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Selected Pyrotechnic
Publications of Dr. Takeo Shimizu,

Part Part 3. Studies on Fireworks Colored Flame Compositions
This volume contains a series of seven articles that originally appeared
in the Journal of Industrial Explosives from 1958 to 1959. The articles were
translated from Japanese to English by Dr. Shimizu. The articles have been formatted into
a 2-column, 8½×11" format. [ISBN 1-889526-11-8]
A review of this book by Barry
Sturman appeared in Issue 10 of the Journal
of Pyrotechnics, Winter, 1999.
Table of Contents (Part 3)
Part
I. Theoretical Development of the Line-Reversal Method for Temperature
Measurement of Flames |
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Abstract: A flame of fireworks
generally contains many solid or liquid particles which cause a continuous
spectrum. In order to apply the line-reversal method of temperature
measurement to such flames, the author introduced a theoretical equation
which denotes the ratio of the intensity of the resonance line part
to that of the neighboring part of time spectrum when the standard
light beam is introduced into the spectroscope through the flame.
This equation shows very clearly that as long as the flame does not
contain so many particles that it prevents the standard light beam
from permeating, the line-reversal method is always effective. Using
this equation a method of measurement of a flame temperature which
is higher than the available maximum brightness temperature of the
standard light is proposed. The author has applied this method to
two examples of high temperature fireworks flames, which consist of
some magnesium powder composition, and we obtained the temperatures
of 3,159 and 3,214 K. |
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Part
II. Temperature Measurement of Flames by Means of Line-Reversal
Method |
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Abstract: Using the theory developed
in Part I, flame temperatures for various fireworks compositions have
been measured by means of line-reversal of Na-D lines.
(1) For the case of low flame temperature compositions The
compositions that contain combustible organic materials (i.e., shellac,
rosin, pine root pitch, etc.) are commonly used in ordinary fireworks.The
author has prepared various combinations of components to see the
influences of oxidizers, fuels, coloring agents, etc. Temperatures
are measured by method 1 from Part I. The result shows that the highest
temperature appears at the base of the flame. Generally potassium
perchlorate gives higher temperatures than ammonium perchlorate.Potassium
nitrate always gives lower temperatures than other oxidizers.
The highest temperature is obtained when the ratio of fuel to oxidizer
(potassium perchlorate, ammonium perchlorate or potassium nitrate)
is about 1/5. For this ratio, the maximum temperatures obtained
are as follows:
| Oxidizer |
Temperature (K) |
| Ammonium perchlorate |
2,480 |
| Potassium perchlorate |
2,520 |
| Potassium nitrate |
2,000 |
(2) For the case of high flame temperature compositions A composition
that contains magnesium powder can create a flame of very high temperature
of more than 2,900 K. Temperatures were measured by method 2 from
Part I. In this case the photographic method was applied to measure
the intensity of spectrum lines, and we have obtained temperatures
of 2,7003,000 K, but the accuracy of these data are not as good
because of the uncertainties of the photographic method due to the
instability of the flame. |
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Part
III. On Backgrounds of Color Flame Spectra |
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Abstract: Blank runs were made with compositions not nominally color-producers
to investigate the lines, bands or continuous spectra which appear
as background and disturb the desired spectra of red, yellow, green,
etc. These sample compositions consist of solid materials such as
oxidizers (ammonium perchlorate, potassium chlorate, potassium perchlorate,
potassium nitrate, etc.), low temperature combustibles (shellac, rosin,
pine root pitch, etc.), and magnesium powder for high temperature
combustibles.
In the case of low temperature class sodium D (Na-D) lines (5890
and 5896 Å, caused by impurity contained mainly in the oxidizers),
continuous spectra (caused by carbon particles and potassium atoms)
and K lines (5802, 5783, 5832, 5813; 5340, 5324, 5360, 5343; 5090,
5084, 5113, 5080; 4044, 4058 Å) are observed. In the case of high
temperature class Na-D lines are also observed, and in addition
to the above, MgO bands and continuous spectra (the latter are caused
by solid metal oxide particles and K atoms) are found.
The main spectra of disturbance are Na-D lines and continuous spectra.
Purification of ingredients is very important to remove Na-D lines
and to obtain fine colored flames. In the case of high temperature
class, the addition of ingredients of chlorine compound such as
polyvinyl chloride, ammonium chloride, etc. to a composition is
effective to decrease intensity of the continuous spectra, and it
is supposed that the metal oxide of the solid phase is converted
into the metal chloride of the vapor phase in the presence of chlorine
or hydrochloric acid in the flame, but this should be ascertained
by further experiments of higher accuracy. The addition of shellac
is also effective to weaken the intensity of the continuous spectra,
decreasing the temperature of the flame.
The permeability coefficients and black body temperature of flames
of basic compositions are measured for reference. |
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Part
IV. On Flame Spectra of Red, Yellow and Green Color Compositions |
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Abstract: Spectra of
flames of red, yellow and green color compositions are examined under
various conditions.
a. Red Flame A red flame is given by bands of some strontium
salts. These bands consist of five main bands [i.e., a
(6013), b (6203), g (6300), d
(6428) and e (6558)], where each figure
shows wavelength of the maximum intensity in Angstroms (Å). The influence
of chlorine on a band is quite different from others, namely a
band is rather weakened by chlorine but others are intensified, and
this effect of hydrochloric acid gas is higher than that of chlorine
gas. Especially in low temperature class this is very clearly observed.
The influence of kinds of strontium salts is very small, and that
of oxidizers which produce either chlorine or hydrochloric acid gas
is very remarkable. If we add some ingredients which have chlorine,
they can intensify each bands only in case of high temperature class.
The effects of calcium (Ca) Salts were also examined.
b. Yellow Flame Composition A yellow flame is given by sodium
salts. The spectrum consists of mainly Na-D lines, but in addition
a continuous spectrum of Na atoms appears between 5,800 and 6,100Å
and changes the flame color to rather white, especially in high temperature
class.
c. Green Flame Only BaCl bands can give green flames when barium
salts are used as color giving ingredients, and no chlorine composition
cannot give green color because in this case, only BaO bands appear,
giving white color to the flames. In presence of chlorine both BaCl
and BaO bands appear and the effect of chlorine or hydrochloric acid
gas in a flame are seemed to weaken the BaO bands and on the contrary
to intensify BaCl bands, and the effect of chlorine gas is rather
lower than that of hydrochloric acid gas. And so, ammonium perchlorate
gives more clear green color than potassium perchlorate . Adding some
kind of chlorine compound is also effective to intensify the green
color. |
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Part
V. On Flame Spectra of Blue Color Compositions |
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Abstract: We can see three kinds
of flame color (i. e., blue, light green and reddish orange) when
we insert a small copper piece into a flame of a burner. The blue
color is caused by CuCl bands, and the strongest lines between 42694560Å.
Our purpose is to use this color to fireworks. This is given by some
copper salts or copper metal powder in the presence of chlorine or
hydrochloric acid gas, but if concentration of gas is small ,the blue
color is disturbed by light green color, which seems to be caused
by a continuous spectrum of other copper chloride bands (52635531Å).
The flame spectra are examined under various conditions. In, the case
of low temperature class, ammonium perchlorate is the best oxidizer
and gives excellent bright blue. In the case of high temperature class
it is necessary to decrease the percentage of magnesium powder, because
the CuCl bands seem to dissociate with increasing of magnesium. |
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Part
VI. On Flame Spectra of Metal Aluminum Composition |
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Abstract: The previous papers showed
the effect of magnesium powder as a combustible in high temperature
class compositions. In this paper the effect of aluminum powder is
examined. In general aluminum melts and is sprayed as sparks out of
the flame, and is not so evaporable because of its high boiling point.
And in this case the intensity of the spectrum of color-giving bands
is not so high as in the case of magnesium. |
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Part
VII. On Composition Series for Practical Use |
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Abstract: (1) The spectroscopic
studies in previous papers are summarized so as to apply the principle
of flame color creation to practical use.
(2) According to the results of (1), various samples of red, yellow,
green and blue of several composition series are prepared. Their
flame colors are examined by the naked eye and good colors are selected.
According to these, effective color zones are written as circular
lines in trigonometrical graphs.
(3) As far as these studies are concerned the important results which
seem to be common for each series are as follows (a) The width
of an effective composition zone in a graph is very narrow In the
case of low temperature class and is fairly wide in- the case of high
temperature one. (b) Ammonium perchlorate is the best oxidizer, for
it can produce HCl in a flame and creates deep color. (c) Polyvinyl
chloride is also the best additional ingredient which can create a
deep-color by producing HCl gas in flame like ammonium perchlorate.
(d) It is necessary to protect compositions from moisture perfectly
in A case of high temperature class lest magnesium and other ingredients
should react each other. For-practical applications deep and brilliant
color flames are obtained only with this consideration. |
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