980, Reactions involving

Fluoride ion. Part 18. Derivatives of perfluoro cycloalkenes : J. Chem.

Soc. , Perkin Trans. 1, No. 2, p. 429-34.

Clark, L. C. , Jr.; Moore, R. E. ; Diver, S. and Miller, M. L. , 1979, A new

look at the vapor pressure problem in red cell substitutes: Int. Congr.

Ser. - Excerpta Med. , V. 486, Proc. 4th Int. Symp. Perf luorochem. Blood

Substitutes, 1978, p. 55-67.

Cottrell, D. W. , 1970, Fluorocarbon dielectric coolants and their applications

Dielec. Mater., Meas. Appl. , Conf . , Imp. Smelting Corp. Ltd., Avonmouth,

Engl. , p. 322-7.

Irving, J. B. and Jamieson, D. T. , 1975, Thermal conductivity of 13 fluorocarbon liquids: J. Fluorine Chem., V. 5, No. 5, p. 449-56.

Lee, R. ; Devotta, S. and Holland, F. A., 1984, Derived thermodynamic design

data for Rankine power cycle systems operating on PP9 : J. Heat Recovery

Syst. , V. 4, No. 1, p. 51-6.

Moore, R. E. ; Clark, L. C. , Jr. and Miller, M. L. , 1979, Synthesis and

biological activity of perf luoroadamantane and some closely related compound

Int. Congr. Ser. - Excerpta Med., V. 486, Proc. 4th Int. Symp. Perf luorochem

Blood Substitutes, 1978, p. 69-79.

Morini, A.; Macchi, E. and Giglioli, G. , 1980, Experimental results on the

thermal stability of some fluorocarbons: Proc. Intersoc. Energy Convers.

Eng. Conf., V. 15, No. 2, p. 992-7.

Nakamura, Y.; Umemura, H. and Yonekura, M. , 1975, Emulsions of fluorinecontaining compounds (Patent): Japan Kokai Tokkyo Koho JP 75121184.

Nelson, J. K. and Manterfield, R. J., 1977, Sparking potentials in fluorocarbons vapors: Proc. Inst. Electr. Eng., V. 124, No. 6, p. 586-8.

Suntech, Inc., 1980, Determination of critical solution temperatures of perf luorocarbons (Patent): Japan Kokai Tokkyo Koho JP 8095868.

Wesseler, E. P.; litis, R. and Clark, L. C. , Jr., 1977, The solubility of

oxygen in highly fluorinated liquids: J. Fluorine Chem., V. 9, No. 2,

p. 137-46.

Yokoyama, K. ; Naito, R. ; Tsuda, Y. ; Fukaya, C. ; Watanabe, M. ; Hanada , S.

and Suyama, T. , 1983, Selection of 53 PFC substances for better stability

of emulsion and improved artificial blood substitutes: Prog. Clin. Biol.

Res., V. 122, Adv. Blood Substitute Research, p. 189-96.
-62-

Section ^J, continued

Yokoyaraa, K.; Suyama, T. ; Okamoto, H.; Watanabe, M. ; Ohyanagi, H. and Saitoh, Y.,

1984, A perfluorochemical emulsion as an oxygen carrier: Artif, Organs, V. 8,

No. 1, p. 34-40.

Yokoyama, K. ; Yamanouchi, K. ; Murashima, R. and Tsuda, Y., 1976, Oxygentransferable fluorocarbon emulsion (Patent) : United States US 654964.

Yonekura, M. ; Nagase, S.; Baba, H. ; Kodaira, K. and Abe, T. , 1976, The electrochemical fluorination of trif luoromethyl-substituted benzenes: Bull. Chem.

Soc. Jpn., V. 49, No. 4, p. 1113-16.
- 63 -

XIV. Tables
-64-

Table 1. X-ray Diffraction Analysis of LiAl/ClO^F Experimental Products

Expt. Max Temp. %Wt. Gain Phases

TGA 650 °C 109.86 a-Li„AlF, Jo, LiF*, A1F0 , A1

3 (isothermal)

TGA 550 °C

(isothermal)

97.58 Al, 3-LiJOQ AlF., A1F , LiF

J

TGA 450 °C

(isothermal)

98.52 Al, 8-Li 0 AlF, , A1F- , LiF, (LiCl)

J b J

TGA 350 °C

(isothermal)

109.26 Al, A1F

3

, Li

3 AlF

6

,

Mass Spec. 900 °C

(non- iso thermal) — YLiA10

2

, Al

TGA 650 °C

(non- iso thermal)

91.69 aLi.AlF, , A1F , Al, LiF

3 b 3

TGA 650 °C 50.43 LiCl, Al, LiAl , yLiA10

2

, LiF

Partial React,

(isothermal)

*LiF apparently contains a small amount LiCl in solid solution, as judged by

x-ray line shifts
Table

2.

Progressive

Oxidation

of

LiAl

alloy

by

Reaction

with

Components

of

C1CLF - 65 - 3 rH m nO CM 00 rH on CM o o nO rH • (V CN m rH CN CTN on <r 1 1 00 o ON 00 in u tH • • 3 a o o o rH CN O O rH o rH o 1—1

tH o i—1 6 + + + + + + + + + + + + + + +

CM CM CM CM O

pH CM t—1

ON tH

CN CN NO CJ CM <

Ph CM rH CM CM + CM o + <T /N ptH CJ i—1 + pH t—1 + CM CTN CN CM /—N

CJ co CJO + ^—s + \ CN co CM + O co /—V 00

rH + \ o CM + O CM N—

fH rH + 00 i—1

rH CM rH co •H CM 'w' rH < < i—1 i—1

CO < rH

X + o CM CM CM <C <1 N-^ 00 CJ CM nO + o + CM CM CM rH

CN ON PH + + + + <1 + tH o + CM CO + + +

CJ

O + pH + i—1 i—1 1—1

NO CM •H CN /—\

/—*\ rH CJ CJ pH pH

C pH o — 00 CN r—1

<c CM •rl •rl •rl •rl CM i—1

co tH CO — c CM i—1 X rJ X X <d PH <! +

ro CO CM CJ CM <r CM <T + co i—1

•H rH + •rl < J pH + cj + + + + + + pH rJ CM CO *H

r—i + NO •rl rH <d NO plH CM CM CM CM CM X + + + e < 1— + 1

pH 1—l o o o O o o + c r*H < rH 1—1

rH rH rH + tH rH rH

H + <c co <3 < < < < CJ CJ CJ CO 3 rH + co •rl •H •rl •rl •rl •H rH •H •rl •H o a rH cj •3 rJ X X X hJ hJ CJ X X hJ CN

cd CJ •3 pH

X CO CO CO co co •rl nO co CN tH

0) •H

J •H f X <

oc; + X 1 rt i i 1 1 t + t 1 + + + + t pH

hHco PH pH pH pH PH PH PH pH pH CO o co co CO CO CO pH CO CO CO Ph

pH co pH

O rH o o O o O co

O o o CO

CO

O CO i—l o tH 1—1 i—I

rH i—1 O rH tH tH o O i—l O CJ CM CJ o CJ CJ CJ i—1

CJu CJ tH

rH cj I—1

NO i—1CM CM <r CM <ra NO NO CM CJ

CJ <t cj + + + + + + + + + + + + + + -1-

rH i—1rH 1—1

rH tH rH rH tH rH tH rH rH pH rH <3 < <! < < c < < < < < < < <3 < •3 •H •H •rl •rH •H •rl •rl •H •H •H •H •H •H •H X rJ hJ rJ r4 X rO X X hJ X X x X X CO CO co m n- m I''' CM ON CO r^- CM 3 3 3 3 3 3 3 3 3 O O O O O O O o O •rl •rl •3 •3 •3

•rl •rl •rl •rH 3 3 3 3 3

4-1 4J 4J 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 c 3 3 3 3 •rl •rl •rl •3 •3 o 3 3 3 3 3 3 3 3 3

•3 00 00 00 00

OO

OOO 3 SO Co So r*N 3 3 3 3 3 3 3 a X X X X i—1 rH rH rH O *—• o

IT) o o o o 13 <3 13 >3 •3 <3 •3

0) 3 3

Pd <-3 u3 3 '-<3 3 3 3

M-t c s c c 3 3 3 3 3 3 3 3 3 3 3 3 O o o o o O 3 O O O O O O O O 00 O 00

•H •3 •3 •rH •rl

O •rl •rl •rl •H •H •rl •3 •3 So •3 So

a)

H 4-1 4-1 4J 4J •rl 3 4-1 4J 3 3 3 3 3 X 3 X

a ctf 3 cd CD 3 4J 3 3 3 3 3 3 3 3 o 3 o

So

C 3 3 3 3 3 3 3 3 3 3 3 3 3 3 H *H •3 •H •rl •rl 3 •3 •rl •3 •rl •rl •rl •3 •3 i3 •H n3 H Sh Pi u 3 a) 3 3 3 3 3 3 3 3 3 O o O o o 00 O O O O o O O O o

rH I—1 3 3 3 ^N i—1

rH 3 3 rH rH rH rH rH

JS

x rH i—1 1—1 XX

X i—1

rH rC

X s:

X SI

CJ

a 14H 4H o CJ 3 13 HH

a o uu

u 3o

•H3a i—i i—i i 1 i 1 r—i 1—1 i—i i—i i—i

i—i r—t 1 1 r

—

1—-1

1—

a)

m VO r~- 00 ON o i—1 CM co

m v£> e'- 00

0) CN CM CN CM CM CM co co co co

m co CO en CO

Pi 1—1 1—1 1—

1—

1—1—1 ‘

1 1—1 1—1 1—

1—1 1—

•—1— 1—
Table

3.

Calculated

Phase

Compatibilities

in

System

Li-Al-O-Cl-F

at

1100 K - 66 - 1—1

CO

CJ ps

/• S vo i—1

vO 1—1 i—i o CN 1 1 m vO r^. i—1

00 Ob <1* Ob rH CO o CN LO o-n m 00 CN <T rH 1—1

vO o 1—1 rH 1 1 rH o UO CO CN o o O o t—1

CN 1—1 ! 1 1 1 rHI 1 1 i + + + + + + i + + + + i 1 1 + i—1 >—

pi

CJJ <3

oo /—\

Z'—\/N z*—S

/•“N o

z-'s oo CO 00

N-^ /—V

rH 'w' CO

/<-N rH z^-n s-x rH CO CJ /T\ CO pH

C=^ <C

a o? •Hu rH rH oo rH rH o?

/—s

V—

•H 'w' '•w' rH hJ /-"N •H CJ < 's—' CJ <J

ex’ t—1

CO rH

C rH CO rH CN rH \-/ /-*N

v

—7 <d co o c CO < + rH < < rH 00

•H •H CN 00 + •H CN CJ + <T <1 V-/ mJ hj + + i—1 + hJ + /TS rH + •H c

CO < + /—N

vO + CJ < /^s + J1 rH

/"“N / N CJ /^N CJ + + O u + /"*N o + CJ /TN CN + CJ /"“N + rH V ' o v-/ CO 'w' a o 1—1

/-N z"“N CN CO o o zT-N CN rH /—s Pm CJ 'w' /TN o O o o O CN CN o o o <c o •H •H rH + 'w' 'w' i—1

CN sw' CN •H rH rH CN •H 'w/ mJ mJ CJ CN CNI < rH •H •H hJ < CO < •H hJ Pm vO CO •H t—1

^~N o o •H < hJ CN CN o •H hJ CO •H mJ CJ

r—1rH j CN 00 CO CN h4 CO hJ f + CO •H 'w' c < CO + + rH 1 CO ji •H •H •H 1 i + <d i +

zTN i CO mJ

C hJ Jl + /^\ /^*S /TS + oo CO O /"N /^s /^N t /^N /**\

CJ rv t

•H /"“N 1 /^s OO CJ Z*-\ vO CO 00 + U o ' 'w' 1—1

rH /-N 'w' co o pH rH

a /—s 1—1iH rH < < CO co o rH CJ CO 00 /^S T—1

c>? CO <c < < •H •H rH o CN CO < i—1rH ' a) C v_x o CN •H •H >J rH o CN i—1

ptH CO < CJ 00

w

PS •H

X—1

CN hj kJ co < i—1

rH < rH •H i—1 1—1 i—1 < i—1 + CN vO + CN < C CN <d tj + c CJ < < + rH + + CN /-N + + + + + + + + /—N + <ti + o /—s a c=^ /T\ + S-/ /T\ /^N o N -TS /—\

/^N /T, zT-S + o CJ CN O u V-/ CN a O C>^ VO C>^ C>? V-/ ^~N o ' v-/ CN o v-/ V-/ w V-/ PH 'w' z^N V—

o o o* rH o CO o rH o o rH 1—1 <—1

rH rH rH rH

CN CNJ <C CN o rH < CN CN CJ CJ CJ CJ < < CJ

•H •H •H •H •H CN <c •H •H •H •H •H •H •H CO •H •H •H

hJ hJ hJ hj rJ rH •rH rJ hJ rJ ji jj kJ mJ •H i-i >J t-j <N CN CO CO CO < CO CO CN vO CO 00 CO •J CO CO

CO co CO \

1 rH 1—1 u CJ CJ co CO co

rH t—1 <1 pH p-l pH

<c <J c rH rH rH i—1 rH 1—1 rH 1—1 rH rH rH rH 1 1 1 C <d < rH rH rH < c < <c < < c c <d r—1

rH rH l i i < < < i i 1 1 1 i 1 i i CJ CJ CJ pH P^ pH l i i •H •rH •H •H •H •H •rH •rH •H •H •H •rH •H •H •H •H •H •H

B hJ

J j J h4

J rJ hJ hJ tj iH .-1 Jl hJ mJ

a) i i i 1 1 1 1 i 1 i i i 1 i i i i i 4J co CO CO CO co CO CO co co CO CO CO CO co CO CO CO O'

C/D o o O o o o o o o o o o rH rH 1—1rH rH r—1

rO CN CN CN CN CN CN CN CN CN CN CN CN cj CJ CJ CJ CJ o

CO i—1 i—1rH rH 1—1rH rH 1 1 r—1rH rH i—1

rH rH I—1rH rH rH < <J < c c c <d c < < <d < < < < < < <

CO i o O o o O o 1 o 1 o o o o r—1

rH rH rH r—1rH CN CN CN CN CN CN CN CN CN CN CN CN o CJ CJ CJ o CJ

•H •H •H •rH •rH •H •H •H •rH •H •H •rH •H •H •rH |J t-i J >j hJ kJ hj rJ hJ .J l-J mJ hJ mJ mJ mJ co

•Huo i—

i—i ii i i r

—i i—i i i r i i—) 1 1 i

i i i »—i 1 1 r—« i

i r—i i

i av o rH CN CO LO VO 00 ON o rH CN CO tO vD

<U CO <r <r NT <r

m I/O U0m UO UO UO

PS 1—

1—1 4—1 •1 •

1 •

1 ' ' 1—

1—1 1—1 '

1 1—1 1 1—1 1—1 4—
lable

j

(.continued;

- 67 -

g

oQ

CN rH o 00 LO 00 CO CO 00 LO 1—

1

o CO 1—

1

00 o v£> vO CO (N 1^ CO CTN m o CN UO CO o O' rH CN 00 1—

1

vO CO r- LO 00 CO oo vo o rH rH 1—

1

rH + + i i + l i + + i 1 1 1 + + 1 + +

fC o

<1

C

o

•H

4-1 0

G

01 on

CO CO CO co CO CO CO CO CO

pH pH pH Ph pH pH pH pH pH rH rH rH i—

i

1—1 rH- 1—

1

rH i—

1

<1 <1

1 <1 < <1 <1 <C <1 <1 1 pH

1 pH1 pHi pH

1 pH

1 Phi pH1 PH1 pH 1—

1

rH rH rH rH iH

•H •H •H •H •H •H •H •H •H < < < < < rH < <

e h-3 t-3 H H! HI hJ 1 i 1 i i < i i <D 1 1 1 1 1 i 1 i 1 •H •H •rH •H •H •H •H •H *H u CO CO CO co CO co CO co CO hJ hJ »-) HI < -j h4 O o O o o O o o O 1 i 1 1 1 1 •H i 1 CN CN CN CM CN CM CM CM CN CO co CO CO CO CO j co co M t—

1

\—

1

rH r—H rH rH i—

1

r-M i—

1

PH pH Ph Ph Ph Ph co pH pH H> < c <£ c < C c < < i—l rH tH 1—

1

rH rH Ph rH rH 3 1 1 1 1 1 i 1 1 1 < < < < < < pH < <

CO O o O o 6 o o o O 1 i 1 1 l 1 < 1 i CN CN CN CM CN CM CM CM CN Ph pH PH pH PH Ph PH Ph Ph

•H •H •H •H •H •H •H •H •H •H •H •H •H •H •H •rH H •tH HH hJ HI HI HI H! HI hJ hJ HI hJ HI M

G

O

•HU

O i 1 i—

i

ii i—

i

i

i

ii i—

i

i—

i

r—

i

i—

i

I 1 »—

i

r—

»

f—

«

r—

«

, . r—

>

G 00 <T> O i—l CN co MT U0 W 00 ON o H CN CO

0) UO U0 UO MO \D vO vO MD vD v£> vO vO vD fs

Pi i . 1—

'

1—1 '—1 1—1 '—

'

'—' 1—1 1—

'' '—

1—•—•• •—*
Table

4.

Calculated

Phase

Compatibilities

in

System

Li-Al-Mg-O-Cl-F

at

1100 K

68 - 1—1

ctf u

Ji 1—1

CN rH M> 00 00 co \—1

M3 rH M3 M3m M3 o o

Pi 00 CN Oh 03 M3 uo Oh

T 1 O CN 03 1 1 CO o CN m <r <r CN 1—1

04 CO CM i—1LO| <r CN o

rH,—| + + + + 1 1 + i + i + + + + + +

pi o

<3

/—s

/'“N

a o Vw' /-N CM CJ O o pH CM b0 pH /N

•H o a •H pj CN

N •H + CM -N CJ rH + /—S

CJ <3

/-s /'“N + o /-*\

^"N CO bO

/*N o + 'w' CJ <r o a /-“N w /—N

CN o 's—j

CM on 'w'

CJ o /-N CJ /*“N /—s

pH co CN bO 1—1 1 1 CM CN '

o »—1

bO o i—1 a <1 + <3 CN 1 1 •H V O \ 'w' CJ /^N a CN <3 CO <r bO

Ph CJ pJ /~\ bO o •H rH rH bo /T-n

a bO bO 1—1 a 'w' CN pJ cj + <3 a + + CJ CO S a + CJ •H •H • •H co •H + hj pJ CN hj /""N + + /-N /“N

CO + + /*—S

pJ CM <—1 • o o 1 • /*s + CJ CM V-/ /“N /—N 'w' CN /TV

/-s CM + bO « 1 rH bO i—1

CJ o /-s CM rH '•w' ""•S a <J CJ Vw^ N ^ O a <3 'W' 1 1 CJ •H bO •H bO bO CN co CO o 'w' CJ bO pj u CN a a a «—1 o

CM bO

a bO •H CM

m in < i + CM

•H 1—1 E 'w'

a o pJ bO rH e pJ CJ CN bO bO + t i + a -r-N /-v <3 o •H + + a a + pJ + C>2 /-N /*s Sm\, t

Nw' V-/ + U • f f

'w' CJ o o* rH rH o /"-s CM <=^ /-s pH v-/ 'w' <3 <3

CO <—1

Vw/ >«- o /-N •H CM Ph rH rH CN

m c>? <U cj rH rH CJ PH •H <3 <3 Vw^ V ^ Pi pH bO cj CJ o '— CM bO pj bO bO 1 1 + + rH

•H S •H •H CN CM •H

a <N

a

a <3 <3

pj pJ -j *H

O Jl + CN CN CN /TN /*“S CO

CN CN CN CO pJ •H CO + + U o + + + v-/ + + + + + + + /'“N /-N + v-/ /-N /-s o o /"S

/-s /—s

/-N /—

N

CM ' o O CJ CN CN CJ

u o CJ CJ CJ 1 1 rH CN V-*' '—

rH rH

v-/ 'w' V-/ 'w' 'W' V-/ CJ CJ rH o o o <3 <3

O o O O o bO 'w' o bO •H CJ bO bO bO bO bO bO

oc bO bO bO

a bO bOa bOaa

aaaa

a S aa CM

a

a CO CO

a CO <1- co co CO i—i rH rH i—i r—i rH CJ CJ CJ CJ o o

pH •H •H •H •pH •rH •H

•rH rJ rJ pj pJ pJ hJ

hJ 1 1 i 1 1 1 CO co co co CO CO t CM CM CM O O o CM CM CN o O O o o O

CM i—1 i—1 r^ CN CN CM r-H i—1 rH CM CM CM CM CM CM e PH CJ CJ CJ •H •H •H CJ CJ CJ pH r—1 i—1 1—1 pH pH

cu bO bO bO bO rJ pj pJ bO bo 00 <3 <3 <3 <3 < <3

4J

aaaa 1 i 1 a

a £ 1 1 1 1 1 1 cn i i i i o o o i i i o o O O o o

kO o o o o bO bO bO pH pH Pn bO bO bO bO bO bO

03 CM CM CM CM

aaa •pH •rH •H

a

a

a

aaa

M3 •rH •pH •rH •pH i i i pJ pJ hJ i i i i i i 3 rJ J) rJ rJ •H •H •H 1 1 1 rH rH r-H rH rH r-H

C/3 1 1 1 1 pj pj pj CM CM CN <3 <3 <3 <3 <3 <3 o o O o i i i pH pH P^ i 1 1 i 1 1 bO bO bO bO bO bO bO bO bO 00 bO bO bO bO bO bO a a a a a a a a a £ a a a a a a co

•H

•UO i—i i—» i—i

r—i i—i i—i (—i i—i i—i r

—\

r—i i—i

i—-« i—i

r—> »—i

cti UO \D 00 Oh

O rH CN co <r LO vO 00 Oh

O $ r^. r- 00 00 00 00 00 00 00 00 00 00 Oh W 1—* 1—1 1—1 1—1 1—1 1—1 1—1 1—1 1—1 1—1 1 1—1 1—1 1—1 1 1—
- 69 -

nju

DC o v£>

m

m o m 00 00 CN cn CN 00 CM

O CM CN

m co c^ vD 00

m r—1

v£> oo CN rH CO 00

m CN 00 00 00 00 00 in rH CN CM CO

m CO i + + + + 1 1 + + + + + 1 + + 1

DC o<
- 70 - 1—1

cti a o o cr\ CO 00

Pi MP \—1

LO CM o o LO CO <r o\—1 + l 1 i i i T 1 'w'Pi a

<i

^—N

CJ 'w' /*"N ““N co PO u o £ V'-X v-^ /*-*S CM PO co O i—1 + £ (H 'w' <3

rH CO <T /—

N + c o / s CM CM + <=^ i—1

/"N S-/ o* + <c /^\ tH tH

CJ

u o tH

/-\ + •H •H cj o CM tH j •H

pM • CM rJ o a PC CM CO

PC £ tH + £ CM CO a f

pM PO /N

PC + £ /—V t £ V/

co CM PO 'w' /~N a £ •H c O t

v-/ f t-l o 'w' + CM

•H -n o 4-* O o CM /T\ + a CM v'-*/ rH 'w'

nj i—1

co < •H /TS

0) <3 pH PC rJ •H

Pi PO tH £ CM hJ

N— £ <3 CO CM /-—s CM + tH + + + CJ + /N •H

/“N cH /T\ rJ U u v-/ • a CM V-/ CM

CM CO tH CM tH

PM o pH o tH

u

PC PO rH PO o PO £ £ <3 £ PO £ CO CO CM CO £

co co co

Ph pH PH rH 1—1 l—1 c < <3 i—i i—i

rH 1 1 1 a u CJ CM CM CM •H •H •H

pH pH PH rJ rJ r4

B PO PO PO 1 1 1 <v £ £ £ CM CM CM

•u l l l rH rH i—1

CO CO CO CO CJ CJ

U £ o o O PO PO PO

co CM CM CM £ £ £ rO rH rH i—1 1 1 3 <3 <3 <3 •H 'H •H

CO 1 1 1 rJ rJ rJ o o o 1 1 1 PO PO PO PO PO PO £ £ £ £ £ £ co

rHU i i i 1 r—t i 1 i i r -i o r-» 00 o tH CM

cO o o o 1—1

tH rH

a) rH tH i—itH i—1tH

Pi 1—1 1—1 •

1 •—• •—i '

00 <r 00 CO • • • • MP UO o

CM1 1 + 1—1 + i—l i + +

/~v

O

/-“s o a v-/ CM '—

CM o

CM o rH

PH 1—t <J

'w' /T-N 60 < •H rH u £ •iH O CO rJ

•H PM +

HI *H +

CM HI + /^N CM a + CJ '•w' + v—' O CM

/-S CM '—

Pli CJ O CM 60 o tH PH £

<r < P0 CM o <r •H £

CM o hJ + tH CM CO < t—1

/T-N 60 < + CJ £ 60 ^ N £ o Pm + a 'w' •H t

Vw^ HI

/—N Nt o CM o <r\ O CM

's-/ CJ CM rH t

CM v»/ rH <c o CM < P0

O

rH

O 60 £ 60 < t—1 £ vO £

•H < CO CM

HI •H + CM rJ + + CM + /^N cH /-N + C>^ w O a V '— PH V-/ vD

v-/

a CO i—1

CO PH CM rH O <3 o tH

rH CM < CM co CM <

PH CO t—1

•H rH CO

60 60 •H <C rJ < •H £ £ HI CM CM <T HI i CM i 1 i i rH CM CM CM CM O PH pH pH pH

P0 PO PO P0 P0 £ £ £1 £1 £1 i o o 1 o o

CM CM CM CM CM

•H *H •H •H •H

rJ rJ j rJ j 1 rH 1 i 1 i co o co co co co o *H O PH O PH O PH o PH CM HI CM CM •H CM •H CM •H I—1 1 r-H j i—1 HI rH tH tH HI <3 co <3 i <3 1 <3 1 <3 1 1 tH 1 co 1 CO 1 CO 1 CO O O O pH O PH 6 PH O Pm PO tH P0 I—1 P0 i—1

P0 i—1

P0 tH £ < £ < £ < £ < £ <c 1 1 —i

r—«r—i i i CO LO vO

tH tH rH rH tH t—1 tH rH i—1 rH i i i—i

i—» > .i i

i
- 71 - H

COoXs—* vO o vD \£> • • • • • o o NT i—1 o <r vO X co oH I 1 i 1 1 T 1 > '0£ o

<3 S—N

<x <X —

V—

X + I—1 < <

/N CM + O + V CN o

pH ^ CO CJ ^ s CM <X o

co CM

X

X <x 00 < + 00 ' S X S X

co < + co X

'w' + X + rH CJ u /—v + v-/ *H o CM CJ '—/

/<—

N

O

N—

vO

X CJ

X

O

•H

—s < oo + XI o X £

x> 00X CM /—\ 2 CM t CM +

'v_X + C vO —s f —s o <X /—V o? X rH '—

<x ''

—/

4-1 < 00 v-^

X

TDO CO s 'w'

X

X

d> CO •H co 00X CO 3 0J rJ £ CM C PS CNI + CM + •H + 4-> + + s c >X —s

CJ o /^s /N u o vO CJ N—

<r

'w'

u

X s-/ < O

CNI i—l CM o CM <r rH CO < o CM X O PlH co r-H X C

QJ CO rH

X < <3 00

X s < XX 00 £

X) CO CNJ CNI

X s CM

cti H o o o X CM CM CM X X X X 1 X X X

CNJ 1 1 1 1 rH co co co co u X o O O

OO i—1CM CM CM s < X i—1

rH 1 1 c < <3

IX CM 1 1 1 e X X o o o

<u XI oo 00 oo oo

4-1 1 rH s E s £ co co U 1 1 1 i >, IX •H X X X X

co i-H

XX

X

X

xa < 1 1 1 1 1 3 1 CO rH rH rH rH

cn CM rH <3 < c <3

pH o i 1 i i 00 rH oo 00 00 00 X < 2 2 2 S coXU i—i

r—« t—1

1—1

r—i

O 00 ON o rH CN

CO rH rH CN CN CN

CU rH rH rH rH rH

Ce2 1
Table

5.

Progressive

Oxidation

of

LiAlMg

alloy

by

reaction

with

Components

of

CIO

F

72-
Table

6.

Calculated

Phase

Compatibilities

in

System

Li-Be-O-Cl-F

at

1100 - 73 - ),

kcal

co rH NO ON CMm i—1 o CO no on CO nO • • 00 CM r—i

00 00 CM on CO CO o o CO ro pH

m uO o CM -d" CO CO m CO m m NO M0 NO rH CO or—i i i 1 1 1 1 i 1 i l 1 1 + + i +

r—1

OS o<

/"No

'w' bO o x--v /—\

'w' o CU <=J CM

'w' /~N

a PQ / s '—

/—

N

iTMH

/"~N <U CJ CJ o CO CJ CJ O PQ /^S 'w' o + '—H

/~> pH Ph /—N '—' CU V«/ + CJ <U CU OJ o CJ a)

CU o PQ

<U 'w' PQ PQ pa QJ v-r pa PQ QJ PQ CU u o? pa o CM *H •H /—s

PQ +

PQ 'w' + + + QJ •H hJ hJ

U + <D <r + pa J CM CM + —N

<3- + PQ /-N /«—S

S~S Ph QJ CJ Ph CJ CU /N + + + + PQ <—>

CJ (U /~s + '—y

'w/ PQ

a cJ Ph

PQ CJ CO pH CM '—

V /^N + •H

pH CM V-/

—\

Ph Ph •H •H Ph CJa o b0 i—l

hJ

•H •H Ph CJ CU CU r4 hJ •H M/ ' H ^—\PJ <r

hJ hJ •H 'w' PQ PQ <r CO rJ pH o o CM

a *H

<3* CO Ph CM •H co •r( QJ CU hJ +

CO •H •H t f rJ PQ PQ

U o CM + hJ CM f CM CU CM c + CM 1 + PQ •H t o /—V i + 1 •J

•H + ' v c-> /N + /—>

<3" 4J '—/

Vw' S"\ <r CO '—' r—v oj t 00 Ph

O CO /*N pH pH cn CJ S-/ -—' CU

CO Ph PH CO <=^ V-/ Vw' 0) CU Ph '— CM CM o ^ N CM PQ

0) <D CU Ph CM CM pa PQ CL) CM Ph Ph o rH CM

pi PQ PQ <U CM Ph Ph CM •H pa pH QJ (U CU o •H CM •H PQ Ph CU (U •H •H QJ PQ PQ PQ o 0) rJ

•H rJ •H <U PQ PQ rJ <T rJ PQ CM CO QJ PQ

hJ <r PQ CM CO + PQ + + + + + + + + + + + + + + /N + s s /—N

“S /-s /^S c>^ /TV c>^ /~s /*\ /—N /^N o CJ a a CJ CJ CJ s-/ o? Vi—

'w'

N ' rH o? '—

i—1

'w' ' 'W' 'w' o O o o o o CJ o CJ •H •H •H •H •H •H CM CM CM CM CM CM •H •H CM *H

iJ hJ kJ hJ hJ •H •H •H •H •H •H hJ hJ •H *-) CM CM CM CM CM CM h4 J rJ hJ CM CM rJ CM

CM CM

rH pH CM <r O’ <r <r <r <-J QJ pH pH pH Ph Ph pH CM QJ PQ

CU QJ OJ QJ OJ QJ rH PQ 1 CM CM CM CM CM CM PQ PQ pa PQ PQ PQ a o 1 Ph

pH Ph pH pH pH PH 1 1 i 1 1 1 QJ QJ rH hH e QJ QJ 0) QJ QJ QJ Ph pH pH Ph pH Ph PQ PQ u rJ

aj PQ PQ PQ PQ PQ PQ •H •H •H •H •H •H 1 1 •H 1 ij 1 1 1 1 1 1 hJ rJ hJ rJ rJ rJ rH O rJ CM

CO pH Ph Ph Ph Ph pH 1 1 1 1 1 1 CJ CM 1 rH

pH'l •H *tH •H

H •H •H o o O o o o •H •rl o CJ

CO

J rJ r4 rJ rJ rJ (U QJ 0) QJ QJ QJ r3 rJ QJ QJ JQ 1 1 1 1 1 1 PQ PQ PQ PQ PQ PQ 1 1 PQ PQ 3 QJ 0) QJ QJ QJ QJ 1 1 1 1 ± 1 0) QJ 1 1 cn pa pa PQ PQ PQ PQ o O O O O O PQ PQ O rH i i 1 1 1 1 CM CM CM CM CM CM 1 1 CM CJ

•H •H •H tH •H

H •H •iH •H •H •H •H •H •H •H •rH rJ rJ rJ rJ rJ rJ hJ rJ rJ rJ rJ rJ rJ rJ rJ rJ co

•H

•U i—i

r—i i—i i—i i—i

i—i i—i i—i(—* i—i i—i i—i ( i r—

r—r—i

CJ

m vO 00 ON

O rH CM CO <rm NO 00 ON o cO ro co co CO CO <r <r 'CT hJ <r <r 'd- >3- m

QJ rH rH rH rH 1—1

rH rH rH rH rH rH rH rH f-H rH rH

pi 1—1 1 1 1 1 i i 1—1 1—1 1 1 1 1 

1 1 1 1 1 « • • 1 •—

— *—
- 74 - ,

kcal 1 1 CO o 00 vO • • • • • CM uo m T—1

r—1 oo

co CM i—iCM r—1 1—1

rHN *PS o

<3 + + l 4- 1

/-sb0

/—

N

CM /*“N rH

—V

'W' CJ

bC CM CD CM

PH PQ pH CM bO CD CD

r-H 'w' PQ + PQ cj CM CM CO

CD i—l PQ

CJ + +

CD

v>—

+ PQ z-s ^d"

—

N Ph

/“N + V—

CD 'w'

CJ rH PQ 1—1 'w' /*\ CJ CM CJ PH CJ •H •H •H •H 'w' hJ hJ hQ

hJ pH CM CO CM CO •HJ i f i 4 CM

/T\ /T\ /-s

C + b0 o* b0 O c>^ 'w' H S—

/"V CM CO CM

U CO rH pH rH U Ph v CJ CD CJ

0) 03 0) CM CD PQ CD 3 03 PQ pH PQ •H PQ C PS •H CD J1 •H J) PQ + <r +

•Uc + + /^N + OO /^N /*\ 'w' /-s V-/ — <=>? o* <r CO

V-/ V-/ PH PH vO pH rH CD rH CD cj CJ PQ CJ PQ

0) •H •H CM •H •rH tH hJ hJ •H J hH JP CM CM h-3 CM CM

o) H

CM CM CM CM CM

Ph Ph Ph pH PH

CD CD CD CD CD PQ PQi PQ PQ PQ i pH i Ph i Ph i Ph i Ph •H •H •H •H •H 6 hJ hj •-j hJ h4

03 1 i i 1 1 u CM CM CM CM CM

C/3 1 1 1—1 rH i—1

rH

fn cj

O

aU o

C/3 CD 0) 03 03 03 rO PQ P3 PQ CQ CQ 3 1 1 i 1 1 CO rH r—l rH rH rH

CJ

U CJ CJU

•H •H •H •H •H

hJ

J tJ

~>>= CoHu i

i i—i r

—ir—i ii o rH CM CO <r m

03 in in I/O

mm

03 i—i i—i

rH rH i—/

PS 1—• 1—1 1—1 1 ’ 1—1
Table

7.

Progressive

Oxidation

of

(Li+Be)

Fuel

by

Reaction

with

Components

of

CIO F

75 -

CN

Eh CN CN o CN —s T—l pH CN CN s— CN CN

Ph CN Ph

O + "

ON

'w' CN i—1

CN

CN CN CN CN -—

CN "

+ o o + t—1 i—1

T—l pH co CN

/-s <J o + ^ 

O

CNI CN CN -o /—v CN \ CN 00 \ pH + CN CN CN \ + CN o S—

CO CO \ T—l rH co CN

'•w' V-/ CN CN i-H

T 1 <j

O CO T—l CN T—l *-/ /-—-* 3 N 

+ PJ + o + CO u CN + PP 3

co v-/ /^N + + r^« + T 1 PP CN CS| CN r—1 T 1 u

rH + pH + \ o o o + 3 •H +

CJ r—1

CD CD •H PP h4 CN CN PP PP + h4 T 1 CN CN T—| CN t—1

&0 co co o u o rH + o + *H + + *H rH s-/ CN + + 3 i-4 i-4 >—, + rH o PP O CO T—l CN <r + O CD O *H co 3 u Ph c + CN (V PQ CN i-4 PQ + •H 3 + o Ph (U PQ CO •H CN + CO >-4 PQ •H CU <D PQ i-4 o CN

4-1 PQ PQ + + + O + CN + + pH o + CN CN •H 3

CO + + rH •H \ Ph *H •H ,-4 PH 3 PP

Cl) rH o i-4 CO •H i-4 rJ CN •H PQ co

OS Ph pHu *H CO s—•* (-4 CN CN k4

H •H h4 + + 1

hJ i-4 + 1 + t + t + pH Ph Ph t + + Ph Ph pH Ph PH CO Ph CO <r PH CO co CO co co o CO O o

pH Ph pH CO o O o OO T—lO T—1

T—l CO CO CO o T—| T—| T—l T—| T—l u i—1 u u o o o t—l O <j C_> o cj CO O CN so

rH T—l rH o u CJ o co + + + + + + + + +

CN + + + + CD <D CD 3 3 3 3 3 3

PP PQ PP PP PP PP PP PP PQ

0) CD CD CD co CO co co CO !•'- CN CN of

PQ DP PP PP + + + + + + + + + + + + +

•H •H •H •H •rH •H •H •H •H

•H •H •H •H i-4 i-4 ,-4 i-4 i-4 i-4 i-4 t4 i-4 hJ i-J 1-4 4 CO co co co CO I-'- CN CN of 3 3 3 3 3 3 3 O O O O O O O •H •H •H

•rH •H -rH •H HI 4-1 Hi

4-1 4-> 4-1 4-1 3 3 3 3 3 3 3 3 3 3 3 3 3 3 •H •H •H 3 3 3 3 P-4 P-i 3

00 00 00 00OO

O

So So So 3 3 3 X X X X T—l T—l T—l 3 o o O o 14H IH4 *4H O

•H -3 •s i-3 sa *a

4-1 O 3 3 3 3 3 3 3 3 3 3 3

cO o OOO 3 3 OOO

O

O

OO

CU *H •H •H •H O'O •H •tH •H •H •r-l •H •H

Pi 4-) 4-) 4-1 4-1 T-l •rH 4-1 4-1 4J 4-J 4-1 4—1 HI

cO CO cO CO 4-1 4H 3 3 3 CO 3 3 3

*4-4 3 c 3 3 CO 3 3 3 3 c 3 3 3 O *r-l •H •H •H 3 3 •H -rH •H •H •H •H rH

P-i S-i

U i-i (D CD P-i Vt Pj

u P4 P-4 P-i 0) o o o o 00 60 O O O o o o o a 3 3 T—1 1—i Po So 3 3 T—l rH I—1

T—l T—l so i—1

r—1

-3 -3

X

X T—l T—l J3 x: JP X.

X

H *4-4 4-1

O

O o O 14H *4-4a o CJ

a

u 3O

T“i

4-1 i 1 i—i i—i i—i

r—i i—>

r—-i i i i—ir—« 1—tT—l f—1 o vO r^ 00 o\ o i—1

CN co -4-m vO 00

cOmm *n

m vO sO \£> <D vO vO SO vO vO

a) i—i

rH i—!T—1T—l T—l T—l T—l T—1rH rH f—1

f-H pi 1—1 4 1 1—1 1 1 ' ‘ ' ‘ 1 ' * ' 1 • *—

*—

[169]

chlorination &

fluorination

8Li +

8Be +

3C10 F

-»•

8BeO +

Li„0 +

3LiF +

3LiCl
-76 i—

COo

pi

m o 00 04

Pi • • • • • • o o CO m LO o CM 00 o CO m o o CM v£> CM CO co i—

1 + 1 + l +

Pi

e><3

Pioo o /^*N rH /^S o t—1 pH 00 /—

•H pH /-N 00

4-> hJ •H 00

CO 00 PM hJ

V <r /-N CJ CM pH Ph 00

PH + CM o 1 + + CM u /-“N + P^ 1 o /-N /^S + CJ

•H

V ' a 00 /-“S

h-1 CM

Vw'

a /"N + O CM

B CM CJ pH CM '

CL) •H CM CJ cj •H o*

4-1 hJ •H CM CM hJ v-/

CO

a hJ •H CM •rH rH o + CM +

co •H + <r

4J /^s + y^N c U 00 00

CO V/ /^N 00

a) CJ CM o /^S

CO Pi p4 Ph 'w' pH 00

<1) cj cj

m pH 00 V-/ •H CM in •H CJ

4-1 + hJ +

•H + + CM + i—

•H /'“N o + CJ /-N rO o V— o H CM /-N CM

4-1 •H pH CJ

O

a pH

CO rJ •H CM 'w' CM •H

Cu

O •H CJ •H

B r—

CM rJ <3* ou

0)CO

cO 40

P-i TO

0)

4-J cO 1—1 0)ai—

cO o 6

0)

4-) pH pH pH Ph Ph Ph • CO 1 1 1 1 1 1 00 |H cj CJ CJ CJ CJ <J

CO 1 1 1 1 1 1 QO 40 •H •H •H •H •H •H rH 3 hJ (-4 hJ hJ rO in

cO H

Co

*H

4-1 i—

r

—

r i r——l i—

r—

U O T—

CM CO <r

m

cO r^ r^ r>> r^

CU t-H rH r-H t-H rH rH

Pi 1—

1—

1—

1 ' 1—1
Table

9.

Calculated

Phase

Compatibilities

in

System

Li-B-N-F

at

1100

-77

I—

ccJ CJ

tfS /"-S Z o LO o o m rH O • • • • • • • O CN o vD 1—1 CM CO o i—I 1—1 O CO CO co

1—

rH rH rH rH

1—

1 + + 1 1 + +

Pi u

<

/-s /•—N a 00 /—N —

00

'w' rs CJ CJ PQ 00 CO Vw' c—

co

•H 'w' pH z CJ eP pM CO PQ PQ 'w' <r CP

Ph a

+ PQ + + CP + +

+ /*-\ /•"S +

u u CJ CJ 'w' /—N 's-c' —

pen PQ •H Z Z •H 'w' •H hJ co CO a hQ •H hJ <r •H H •H o CO hJ CO hJ hJ hJ •H CO + co U + f t 1

CJ t /—s i

a) /-s /—

O /—s

(U 00 a 'w' /—s CJ CJ Pi V-/ a V-/ PQ cj '—

CO PQ •H v—

z z

p

PQ CO CP CP CP

PQ

4- + + + + + +

/~N /-"*N /~N —v

\ O u a a cj CJ 'w' Vw' S ' s_

'w/ pH PH is Z CP PM

•H •H •H CO co •H •H

i-l hJ •H H t-J hJ CO CO hQ CO co

co

Pm

CP 6 CO CO CO z Z l a) pH pH PQ CP CP Pm

.u PQ PQ PQ 1 1 1 •H

cn 1 1 1 23 Z Z J

Po Ph pH pH CO co co 1 Cfl •H •H •H •H •H •H z

rO hJ hJ i-l CP 3 1 1 1 1 1 1 l cn PQ PQ PQ PQ CP CP z

1 1 1 1 1 1 CO

•H •H •H •H •H •H H

hQ hJ J h4 hJ

=s=d

o

•H

4-i i—i r—

i—i i—i i—i i—i i—

O CO os O i—

CM co

nJ r^ 00 CO 00 00

<u rH rH «—

1—1 T—i—

1—1 Pi 1 ' i , i—

1—1—1 1—1—1
-78-

Table 10. Progressive Oxidation of LiB by NF^

Reaction # Reaction

[184] 3LiB + NF

3 2B + 3LiF + BN

[185] 3LiB + 2NF

3

-> 3LiF + BF

3 + 2 BN
79-

S3M

a.

p—i

rH

CO CO X CJ

4-1

X * c —

w 3 4J •H 3 X cO CD x X

4-1 •rl CO o X

rH o o 3 rH O rH rH

cO 4—1 1—1

CJ CO CD3

pH

X MH

CO rH v-/

4J CD O •H H >-<

COe CD o M c CO

•rl cO o U

4-1 4-1 'rH CJ

CJ CO 4-1 3

CO CJ

X

CD X) cO o

OS

C CD 3

CM

X PH BO33cw

COO

•HE

Cl) X

CJ

XI

(D

<D co3o

cn •H3

cOaeo

cjX

cO H

aiM(

cO 4J COX3

CM

CDM|

cO

4-J CO

4-1 CO

CD3

PHyCOE

•rl

S-i P-i

00

mjsO

<r <r

ro

<r o<r

00 00 vO so LO 1—1 o

CO CO CO CO CO rn CO CM o

04

PC o

CM

PC 04

PC o

04

PC 04

04 04 o 6 o

CM /-s PC CM + CO

CM | CM I 1 CM PC o o O O 3 3 X EZ 04 CM

u CJ o 3 •H

4—> O cn •rH CM rH VS 4-1 * PC CJ rH i—i

CJ Pm •H CJ

CTJ 3 •H Vs •H

4-J 3 3 X hJ o

d) PC 4-1 o Vs 00 S CJ V. CM CM Pm Vs £ 3 3 o PC CM rH •H Pm CO M X CM CM PC < hJ •H VS CM CM CN •H 3 o P3 •H 53 vs M CM hJ PS •H PC D 4-1 3 X PQ CM vs S Vs PC o Pm hJ

cr CO PH Vs o CO CO VS CM Vs •H

r •H o Vs Vs 1—1 o V» o Vs CM rH PC VS PC

hJ 4-1 CMO < CMO CM o pH

C o Pm o

CO •H 3 •H

H rH

M i—1 M 00 00 •H Vs •H •H X) rH PC < £ < £ £ £ X CJ hJ X

P-I o

CM

O

CO O CO o o oCO O o

CO O o

pH

r* CM rH Pm CM CM CM rH CM r—\ CM r- PC CJ PC PC PC CJ PC CJ PC o

\D

pH

CO PC

PC

•rH

•rl 3 X

PC 00 + + £ 1 1 rH rH rH

•H < <2 <c <d

•rl

X •H rH 00 •H 00 •H

rC CM rJ <C £ X £ X

•H

hJ •HrJ

CTs s£> SO

00 i—> i—I 04

00

00

CM

X roo

O- rH

<r

co

so

o> o i—I CM

Calculation

ignores

weight

of

recycled

water

in

dual

stage

reactions
XV. Figures
FRACTION

WEIGHT

GAIN

Figure 1.

-81-

Thermogravimetric analysis of reaction of powdered lithium

metal with flowing water-saturated argon at 25 and 100 °C.
-82-

Figure 2.

REACTION TIME (MINUTES.)

Thermogravimetric analysis of reaction of powdered sodium

superoxide with flowing water-saturated argon at 25 and

100 °C.
FRACTIOH

WEIGHT

GAIN

-83-

0.350

0.300

E 0.250

<ro

•

WEIGHT CD •

ro CD CD

2 0.150 —

o

*

<xOlu

0.100

0J3 50 - •

0 1 . i i i. * i A. — —1 . i — . . i 0 100 20Q 300 400 500 600 700 808 900 1000

REACTION TIME (MINUTES)

Figure 3. Thermogravimetric analysis of reaction of powdered MgAl all*'

with flowing water-saturated argon at 650 °C.
FtffiCTIOH

HEIGHT

GAIN

-84-

Figure 4 Thermogravimetric analysis of reaction of powdered LiAl alloy

with C10 3 F. (a) 350 °C; (b) 450 °C; (c) 550 °C; (d) 650 °C.
-85-

0 0

Cl

Figure 5. Quaternary reciprocal systems relevant to oxidation of LiAl

alloy by CIO 3 F.
- 86-

Figure 6. Calculated phase compatibilities in ternary reciprocal subsystems of the system Li-Al-Cl-O-F at 1100 K, 1 atm.
-87-

0

a)

Cl

0

Cl

Outline of 1100 K, 1 atm phase compatibilities relating to

oxidation of LiAl alloy by C10 3 F. (a) chlorination and oxygenation; (b) fluorination and oxygenation; (c) fluorinat

and chlorination.

Figure 7.
Figure 8.

A1C1

LiCl

Outline of 1100 K, 1 atm phase compatibilities among products

of complete oxidation of LiAl alloy by CIO3F.
-89-

A1C1

A1F

3

Figure 9. Quaternary reciprocal systems relevant to oxidation of

LiAlMg alloy by CIO 3 F.
-90-

Figure 10. Calculated phase compatibilities in ternary reciprocal subsystems of the system Li-Al-Mg-Cl-O-F at 1100 K, 1 atm.
-91-

MgCl,

MgF„

Figure 10 continued

.
-92-

Figure 10, continued.
-93-

Figure 11. Outline of 1100 K, 1 atm phase compatibilities relating to

oxidation of LiAlMg alloy by CIO 3 F. (a) chlorination;

(b) f luorination; (c) oxygenation.
-94-

A1C1.

a) b)

aici

3

Figure 12. Outline of 1100 K, 1 atm phase compatibilities among products o complete oxidation of LiAlMg alloy by C10 3 F. ( a ) chlorina- tion and oxygenation; (b) fluorination and oxygenation;

' c ' fluorination and chlorination
-95-

F

Figure 13. Quaternary reciprocal systems relevant to oxidation of I.i/lV

mixtures by CIO 3 F.
-96-

LiF (L1

2 BeF

«

) < LiBeF

3

)

Figure 14. Calculated phase compatibilities in ternary reciprocal subsystems of the system Li-Be-Cl-O-F at 1100 K, 1 atm.
-97-

C1 F

F

c)

Cl

Figure 15. Outline of 1100 K, 1 atm phase compatibilities relating to

oxidation of Li/Be mixtures by C10 3 F. (a) chlorination and

oxygena tion j ( b ) fluorination and oxygenation, (c) 1 im.i tion and chlorination.
-98-

Figure 16. Outline of phase compatibilities among products of complete

oxidation of Li/Be by CIO 3 F at 1100 K, 1 atm.
-99-

C

Li LiF F

Figure 17. Calculated phase compatibilities in the system Li-C-F at

1100 K, 1 atm.
-100-

F

Quaternary reciprocal systems relevant to oxidation of LiB

alloy by NF 3 . Figure 18.
- 101-

LiF BF

3

Figure 19. Calculated phase compatibilities in ternary reciprocal subsystems of the system Li-B-F-N at 1100 K, 1 atm.
- 102-

LiF

Figure 20. Outline of phase . compatibilities ajnong products of complete

oxidation of LiB by NF 3 at 1100 K, 1 atm.
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BIBLIOGRAPHIC DATA

SHEET (See instructions)

1. PUBLICATION OR

REPORT NO.

NBSIR 85/3282

2. Performing Organ. Report No. 3. Publication Date

DECEMBER 1985

4. TITLE AND SUBTITLE

Survey of Alternate Stored Chemical Energy Reactions

5. AUTHOR(S)

L.P. Cook and E.R. Plante

6. PERFORMING ORGANIZATION (If joint or other than NBS, see in struction s)

NATIONAL BUREAU OF STANDARDS

DEPARTMENT OF COMMERCE

WASHINGTON, D.C. 20234

7. Contract/Grant No. N00014-83-F-0117 and

NQQQlfl~8fl- F-Q20A

8. Type of Report & Period Covered

Annual Report

9.

SPONSORING ORGANIZATION NAME AND COMPLETE ADDRESS (Street, City. State. ZIP)

10.

SUPPLEMENTARY NOTES

Document describes a computer program; SF-185, FIPS Software Summary, is attached.

11.

ABSTRACT (A 200-word or less factual summary of most significant information. If document includes a significant

bibliography or literature survey, mention it here) A survey of eight alternative liquid metal stored chemical energy reactions has been

made for purposes of comparison with the lithium-aluminum/water, lithium/sulfur

hexafluoride, and other reaction schemes. The objective of the study was to survey the

potential of these eight reactions as alternate stored chemical energy systems and to

develop priorities for future study. Experimental data on the products of reaction and

kinetics of reaction are presented for: (Li/H

? 0; H? /0? ), (Li/H? 0; NaCL/bLO; bL/CL),

(MgAl/H-O; H^/O-), and (LiAl/ClCLF) . These data have Deen collected using thermogravimetry and Knudsen effusion mass Spectrometry, with x-ray diffraction analysis of

experimental products. Among other results, the data show that the aluminum component

of the fuels is relatively inert to oxidation up to 650 °C. Above this temperature,

materials limitations have hampered the collection of experimental data.

Thermodynamic analysis has been used to extend the data on each of the eight reaction

schemes, and to predict the chemical reaction with best represents the complete oxidation of each fuel by the indicated oxidant at 1100 K. Enthalpies have been calculated

for each fuel/oxidant combination. Safety considerations are also discussed for each.

Suggestions for future research are given, including suggestions for overcoming the

materials problems encountered in this study.

12.

KEY WORDS (Six to twelve entries; alphabetical order; capitalize only proper names; and separate key words by semi' enthalpy yield, kinetics, liquid metal combustion, lithium, lithium-aluminum

lithium -boron, lithium-beryllium, magnesium-alumium, nitrogen trifluoride, water

13.

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