NASA: BARIUM
- Chemical Formulas/Suppliers
source:
gisgaia / SOshanna
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This is the "Description of Preferred Embodiments" link
in the NASA Barium Patent listed above. Astounding that this information
was generated in l969 and now,30 years later, there is evidence
of Barium saturation in our atmosphere.
www.delphion.com/details?...etd=1#detd [NOTE: The text has been enlarged for easier reading]
The Barium/Fuel mixtures are listed below along with the suppliers. There is much technical info along with helpful hints(?) contained in this description, for example "This system caused clogging of the feed valves due to precipitation of the Ba(NO3)."
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Description of Preferred Embodiments:
Referring now to the drawings and more particularly to FIG. 1,
there is shown a segment of a suitable carrier vehicle 10, such
for example a rocket motor. Vehicle 10 is employed to carry fuel
tank 11, insulated oxidizer tank 13 and combustion chamber 15,
along with the necessary instrumentation, from earth into the
upper atmosphere or into interplanetary space. Fuel tank 11 is
in fluid connection with combustion chamber 15 and oxidizer tank
13 is in fluid connection with combustion chamber 15 by way of
respective conduits 17 and 19. A pair of valves 21 and 23 are
disposed within the respective conduits 17 and 19. Valves 21 and
23 are adapted to be selectively and simultaneously opened by
a suitable battery-powered timing mechanism, radio signal, or
the like, to release the pressurized fuel and oxidizer from tanks
11 and 13. The fuel and oxidizer then flow through conduits 17
and 19 and impinge upon each other through a centrally positioned
manifold and suitable jets (not shown) in combustion chamber 15
where spontaneous ignition occurs. The reaction products are then
expelled through the open ends of combustion chamber 15 as plasma
which includes the desired barium neutral atoms and barium ions
as individual species.
The fuel utilized in fuel tank 11 is either hydrazine (N2 H4)
or liquid ammonia (NH3) while the oxidizer employed is selected
from the group consisting of liquid fluorine (F2), chlorine trifluoride
(ClF3) and oxygen difluoride (OF2). When using hydrazine as the
fuel, barium may be dissolved therein as barium chloride, BaCl2,
or barium nitrate, Ba(NO3)2, or a combination of the two. When
using liquid ammonia as the fuel, barium metal may be dissolved
therein. The combination found to produce the highest intensity
of Ba° and Ba+ resonance radiation in ground based tests involved
a fuel of 16 percent Ba(NO3)2, 17 percent BaCl2 and 67 percent
N2 H4 ; and as the oxidizer, the cryogenic liquid fluorine F2
and in which an oxidizer to fuel weight ratio was 1.32.
Other combinations of ingredients tested are set forth in Table
I below:
TABLE I
______________________________________
System Optimum O/F Percent
Ionization
Calculated
______________________________________
16.7% BaCl2 -
83.3% N2 H4 /ClF3
2.36 68.0
26% BaCl2 -
74% N2 H4 /ClF3
2.08 70.0
50% Ba(NO3)2 -
50% NH3 /ClF3
1.52 -
42.9% Ba(NO3)2 -
57.1% N2 H4 /ClF3
1.19 50.0
16.7% BaCl2 -
83.3% N2 H4 /F2
1.95 68.8
26% BaCl2 -
74% N2 H4 /F2
1.71 70.6
21% BaCl2 -
9% Ba(NO3)2 -
70% N2 H4 /F2
1.57 68.5
17% BaCl2 -
16% Ba(NO3)2 -
67% N2 H4 /F2
1.31 68.1
13% BaCl2 -
21.5% Ba(NO3)2 -
65.5% N2 H4 /F2
1.34 63.7
9% BaCl2 -
30% Ba(NO3)2 -
61% N2 H4 /F2
1.04 63.7
42.9% Ba(NO3)2 -
57.1% N2 H4 /F2
0.976 43.0
42.9% Ba(NO3)2 -
57.1% N2 H4 /OF2
0.694 46.9
26% BaCL2 -
74% N2 H4 /OF2
1.22 52.8
______________________________________
The conditions under which each of the combinations listed in
Table I were tested were ambient and the percentage ionization
was calculated by equations set forth in NASA Contract Report
CR-1415 published in August 1969.
The chemical supplier and manufacturers stated purity for the
various chemicals employed are set forth in Table II below:
______________________________________
Chemical
Supplier Purity
______________________________________
N2 H4
Olin Mathieson Chemical
Technical Grade
Company, Lake Charles,
97-98% N2 H4
Louisiana (2-3% H2 O)
NH3
Air Products and Chemicals
Technical Grade
Allentown, Pa.
BaCl2
J. T. Baker & Co. Reagent Grade
Phillipsburg, N.J.
Ba(NO3)2
J. T. Baker & Co. Reagent Grade
Phillipsburg, N.J.
F2 Air Products & Chemicals
98%
Allentown, Pa.
ClF3
Allied Chemical Co.
99.5%
Baton Rouge, La.
OF2
Allied Chemical Co.
98%
Baton Rouge, La.
______________________________________
A solubility study of various
mixtures containing Ba(NO3)2, BaCl2 and N2 H4 was made at room
temperature and is shown in the triangular plot of FIG. 2. Seven
solutions that were used in the tests enumerated in Table I are
indicated by reference letters in FIG. 2 as follows:
a. 16.7% BaCl2 - 83.3% N2 H4
b. 26% BaCl2 - 74% N2 H4
c. 21% BaCl2 - 9% Ba(NO3)2 - 70% N2 H4
d. 17% BaCl2 - 16% Ba(NO3)2 - 67% N2 H4
e. 13% BaCl2 -21.5% Ba(NO3)2 -65.5% N2 H4
f. 9% BaCl2 - 30% Ba(NO3)2 - 61% N2 H4
g. 42.9% Ba(NO3)2 - 57.1% N2 H4
A mixture below the Saturation
Line, that is toward the Ba(NO3)2 or BaCl2 corners contained a
solid and a solution phase whereas the salts were in complete
solution above the saturation line.
All fuel mixtures or systems described were easily handled except
the 50 percent Ba(NO3)2 -50 percent NH3 system. This system caused
clogging of the feed valves due to precipitation of the Ba(NO3)2.
In addition the light values obtained using this system was relatively
low.
In testing of each of the fuel mixtures set forth in Table I the
Ba° light was greater than the Ba+ light for a given oxidizer/fuel
ratio in each of the mixtures. The maximum light occurred in all
systems at a point located between the stoichiometric O/F and
3 percent less than the stoichiometric O/F. The stoichiometric
O/F is defined as being equivalent to the oxidizer to fuel weight
ratio in a balanced equation assuming the salt is converted to
free Ba, F to HF, Cl to HCl and O to H2 O. For example, one system
tested had an O/F ratio of 142 grams oxidizer per 100 grams fuel
or 1.42/1.00. If the barium is assumed to be converted to BaF2
then the stoichiometric O/F is 1.47. Since the greatest light
output in all cases occurred with O/F less than stoichiometric
it is apparent that little of the Ba was combined as BaF2 or BaCl2.
This was confirmed by spectrographic analysis.
In Table II the various systems are listed in decreasing light
output or relative light intensity as measured by phototubes in
millivolts, thereby indicating the relative barium yield.
TABLE III
__________________________________________________________
SYSTEM MAXIMUM RELATIVE
(percent weight for fuel)
INTENSITY, millivolts
Ba° 5535 A
Ba+ 4554 A
___________________________________________________________
17% BaCl2 -16% Ba(NO3)2 -67% N2 H4 /F2
27600
11800
13% BaCl2 -21.5% Ba(NO3)2 -65.5% N2 H4 /F2
23600
8340
21% BaCl2 -9% Ba(NO3)2 -70% N2 H4 /F2
20600
9100
9% BaCl2 -30% Ba(NO3)2 -61% N2 H4 /F2
16600
5970
26% BaCl2 -74% N2 H4 /F2
16600
6520
26% BaCl2 -74% N2 H4 /OF2
11800
2100
16.7% BaCl2 -83.3% N2 H4 /F2
9100 3350
42.9% Ba(NO3)2 -57.1% N2 H4 /F2
9000 1800
42.9% Ba(NO3)2 -57.1% N2 H4 /OF2
7300 1330
42.9% Ba(NO3)2 -57.1% N2 H4 /ClF3
663 94
50% Ba(NO3)2 -50% NH3 /ClF3
221 44
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From the above information,
it is readily seen that the 17 percent BaCl2 -16 percent Ba(NO3)2
-67 percent N2 H4 /F2 system gave the greatest amount of light
intensity of the 4554 A Ba+ and 5535 A Ba° spectral lines.
Ambient tests showed that the optimum oxidizer to fuel ratio of
this system was 1.32 to 1.00. This system containing 8.52 weight
percent barium was estimated to be 68.1 percent ionized. Also
since this system had the largest relative light intensity it
would be expected to give the greatest amount of Ba° and Ba+
and would appear to be the optimum system for a barium payload.
In all systems tested it was found that the relative light reached
a maximum at the O/F corresponding to the stoichiometric equation
yielding barium as one of the reaction products and that the relative
light output was sensitive to the O/F. Moving to either side of
the optimum O/F caused a sharp decrease in relative light.
In vacuum tests the ignition of each system tested was smooth
and like the ambient tests, took place in the combustion chamber.
The rapid expansion in vacuum caused a decreased atom and ion
density in the luminous flame which caused the light intensity
to be about 1/37 to 1/50 the intensity measured in ambient tests.
The percentage ionization was approximately the same for vacuum
and ambient tests.
The operation of the invention is now believed apparent. Initially,
fuel tank 11 is charged with the fuel containing the desired quantity
of dissolved barium salt and pressurized with helium. The fuel
tank pressure may be in the range of 6.89 to 20.06 ¥ 105 Newton/meter2.
Oxidizer tank 13 is also charged with the appropriate oxidizer
and pressurized. Cryogenic oxidizers such as OF2 and F2 are condensed
from gases in the closed oxidizer tank which must be maintained
enclosed in a liquid nitrogen bath. The oxidizer feed valve 23
and conduit 19 must also be maintained at liquid nitrogen temperature
with a liquid nitrogen jacket when employing a cryogenic oxidizer.
The noncryogenic oxidizer, ClF3, may be pressurized into the closed
oxidizer tank 13 from a supply bottle with super dry nitrogen.
Combustion chamber 15 is formed of stainless steel, aluminum,
or the like F2 compatible metals and is internally partitioned
by the manifold, not shown. The conduits 17 and 19 terminate in
a manifold having injector orifices (not shown) mounted 90°
to each other within each end of chamber 15 and sized for pressure
drops of 5.24 to 10.2 ¥ 105 Newton/meter2 across the orifice.
Fuel and oxidizer flows are in the range of 2.05 to 6.82 Kg/sec
each. The entire system is carried into the upper atmosphere or
interplanetary space by rocket vehicle 10 where, in response to
a suitable signal, timing mechanism or the like, valves 21 and
23 may be selectively opened and closed and the pressurized liquid
fuel and oxidizer will flow through conduits 17 and 19 into combination
unit 15. When the hypergolic liquids impinge upon each other,
they spontaneously ignite to expel reaction product gases or plasma
including the highly luminous barium neutral atoms and barium
ions as individual species. All of the barium reaching the combustion
chamber is vaporized and released through the opposite ends thereof
so that a high yield efficiency is obtained. The resulting high
flame temperature, approximately 4,000°K., and some as yet
not determined chemical activation, produces a relatively large
amount of barium ions in the flame which is a highly desirable
condition. It has been estimated from spectroscopic measurements
that the degree of ionization may be as high as 75 percent in
the released plasma in comparison to being on the order of 1 percent
for the previously used Ba-CuO solid system which depends almost
entirely on solar photoionization, a time-dependent phenomena
which further reduces the usable barium yield of this known system.
Thus, it is readily apparent that the present invention provides
an inherently more efficient process of producing barium clouds
wherein the degree of ionization in the released plasma is much
greater. The selectively opening and closing of valves 21 and
23 gives the possibility of a payload with multiple releases permitted
due to the start and stop capabilities of the liquid system. Also,
the liquid system of the present invention gives the possibility
of controlling rates so that a trailtype release can be obtained
as well as a point-source type. In addition, the liquid system
of the present invention effects the formation of barium atoms
and ions at the time of combustion and expansion at high temperatures
and results in little opportunity for the barium to condense during
release.
There are obviously many variations and modifications to the present
invention that will be readily apparent to those skilled in the
art without departing from the spirit or scope of the disclosure
or from the scope of the claims.
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Blessings to all - rhonda
May this effort benefit all sentient beings in creation...
OM AH HUM VAJRA GURU PADMA SIDDHI HUM - HRIH