CONTRACT(Sanitized)

• Document Type: CREST
• Collection: NGA Records (Formerly NIMA)
• Document Number (FOIA) /ESDN (CREST): CIA-RDP78B04770A002800030038-9
• Release Decision: RIPPUB
• Original Classification: C
• Document Page Count: 41
• Document Creation Date: December 28, 2016
• Document Release Date: June 3, 2005
• Sequence Number: 38
• Publication Date: September 13, 1965
• Content Type: LETTER

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25X1 Subject: Contract
Task Order No. 93
?
25X1
DICK S.
Dear Dick:
COKFIDENTIAL
164-5-27
Copy/of 3
Enclosed are four copies of the Final Technical Report on
the subject task. We have forwarded one copy of this report to
the Contracting Officer for his file. This report is the final
item to be delivered under Task 93 and completes the technical
reporting requirements.
Enclosures
Final Report "Black and White Films"
30 August 1965 (four copies)
Declass Review by NGA.
CROUR 1
aCLUDED FROM AUTOMATIC
DOWNGRADilIG
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Non-Reversible Color - Study
Progress Report No. 8
Financial Status
Amount Authorized
Estimated expenditures thru 28 Feb 65
Funds Committed
Funds Remaining
Technical Status
The engineering progress report for the month of
February 1965 is attached.
3/8/65
410 Distribution:
Technical Representative - two copies
Contracting Officer - one copy
File - one copy
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Progress Report #8
Black and White Films
February 1965
The effort in the month of February was spread over a variety of
activities. The anthraquinone dyes were studied further with rate and quantum
efficiency results to be described later in this report. The apparatus has been
overhauled and modified with the view towards greater operating efficiency and
accuracy of results. A considerable period of time was spent in reformulation
and reassessment of ideas on the nature of the process, some of which were
incorporated in the proposal for continuance of the project. Finally, some
experiments were run comparing the ASA rating of some of the films with those
obtained on silver halide films of known sensitivity. Previous results, obtained
by use of a laser beam, indicated an ASA equivalent of 0.5 to 0.09. When the
comparison was made using a 500 watt projector as the light source, an ASA
of about 5 x 10-4 was obtained. A more comprehensive comparison of film
speeds is planned for March.
The remainder of this report will be given over to a review of the
reaction rate experiments performed during the work on this project, a summary
of the quantitative results achieved, and of their significance to the objectives of
the project.
Experimental Apparatus
The experimental apparatus (MEA) was described in Progress Report #3
for September 1964. In brief, the apparatus functions by moving a slide into and
through a beam of light, which may be monochromatic, or may be white light.
Both before and after exposure, the absorption of monochromatic light at the
wavelength of maximum absorption of the dye is measured as a function of
distance along the slide. This is done by moving the slide past a narrow slit
while monitoring the intensity, of transmitted monochromatic light by means of
a photomultiplier. A typical result is shown in Figure 1. The section of curve
marked A corresponds to the portion of the film which was in the light beam at
the start of illumination, and which moved out of the beam as the film
corresponding to section B moved into the beam. Thus, each half of the curve
constitutes a plot of intensity of transmitted light against exposure.
This technique of obtaining the rate of dye bleaching has several advantages.
It is simple, rapid, and results in a sample in which the effect of variation in
exposure may be visually examined as well as measured intrumentally. The
method is useful, however, only for experiments in which high accuracy is not
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important, because it is difficult to incorporate corrections due to variations
in slide thickness in the calculations. When it is necessary to achieve high
accuracy, a stationary sample is used. In the stationary sample technique, a
small area of the sample is illuminated by the desired light. Simultaneously,
the transmitted light is passed through a monochromator if it is not already
monochromatic, and monitored by a photomultiplier. A curve obtained by this
technique is shown in Figure 2.
Analysis of Data
The data obtained by these two techniques is in the form of plot of percent
transmittance against time. Optical density D is defined as log 10/I, where 10
is the intensity of the incident light, and I that of the transmitted light. In the
usual run, a full scale deflection (100) is adjusted to correspond to light
transmitted by a blank slide. In this case, us percent transmittance. By Beers
law, D = log 10/I = Cl, where E is extinction coefficient, C concentration and
1 thickness of sample. If the absorption curve of a solution of dye of known
concentration is obtained, E can be calculated. Assuming that 6 is the same
in solution as in the film, C can be calculated at any time during the run. The
analysis of the mathematical relationship between concentration and time is
termed the kinetics of the reaction.
For simple, one step reactions in which one molecule of species A reacts
with one molecule of species B, we can write - d(A)/dt = k(A) (B), where the
parentheses connote concentration. In a rigid medium such as a polymer film,
such simple reactions are likely, since diffusion of reactive intermediates towards
each other is hindered.
In the experimental investigation of these reaction rates, one may choose
conditions of concentration in various ways, to fulfill different objectives. For
example, one may work with films of optical density greater than two, less than
0.1, or of intermediate density. For the initial study, we chose to work at
intermediate densities, for several reasons. This region is easiest to handle
experimentally, much of the equipment was available in the laboratory, and in
addition, the color changes in the film are readily produced and readily observed.
However, the regions of very high and very low optical density yield quantitative
data of greater significance, as will be shown below. For this reason, a new
instrument has been purchased and equipment designed and built to make it possible
to investigate all regions of optical density, and to compare the results and
conclusions derived from each. The new instrument has much greater stability
than the photomultiplier used previously, and has accurate range switching
capabilities, thus allowing high accuracy independent of optical density.
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We consider next the significance of the results obtained in the extreme
regions of optical density.
A. Initially High Optical Density - When the initial optical density is
around two or more, large changes in the concentration will produce only small
changes in the number of photons absorbed. Since the extent of reaction is
directly proportional to the number of photons absorbed, and the number of
photons absorbed remains relatively constant, it follows, that the extent of
reaction will be independent of the concentration of the dye. The flux of photons
is constant, and can be absorbed into the rate constant. Since we are used to
thinking of rate constants in terms of concentrations of reactants, we will call
the constant for this situation the zero order rate constant 1(0. Since very little
of the light is transmitted, this is an experimentally difficult region to investigate.
To summarize the relationship
d(C)
-ko = k(C1 )P
dt
where C1 is a limiting concentration and P is the flux of photons per unit area
per unit time.
B. Initially Low Optical Density - When the initial optical density is
around 0.1 or less, the changes in photon flux from the front of the film to the
back will be relatively small and relatively unaffected by changes in the
concentration of the dye. In this case, the rate of loss of dye will be directly
proportional to the concentration of the dye. We call this rate constant a first
order rate- constant,- again incorporating the photon flux into the constant.
d(C)
dt
k1 (C) = k(C)P
For intermediate optical densities in the region of about 0.7 - 0.1, first
order kinetics are reasonably well followed, but the interpretation of the results
may be more complicated due to the variation of photon flux through the film.
Most of the results obtained to date have been in this intermediate region, since
the experimental technique is much easier and more accessible. As mentioned
above, the new equipment will make it possible to correlate the results in the
three density regions. The results which will be discussed below are primarily
from the intermediate region of density .07 - .01.
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To obtain the rate constants, the above equations are integrated, resulting
in, respectively,
and
C=kt+C
o o
in C = k t
Co
Since C = D/8 1, a plot of D against t will result in a curve with slope
ko 6 1. If zero order kinetics are followed, this will be a straight line. Such a
curve is illustrated in Figure 3. A plot of log D against t will result in a straight
line if first order kinetics are followed. The slope will be kJ., all the other
constants affecting only the intercept. In practice, one must factor into the
calculation the absorption of the reaction products, leading to a somewhat more
complex equation. The result of a plot of this equation is illustrated in Figure 4.
One criterion of reactivity of great interest is the quantum efficiency.
This is defined as the number of molecules which react divided by the number
of photons which have been absorbed. That is to say, it is the effectiveness of
an absorbed photon in producing a chemical reaction. The photon flux must be
known in order to calculate quantum efficiency. Photon flux is arrived at through
a calibration of the apparatus with an absolute energy measuring device, the
multijunction thermopile. In our case, a twelve junction Eppley thermopile was
used to calibrate the irradiation system at. each of the many wavelengths. From
the energy falling on unit area at the plane in which the sample is kept and from
the wavelength of the light, the number of photons per unit time can be calculated.
The change in concentration per unit time is given by the first order rate constant
times the concentration. This number in units of molecules bleached per minute
per cm2 is divided by the number of photons absorbed per minute per cm2,
obtained by multiplying the photon flux by the initial fraction of light absorbed.
CH
- -
Et EtI
methine dye
anthraquinone dye
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Tables 1 and 2 give lists of the dyes for which quantum efficiencies have
been measured and information on the structures of the dyes. In Table 1 the
methine dyes are listed. A correlation between the basicity of the heterocyclic
rings in the dye molecules and the quantum efficiency can be shown. This
indicates that the reaction is a reduction reaction since basicity can be considered
to be the tendency to push electrons into the molecule. When there is a high
concentration of electrical charge, or rather of electrons at the reactive points
in the molecule, these sites are more prone to reaction with protons or similar
chemical entities, thus leading to reduction of the double bond and destruction
of the resonance between the heterocyclic rings in the molecule. In the
anthraquinone series shown in Table 2, the quantum efficiency varies over a wide
range. The two compounds which have the highest quantum efficiency, about 2. 6,
both have amino groups situated on the anthraquinone molecule and have no other
substituents elsewhere in the molecule. The structure of the one compound,
code no. 139, is not completely known. Some of the amino groups are substituted
with methyl in place of hydrogens, but it is not known which ones or how many.
The other compound has only two amino groups. The contrast between that
compound, no. 181 and no. 95 which has one methyl group substituting for a
hydrogen on one of the two amino groups, and otherwise identical structure, is
very great, a factor of over five in quantum efficiency. In point of fact, the
derived results on quantum efficiency for compounds no. 181 and 139 are very
high and the data for these materials will be rerun to assure precision. If the
quantum efficiencies are actually greater than one, then the process has a built-in
multiplicative factor which, if properly exploited, can lead to high speed films.
It should be noted that these two compounds have relatively low extinction
coefficients. The method of procedure indicated by these results is as follows.
Molecules are to be sought which have the same ability to force electrons into
the conjugated resonance aromatic ring system but which in addition have high
extinction coefficients and thus are more effective in terms of photographic
properties. For example, compounds which may be used to test this hypothesis
are those with amino groups in the one and four positions and methoxy,Jpromo,
or similar groups in the two position. These compounds are predicted to have
similar reactivity and higher extinction coefficients than the ones with which we
are comparing them.
The foregoing discussion has been designed to describe, clarify and
illustrate the measurements and calculations which are being made on this project,
to indicate the type of conclusions which can be drawn from the measurements,
and to illustrate also the way in which the conclusions drawn direct further attack
and approach to the problems. Thus, the experiments on the anthraquinone dyes
indicate the structural factors of importance to the bleaching process. Dyes are
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then obtained accenting these structural features. If the results agree with the
predictions, further improvements in structure can be sought; if not, the
theory is revised to accommodate the new data, and the process is repeated.
Thus, this repetitive, cyclic process leads to dyes of greater sensitivity in the
bleaching process and to a knowledge of which structural factors can be safely
modified in attempts at obtaining different initial colors. In addition, when
other classes of dyes are investigated, relatively few experiments should
determine whether similar factors are operative.
Plans for March
Much of the work for March has been indicated in the above report.
Several dyes will be examined for speed values under identical conditions as
silver halide films of known ASA rating. Each of several dyes will be
investigated in films of low, intermediate and high optical density and the rate
constants compared. Dyes predicted to be sensitive will be obtained or _prepared
and investigated. Dye screening will be continued in classes other than methine
and anthraquinone dyes.
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Table I
Quantum Efficiencies of Methine Dyes
No.
Name Structural Groups
Color
Wavelength
Quantum
Efficiency
53
Orthochrome T N-ethyl 6 methyl quinoline
Violet
570
0. 1
81
3, 3' -diethyl-2, 2' selena carbocyanine iodide
Violet
580
O. 061
84
3, 31-diethyl thiocarbocyanine iodide
Green
570
0. 042
120
Sevron Brilliant Red 2B Diethyl aniline
Magenta
550
0. 26
1, 3, 3 trimethylindole
143
Genacryl Red 6B 3 Methyl N(2 chloroethyl)ethyl
aniline 1, 3, 3 trimethylindole
Magenta
550
0. 14
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Table II
Quantum Efficiencies of Anthraquinone Dyes
No.
Name
Substituents
Color
Wavelength
Quantum
Efficiency
88
Waxoline Blue GA
1-NHCH3' 4-NH-C6H4-CH3
Blue
600
.065
95
Oracet Violet B
1-NH2' 4-NHCH3
Blue
620
0.43
139
Palacet Blue 3G
1, 4, 5, 8-NH2 (methylated)
Blue
640
2.78
140
Celliton Fast Blue FBBN
1-NHCH3' 4-NHC2H40H
Blue
600
0.10
141
Celliton Fast Blue Green BA
1, 4-NHC2H4OH, 5, 8-0H
Blue
630
0.023
181
Amacel Heliotrope R
1, 4-NH2
Violet
590
2. 64
186
Cibacet Brilliant Violet 3B
1, 4-NH2, 5-NO2
Blue-violet
570
O. 104
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Non-Reversible Color - Study
Progress Report No. 7
04770A002800030038-9
Financial Status
Amount Authorized
Estimated expenditures thru 26 Jan 65
Funds Committed
Funds Remaining
Technical Status
The engineering progress report for the month
of January 1965 is attached.
Distribution:
Technical Representative - two copies
Contracting Officer - one copy
File - one copy
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Progress Report #7
Black and White Films
January 1965
800030038-9
The criterion, discussed in the previous report, for the comparison of
the reactivity of various dyes to light is the quantum efficiency of the photo-
bleaching process. That is, it is the probability that an absorbed photon will
lead to a reacted molecule. The quantum efficiencies measured for the methine
dyes have been correlated with the basicity (the tendency to repel an electron)
of the heterocyclic groups of the dye molecules. The correlation is not precise,
but is very suggestive of an oxidation or reduction reaction. Polarographic
experiments have been started to determine whether a relationship between
potentials at which oxidation or reduction takes place, and quantum efficiency,
exists.
Further runs have been made on the kinetics of bleaching of anthraquinone
dyes. The calculations on these have not been completed. Changes have been
made in the apparatus to achieve greater accuracy and sensitivity, and further
changes are being planned. Delivery and installation of the necessary components
should be complete by the first week in March. Further precise work on quantum
efficiency measurements will be resumed when the apparatus has been reassembled.
Four dyes were tested as to the effect of heating after exposure on the
extent of bleaching. In one case, bleaching was increased by a factor of about
two. In another case, bleaching was considerably decreased. In the other cases,
the effect was slight. The significance of these observations is that the heat
fixing step may eventually provide a technique for control of gamma or of
sensitivity.
Experiments have been carried out to quantitatively determine the efficacy
of heating in fixing the films. In these experiments, the rate of bleaching after
heat fixing was measured and found to be immeasurably slow. Previous
qualitative results, indicating that the dye films were stable to light after heat
fixing were corroborated.
The results of a comparison between one of the dye films and two silver
halide films of known ASA rating indicate an equivalent speed for the dye of
approximately 0.5 to 0.06. This experiment was performed with high intensity
monochromatic light produced by a helium-neon laser. It is possible that this
type of radiation will produce results which are not representative of the
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materials. Experiments are being set up to accomplish the comparison at a
lower intensity, so as to provide results more pertinent to the intended end
use of the films.
Plans for February
The apparatus modifications mentioned above are to be completed.
Comparison of sensitivity of dye films with silver halide films of known ASA
rating is to continue. The results of the polarographic studies will be
analyzed to help complete the assignment of the reaction mechanism for the
cyanine dyes. Studies of the anthraquinone dyes will be continued.
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Non-Reversible Color - Study
Progress Report No. 6
Financial Status
Amount Authorized
Estimated expenditures thru 31 Dec 64
Funds Committed
Funds Remaining
00030038-9
Technical Status
The engineering progress report for the month of
December 1964 is attached.
1/14/65
Distribution:
Technical Representative -- two copies
Contracting Officer -- one copy
File -- one copy
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Progress Report #6
Black and White Films
December 1964
The observation, noted in the last report, that some dye-iodoform
systems are sensitive to light absorbed by the dye, has prompted a
reconsideration of the experimental methods to be used to evaluate reactivity.
If only light absorbed by the iodoform were active, as is the case for some
systems, comparisons of reactivity will be valid as long as a constant light
source at a fixed distance is used. In this case, the flux of photochemically
effective photons is constant. If, however, photons absorbed by the dye are
also active, as is the case in other systems, the flux of photochemically active
photons will depend on the absorption characteristics of the dye. For this
reason, an action spectrum was measured for one dye. That is, the rate of
reaction caused by illumination by nearly monochromatic light was measured
at each of several wavelengths. Within experimental error, the rate of
reaction of each wavelength was directly proportional to the rate of absorption
of photons.
The criterion for comparison of reactivity of dyes is the relative
probability of bleaching of the dye-iodoform complexes on the absorption of
a photon. Therefore, to obtain meaningful interpretation of data from exposure
to white light, we must go through a complex procedure involving multiplication
of the number of available photons at each wavelength by the fraction absorbed
at that wavelength, and a numerical integration of the resulting curve. As an
alternative to this procedure, we have adopted the technique of irradiating the
samples with nearly monochromatic light. The wavelength range is about 100
Angstroms, and is centered on the absorption peak of the dye. For slow
systems, the wavelength range can be increased to 200 Angstroms. While this
technique adds experimental complications, it enormously simplifies the
calculations.
Using this technique, rate constants and quantum efficiencies were
measured for all of the available methine dyes which showed bleaching, and
several of the anthraquinone dyes. Quantum efficiencies measured to date lie
in the range of 0.01 to 0.25. An attempt at correlation of these results with
the structural features of the dyes is in progress.
Further experiments included comparison of quantum efficiency of light
absorbed by a dye with that for light absorbed by iodoform. For the dye studied,
the ratio was about 6:1, with the iodoform absorption the more efficient. A
measurement of the effect of intensity on rate of bleaching showed the expected
effect, that is, that rate is approximately linear with intensity.
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Approved For Rise 2005/06/23 : CIA-RDP7813047704800030038-9
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The work on determination of changes in infrared spectra caused by
the bleaching reaction has continued. Several techniques of sample preparation
have been tried. Of these, a technique for obtaining infrared reflection spectra
shows promise. The standard methods of solution spectroscopy and KBr pellet
spectroscopy are not applicable since the reactions which take place in these
media differ from the bleaching reaction in the polymer film.
Plans for January
Work in the areas described above is to be continued: kinetic measure-
ments on anthraquinone dyes, structure-reactivity correlations, and infrared
spectra. Some modification of experimental procedure is planned, to reduce
experimental error and to increase efficiency.
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?
25X1
?
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Non-Reversible Color - Study
Progress Report No. 5
Financial Status
Amount Authorized
Estimated expenditures
thru 27 November 1964
Funds Committed
Funds Remaining
Technical Status
The engineering progress report for the
month of November 1964 is attached.
Distribution:
Copies 1 and 2 - Technical Representative
Copy 3 - Contracting Officer
Copy 4 - File
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?
?
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se 2005/06/23 : CIA-RDP781304770/40800030038-9
Progress Report #5
Black and White Films
November 1964
The effort during November has continued to be concentrated on the
quantitative evaluation of dyes as described in previous reports. Formulas
have been derived expressing the rate constant for dye bleaching in terms
of experimentally observed quantities. A punched card system for storing
dye data has been developed. This system simplifies the collation of data and
the ordering of structural information. One hundred sixty-lour dyes have been
recorded on the cards, of which 92 have knownformulas. Absorption spectra
have been obtained for 73 dyes, before and after illumination, some under a
variety of conditions and 28 of these have been evaluated on the MEA.
It has been found that some of the dye-iodoform systems are sensitive
to light absorbed by the dye as well as that absorbed by the iodoform. Thus,
for a given light source, many more photons are available to participate in the
reaction, and the film will be faster. In addition, this observation means that
in order to calculate a meaningful rate constant for dye bleaching, it will be
necessary to make a careful determination of the action spectrum of several of
the dyes and to determine the relationship of the action spectrum to the
absorption spectrum. (The action spectrum is the relation between the wave-
length of incident light and the extent of reaction.) If there is a simple
relationship between these spectra, a knowledge of the absorption curve will
suffice for the calculation of rate constants. Otherwise, action spectra may
have to be determined for many of the dyes. Apparatus has been ordered to
permit determination of action spectra. If it proves necessary to determine
action gpectra for most dyes, it seems feasible to modify the instrumentation
so that it can be used in conjunction with the MEA to obtain action spectra
automatically.
A start has been made on the problem of determination of infrared
spectra of dye systems. Several experiments have been planned, and project
personnel have learned the operation of the available infrared spectrophoto-
meter.
Plans for December
The measurement of rate of bleaching of all the dyes of known formula
which have been obtained thus far is to be completed. The correlation of
reactivity with structure is to be continued. It may be necessary to procure
additional dyes to augment the data, and to fill in gaps on the correlation.
Further work is planned on the action spectra of the dyes late in the
month. The investigation of feasibility of infrared spectra will be continued.
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tIIVi
15X1 Contract No. CONFIDENTIAL 1:7
36 06
Non-Reversible Color - Study
Progress Report No. 4
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038-9
?
25X11,
Financial Status
Amount Authorized
Estimated expenditures
thru 30 October 1964
Funds Committed
Funds Remaining
144-41-13
Copy /of 4
Technical Status
The engineering progress report for the
month of October 1964 is attached.
11/0/b4
Distribution:
Copies 1 and 2 - Technical Representative
Copy 3 - Contracting Officer
Copy 4 - File
CR:TIP 1
TWAY 161647a10. NO :77 ::,. 3 :Cf r.03,;:;*:-; OD .:7,E7 Cl 7 Et IL! CONFIDENTIAL
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25X1
Approved For Rose 2005/06/23 : CIA-RDP78604770
Progress Report #4
Black and White Films
October 1964
800030038-9
The effort in October has been concentrated on the quantitative evaluation
of a series of dyes, some of which had been previously examined qualitatively.
The MEA (materials evaluation apparatus) described in the previous report is
proving useful and versatile in these evaluations.
A routine screening process has been put into operation. This process
includes three steps. In the first step, a slide of the material to be evaluated
is run through the exposure step in the MEA. If a color bleaching is observed,
spectrophotometric curves are obtained of a sample before and after illumination.
A fresh slide of the material is then run through the MEA. The wavelength of
maximum decrease of absorption, as shown by the spectrophotometric curves,
is used in the evaluation or readout step of the procedure.
Twenty-seven dyes have been examined by this procedure during October,
in one or both of two media, to be described below. Of these, eleven were
processed through the three steps of the cycle. These showed a variety of
responses to illumination, ranging from fast to slow, and from large changes
in optical density to small changes.
Two media have been chosen for the more polar dyes. These are Carboset
resins, dissolved in tetrahydrofuran (THF), or in a mixture of THF and ethyl
alcohol. We have shown that the solvent has a large effect on the photosensitivity
of the dye, even though the solvent is evaporated before the illumination of the
dye. Of the solvents which have been evaluated, THF has proven the best, and
a THF-ethyl alcohol mixture almost as effective. At the other extreme, methyl
alcohol seems to inhibit photosensitivity. These results are strictly applicable
only to the dye systems used in the solvent evaluation. If the interaction is
between solvent and iodoform, as seems possible, the relationship will hold for
all dyes. This, however, will have to be checked with several additional dyes
of various dye classes.
Plans for November
Screening of dyes is to be continuethas is the correlation of structure
with photosensitivity. Further tests of the effect of solvent on photosensitivity
will be made. An investigation of the feasibility of obtaining infrared spectra
of the dye systems which can be useful in the elucidation of the reaction
mechanisms will be started.
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25X1
5X1
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CONFIDENTIAL
Non-Reversible Color - Study
Contract No.
Progress Report No. 3
Financial Status
Amount Authorized
Estimated expenditures
thru 9/25/64
Funds Committed
Funds Remaining
4
-6
frP}( ?
Technical Status
The engineering progress report for the month
of September 1964 is attached.
10/2/64
Distribution:
Copies 1 and 2 - Technical Representative
Copy 3 - Contracting Officer
Copy 4 - File
Ems 130111141. 341NTANS INFORMATION IFFICTINS THE
tbAtt13AL DEFENSE OF THE UNITED STATES WITHIN THE
PhaStINDp rpm ESPIONACE LAWS, TITLE IS, D.S.C..
WW. yn AND 734, ThE TEA *SH BE HEYALATION
W WHIN IN ANY MANNER TO AN 1171A0T1!ORIDED FEW*
IS felAWSITED BY LAW.
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GROOM
EXCLUDED FROM AUTOMATIC
DOWNGRADING
B04770A0028000306rAND
rAnIFICATION
25X1
Approved For Ripe 2005/06/23 : CIA-RDP78B04770A40800030038-9
Progress Report #3
Black and White Films
September 1964
During September, the effort has been concentrated on exploration of
the experimental parameters affecting the photoprocess, and on making
operational the new materials evaluation apparatus (MEA) constructed in the
previous month. The operation of the apparatus will be described in some
detail, with examples of results obtained. Following this, the parametric
studies will be described briefly.
1. Apparatus. The apparatus designed for the evaluation of materials (MEA)
is shown in Figures 1 and 2. Figure 1 is a photograph of the apparatus as it is
set up, and Figure 2 an exploded view. The apparatus is used to expose a
slide to light from the projector, and then to evaluate the results of the
illumination.
In exposure, a 1" x 3" microscope slide, coated with a sample to
be evaluated, is inserted in the slide holder. The slide initially is shielded
from illumination. It is then caused to move into the field of illumination at a
constant rate. When the leading edge of the slide has traversed an appropriate
distance, the light is shut off by means of a microswitch activated by the slide
carriage. The slide then has had an exposure which varies linearly from the
total time of exposure at one end of the exposed area to zero at the other. If
we wish to investigate the effect of illumination by light of a particular
wavelength region, we can insert an appropriate filter combination in the
space provided, as shown in Figure 2.
For evaluation of the results of illumination, a thin slit is interposed
between slide and projector. A monochromator, set at the wavelength of
maximum absorption of the dye, monitors the transmitted light, which is then
picked up by a photomultiplier. The output of the photomultiplier is recorded
by a potentiometric recorder. For precise quantitative work, it is necessary
to run a similar curve on the sample before exposure in order to get a base
line, which reflects variations in thickness of the sample. This is illustrated
by the lower curves in Figures 4 and 5.
Figures 3 and 4 illustrate the results obtainable with this apparatus.
Figure 3 is reproduced from the first progress report in this series. It shows
the absorption spectrum of Brilliant Oil Blue with iodoform in polystyrene after
various exposures to a tungsten source. From the curve, it is seen that the
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wavelength of maximum absorption of the dye is at 6500 A. Illumination causes
a maximum change in absorption of the dye at this wavelength. When a slide of
the same dye, made up in the same way, is run through the MEA, with the
monochromator set at 6500 A, the curves of Figure 4 are obtained. The lower
curve shows the absorption of the slide before illumination, the upper curve
after illumination. The time of traverse of the slide was 107 seconds.
Illumination was by a Prado 500 watt projector, set up as shown in Figure 1.
To determine the evenness of illumination across the slide, a slide
of Sudan Blue with CHI3 was illuminated while stationary, in the position it
would normally occupy at the end of a run. The slide was then evaluated in the
way described above, with the results shown in Figure 5. As is evident from
the figure, the distribution of intensity is highest in the center of the field,
falling off seriously at the ends. To overcome this problem, the central portion
of the field only will be used, corresponding to the horizontal line marked A on
the figure, which subtends a space of 0.5 inch. The variation of intensity in
this area is +3% of the average intensity.
2. Parametric Study. In order to make meaningful comparisons of
dyes, and correlations between dye structure and reactivity in the photoprocess,
it is essential that the experiments be carried out under as nearly identical
conditions as possible. If this is not done, extraneous factors, such as
interactions between photosensitive reagent and solvent or binder, may
invalidate the comparisons. To obviate the effect of such extraneous factors
on the dye itself, experiments should be done, if possible, in more than one
solvent-binder system. For non-polar dyes, a good system is available, that
is, polystyrene in benzene. Here, interactions are at a minimum, and the
photosensitive reagent currently in u, iodoform, is sufficiently soluble. For
more polar dyes, the situation is not as favorable. We have been experimenting
with the Carbosets, a family of acrylic resins, in a variety of solvents. We
have not as yet chosen a standard reference solvent-binder system, since none
of the combinations we have tried is completely satisfactory. Work in this area
is continuing. We hope to standardize on a pair of solvent-binder systems for
polar dyes in the near future.
Other parameters which have been under study are the temperature
to be used in the film drying step, and in the heat-locking step, and the
concentrations of dye and iodoform that are most effective. In the study of dye
to iodoform ratio, good results were achieved at a dye/CHI3 ratio of 1:2, but
the system gets faster, in the photographic sense, as the ratio goes to 1:5, at
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Approved For Rillase 2005/06/23 : CIA-RDP781304770.2800030038-9
-3-
the expense of a deepening of the yellow iodoform background color in the
exposed areas. The temperature at which the films are dried is found to be
important. A drying routine of 10 minutes at 1000C is found to be sufficient
to deactivate the films. A temperature of 750 gives good results, and has
been adopted as routine. Heat locking of the exposed films can be accomplished
in about five minutes at a temperature of 1400. The discrepancy between the
conditions for film casting and for heat locking is undoubtedly due to the higher
mobility of the iodoform in the liquid, so that it is more readily evaporated in
the film casting process.
The effect of delaying the casting of slides after preparation of the
solution on slide quality and sensitivity was also investigated. Adverse effects
were noted when the solution was stored overnight before casting.
3. Plans for Future Work. The apparatus will be modified as described
in Section 1. It will then be calibrated, and a routine procedure developed.
This will result in consistent and meaningful quantitative data.
The testing of solvent-binder systems for polar dyes is continuing,
and selection of standard systems will be made. When this has been done,
continuation of the dye screening work, and review of some of the dyes already
screened in the light of the improved solvent-binder systems is scheduled.
When sufficient data are available for meaningful correlations to be made, a
comprehensive review will be written and included in the appropriate progress
report. The present target date for this review is Progress Report #6, the
half-year report.
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Approved For Rose 2005/06/23 : CIA-RDP78B047701,800030038-9
Approved For Release 2005/06/23 : CIA-RDP78604770A002800030038-9
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Approved For Re 2005/06/23 ? C M110
CONFIDENTIATB?4??A
Non-Reversible Color -
Study
25X1
Contract
Progress
Report No. 2
Financial Status
25X:14,
Amount Authorized
Estimated expenditures thru 8/28/64
Funds Committed
Funds Remaining
800030038-9 144-23-28
Copy / of 4
L69
Technical Status
The engineering progress report for the month
of August 1964 is attached.
Distribution:
Copies 1 and 2 - Technical Representative
Copy 3 - Contracting Officer
Copy 4 - File
WRIMINAR MINTAITM IMORWATION APFUTHEO THE
INATTONAL DEMME OP TM UNITED STATES WITHIN THE
IMAKIND Of THE WIGWAM LAWS, TITLE tE, RJR.,
S. 793 AND 794, THE laisUltIS11/1 REVELMICH
Of WerA IN ANY MANNER TO LH IINAUTITURIZED?PERSO
ID PROYMBITED BY LAW. pprovea -For eiease 2005/CAFID
GROUP 1
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DOWNGRADING
AND
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25X1
?
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Approved For Rise 2005/06/23 : CIA-RDP78B0477040800030038-9
Progress Report
Black and White Films
August 1964
During the subject period, work has continued on the three areas previously
described, that is, screening of materials, mechanism studies, and equipment
design and construction. In addition, a new process has been discovered and
investigated.
1. Screening of Materials. The screening of dyes and pigments has
continued, with about fifty dye-binder combinations being tested. Of these, three
dyes showed good color changes, and were also heat locked. Twenty samples
showed good color changes, but did not heat lock (i.e. were not made immune to
further photoreaction by heating). Some of these, in fact, reversed the color
change on heating. Twenty-seven samples showed no color change or only slight
color change on illumination.
Comparison of a series of binders was started. Carbosets 511, 514,
and 525, all of which are acrylic resins, were compared using a series of dyes.
In most cases the results were similar in all three binders, but in some cases
the same dye behaved differently in the different Carboset resins. The conditions
for heat locking the Carboset formulations seem to be the same as for polystyrene,
that is, heating for 30 minutes at 120?C.
An attempt was made to produce an opaque film by loading with Ti02.
When sufficient TiO2 was used to render the film opaque, it caused a grainy
appearance and also decreased the speed of the films.
2. New Process. A process was discovered which utilizes a film
consisting of a complex between pyrene, dichlorodicyanobenzoquinone (DDQ) and
iodoform in polystyrene. When this film is irradiated with light, it turns black
in the irradiated areas. This process seems to be somewhat slower than the dye
decolorizing process, but gives excellent contrast and definition. The effect of
changes in concentration of the various components was investigated, and an
optimum combination determined. There seems to be no way to render the images
permanent as yet. However, if the images are protected by a yellow filter, such
as Kodak Wratten #15, excellent protection is obtained. The slides protected in
this way can be projected in the 500 watt projector for over ten minutes with no
trace of deterioration of the image.
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Approved For Re 2005/06/23 : CIA-RDP78130477011111800030038-9
-2-
3. Mechanism Studies. Several spectra of the type described
previously have been obtained. These will be compared with the spectra
produced when the dyes are caused to undergo chemical reactions, to see if
the effects of the photoreaction can be duplicated.
4. Equipment. The slide carrier has been completed and is being
checked out and calibrated. A scanning monochromator with a photomultiplier
readout is being used with the slide carrier to monitor the data.
5. Plans for September. The optical set-up for the slide carrier
will be improved. The illumination of the active area of the slide carrier is
not sufficiently uniform, and will have to be improved. The output of the
photomultiplier is not sufficiently linear, so some trouble-shooting and perhaps
some electronic equipment construction will be required. When this has been
completed, quantitative studies on the rates of the photoreactions will be
started.
Concurrently, work will proceed on the screening program, with
emphasis on the role of the binder, so as to find an optimum binder-solvent
system for the more polar dyes. Sufficient data is being accumulated so that
the correlation of reactivity and structure will be commenced.
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71#
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Approved For Rose 2005/06/23 : CIA-RDP78604770
CONFIDENTIAL
Non-Reversible Color -
Study
25X1
Contract No.
Progress Report
No. 1
Financial Status
251,
Amount Authorized
Estimated expenditures
thru 7/31/64
Funds Committed
Funds Remaining
144-16-1
CopyA of 4
800030038-9
Technical Status
The engineering progress report for the month
of July 1964 is attached.
8/6/64
Distribution:
Copies 1 and 2 - Technical Representative
Copy 3 - Contracting Officer
Copy 4 - File
TN* DIATIONAL CONTAINS INFORMATION AFFECTING THE
NATIONAL WEIN! OF THE UNITED STATES WITHIN THE
DIDANING Of THE ESPIONADE LAWS, TITLE IS, LS .C.,
NM. MI AND 794, THE TRANSMISSION Oft REOLLATION
ff MON IN ANY MANNER TS Al VIASTRORITEll PERSON
IR PIONIBITED BY LAW.
Approved For Release 20050
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DOWNGRADING
281304770A00280003003.8-.0
1XLIASASTICATION
25X1
----: ,.
ri Approved For Allse 2005/06/23 : CIA-RDP78604770A 00030038-9
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1
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Progress Report
Non-Reversible Color
July 1964
Work on this project was commenced on July 8, upon receipt of
authorization. This report covers the period July 8 - July 31, and each
subsequent report will cover a calendar month.
During the subject period, effort has been expended on 1) screening
of materials, including dyes, photosensitive materials and binders,
2) initiation of mechanism studies, and 3) calibration and design of equipment.
1. Screening of Materials. Twelve pigments were obtained from
General Aniline and Film and from Allied Chemical Corp. These pigments
are in the oil-soluble and spirit-soluble classes, in black, blue or brown.
Films of the dyes were made up in each of three binders: polystyrene, saran
and Carboset 511. The Carboset is a more polar material than the other two
and should act as a vehicle for dyes too polar to remain in solution in
polystyrene. It also forms smoother films than we have been able to obtain
with saran. The photosensitive material for the first series of tests was
iodoform. Four of the dyes gave usable color changes in 30 seconds of
exposure to a 500 watt projector, when dissolved in polystyrene or in saran.
In Carboset, three of the same dyes gave similar results.
A comparison was made between iodoform as the photosensitive
agent, and trichloromethyl-sulfonylchloride (TCSC). The four dyes giving
positive results with iodoform, as well as two others and the previously studied
indophenol blue were tested. Of these seven dyes, two gave positive results
with TCSC. When this comparison was repeated in Carboset, none of the dyes
gave positive results with TCSC. The successful use of TCSC in polystyrene
indicates that the reaction can occur with reagents quite different than iodoform.
The end product of the use of TCSC is usually a pink color, rather than the
yellow of iodoform. One of the objectives of the project is to find a reagent
whose end product is colorless.
A series of tests were run to determine the heating conditions to
be used after exposure of the film needed to protect the film from further photo-
bleaching in the projector. Thirty minutes of heating at 1200 or fifteen at 1300
gave excellent protection to dyes in combination with iodoform in a polystyrene
film, 5% iodoform by weight.
Several other dyes have been ordered, and will be similarly tested
when received. As the work progresses, correlations between the structures of
the dyes and their reactivity (or non-reactivity) will be made.
Approved For Release 2005/06/23 : CIA-RDP78604770A002800030038-9
^
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2. Mechanism Studies. The initial mechanism studies consist of
the determination of the changes in the absorption spectrum of the dye due to
the photoreaction. A typical set of spectra is shown in the figure. The
increase in transmission at long wavelengths corresponds to bleaching of the
dye, while the decrease at short wavelengths is due to the darkening of the
iodoform. We plan to obtain similar curves for all reactive dyes, and to
compare the effects of various photosensitive agents. We then plan to react
the dyes with various reagents, such as oxidizing and reducing agents, to see
if the photoreacted spectra can be duplicated.
3. Equipment. Light sources used on the project include 500 watt
and 300 watt tungsten sources, a 100 watt mercury lamp, and a 150 watt xenon
lamp. The 500 watt tungsten source is used routinely, with the other types to
be used to evaluate the effectiveness of the low wavelength end of the spectrum.
The 500 watt tungsten lamp has been calibrated to give the total energy per
unit area incident on the plane of exposure. The wavelength distribution of
this source is approximately known from previous work.
A slide carrier is being designed to provide a continuous smooth
motion of the slide in the exposure plane, so as to provide a continuous variation
in time of exposure across the slide. This will provide more accurate rate of
color change data than is available by the present method of discrete exposures.
4. Plans for August. Work is to be continued in all of the areas
outlined above. Several more dyes will be screened, new photosensitive agents
will be tried, and new binders will also be evaluated. Mechanism studies will
be continued as discussed in Section 2. The slide carrier will be completed,
and its use compared with present techniques. No unexpected problems have
been encountered as yet.
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