PROJECT 325B SUMMARY REPORT PERIOD: 1 JANUARY 1972 TO 31 JANUARY 1972

• Document Type: CREST
• Collection: NGA Records (Formerly NIMA)
• Document Number (FOIA) /ESDN (CREST): CIA-RDP80T01137A000100010009-0
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• Original Classification: S
• Document Page Count: 31
• Document Creation Date: December 28, 2016
• Document Release Date: March 18, 2010
• Sequence Number: 9
• Content Type: REPORT

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PROJECT 325B
SUMMARY REPORT
PERIOD: 1 January 1972 to 31 January 1972
Submitted By:
25X1
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PROJECT 325B
SUMMARY REPORT
PERIOD: I January 1972 to 31 January 1972
Submitted By:
Project Manager
Copy & of 7
25X1
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TABLE OF CONTENTS
Section Page
1.0 CHEMICAL R and D . . . . . . . . . . . ... . . . 1
1.1 Leuco Dye Program . . . . . . . . . . 1
1.1.1 D260 . . . . . . . . . . . . . . . . . 1
1.1.1.1 TMB Film Evaluation . . . . . 1
1.1.1.2 Michler's Hydrol Purification. 2
1.1.1.3 Michler's Hydrol Synthesis . . 4
1.1.1.4. Alternate Synthesis Route to
D260 . ... . . . . . . . .
1.1.1.5 D260 Decay Properties . . . .
1.1.2 Other Leuco Dyes . . . . . . . . . . 6
1.2 . CBr4 . . . . . . . . . . . . . . . . . . 7
1.2.1 Film Additions of Halogen and Halogen
Derivatives . . . . . . . . . . . . 7
1.2.1.1 Hexabromoethane . . . . . . . 7
1.2.1.2 Hydrogen Chloride . . . . . . 8
1.2.1.3 BF3.OEt2 . . . . . . . 8
1.2.1.4 Bromine . . . . . . . . . . . 8
1.2.1.5 CBr4 - DABCO Complex and
DABCO . . . . . . . . . . . 9
1.3 N-Oxide Program . . . . . . . . ... . . . . . 10
1.4.1 Pressure Chemical Standard Polysty-
renes . . . . . . . . . . . . . . . . 10
1.4.2 Commercial Grade Impurity Studies . . 10
1.5 Environmental Studies . . . . . . . . . . . 11
1.5.1 Air Sampling . . . . . . . . . . . 11
1.6 Other Film Systems. . . . . . . . . . . . 14
1.7 Film Analysis of Decay Products . . . . . . 14
(continued)
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TABLE OF CONTENTS (Continued)
Page
1.8 Dye Identification . . . . . . . . . . . . . 14
1.9 System Nonuniformities . . . . . . . . 14
1.9.1 Silicone Oil Addition . . . . . . . . 14
2.0 ENGINEERING
2.1 Calibration and Maintenance . . . . . . . . . 16
2.2 Mechanical . . . . . . . . . . . . . . . . . 16
2.3 Shelf Life . . . . . . . . . . . . . . . 16
Problems . . . . . . . . . . . . . . . . . . . 16
3.0 PERKIN ELMER INTERFACE - QC/QA
3.1 Supply of Film and Equipment . . . . . . . . 18
3.1.1 Delivery of 325B Film . . . . . . 18
3.1.2 Delivery of Solvent Rinse . . . . . . 19
3.1.3 Delivery of Red Light Dev. Units . . . 19
3.3 Evaluation of Production,Shipping and Contami-
nation . . . . . . . . . . . . . . . . . . 20
3.7 QC/QA . . . . . . . . . . . . . ... . . . . 21
PROBLEMS . . . . . . . . . . ... . . . . . . . . 23
PLANS FOR NEXT REPORTING PERIOD . . . . . . . . . . 23
FINANCIAL . . . . . . . . . . . . . . . . . . . . . . . 23
REFERENCES . . . . . . . . . . . . . . . . . . . . . 24
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Project work continued uninterrupted during January.
A complete briefing was given at the customer. facility
covering the entire project from its inception to 1972. A
proposal and detailed work statement was submitted for a
six month effort with emphasis on the mechanism of shelf
life/speed decay. Such work is underway, although no offi-
cial go ahead has been received.. A complete briefing on
the work statement was held for the customer at
Engineering forecasts completion of the six laboratory
HID-2 red light units by 15 February. Detailed experiments
have been planned for reactivation studies. Performing
these during February and March is dependent on the use of
the engineering darkroom; the present environmental con-
tamination level of which prevents such studies. All
attempts to reduce the level have not produced significant
results. A separate enclosure for such studies is under
construction in an isolated area of the building.
The Perkin Elmer interface with sample films was begun.
The results to date are encouraging. Detailed results are
given in Section 3.0.
Chemistry
The impurity in D260 which destroys photographic sensi-
tivity is N,N,N',N'-tetramethyl benzidine (TMB).
Its separation from D260 is difficult which explains the
difficulties which have been encountered in preparing photo-
grade D260 in good yield.
TMB is introduced as in impurity in Michler's hydrol
which is an intermediate in the synthesis of D260.
It is not produced during speed decay.
Suitable procedures have been devised for eliminating
TMB from Michler's hydrol and also from D260, but the latter
is less desirable.
An alternate synthesis of D260 is underway. It circum-
vents the use of Michler's hydrol and hence the introduction
of TMB as an impurity. .
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Acids have been shown to definitely enhance blotching
(high density, irregular fog patterns) to the detriment of
image formation.
Bromine in the amount. of 8, ppm by weight of CBr4 has no
effect on sensitometric.properties.
Pressure Chemical's polystyrene standard of 200,000
(200K) molecular weight has been. found to simulate the
photographic properties of MX4500.
Air analysis for the identification of airborne contami-
nants continues. Incomplete data shows good correlation
between poor film and oxidants. Ozone is a probable suspect.
Eleven silicone oils were screened in reference to
Dow Corning's DC510 for the elimination of"orange peel"
(cf. Ref. 1, 3.3.10, p. 69). One, R631, a product of Union
Carbide, is superior to DC510.
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1.0 CHEMICAL R and D
1.1 Leuco Dye Program
1.1.1 D260
Small batches of D260 were purified during January
to provide material for continued film studies. In addi-
tion, a 165 g sample of Michler's hydrol, purified by the
benzene-petroleum ether technique, was converted to D259.
The usual chromatographic purification of this material was
carried out and after the D259 was eluted, the chromatographic
column was treated with acetone followed by methanol to
elute virtually all materials adsorbed on the column. The
cuts taken in this way were concentrated to give fairly
mobile fluids. These cuts will be examined by VPC on arrival
of Horizons' new gas chromatograph.
Thin layer chromatographic (TLC) examination of the
D260 delivered to us most recently by ChemSampCo revealed
a gross impurity eluting just ahead of the D260. The impurity
was definitely established as deleterious photographically,
as reported in December. Elemental analysis-of this impurity
was correlated with infrared spectral data and physical
properties. It is N,N,N',N'-tetramethyl benzidine (TMB).
This compound arises by oxidative coupling of dimethylaniline
in the preparation of Michler's hydrol and is carried through
unreacted in the synthesis of D260. Work in January showed
that the best way to remove this impurity (present in large
quantity in ChemSampCo material) is by several triturations
in hot ethanol in which D260 is only sparingly soluble. It
was discovered that practically all of the TMB can be removed
in this way by one alcohol trituration of material prepared in
our laboratories, provided the Michler's hydrol had gone
through at least one cyclohexane recrystallization prior. to
use in D260 synthesis.
The maximum amount of TMB that can be added to the 5/D7
system without changing its photoresponse is 1 gg (10 ppm).
Increasing the amount to 10 ?g (100 ppm) gives a film with
lower maximum density (1.78 and a higher fog density (.24)
than the normal control (ODmax -0.24,AFog +0.09). Addition
41
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of 100 ?g (1000 ppm) of the impurity destroys the film com-
pletely (only a slight image can be seen with absolutely
no fog after 300 seconds. development)..
Prior to the identification of TMB it was thought that
this impurity was connected with speed decay since the
photoresponses just described are similar in appearance to
those of aging films. Attempts failed. t.o, detect. its presence
in decayed film by TLC. Now that its structure has been
determined as TMB, it is realized that it cannot result from
degradation of D260. Its presence. to varying degrees in
various D260 samples does, however, explain the varying uni-
formity of these samples with respect to. photographic
properties, while the extreme difficulty in separating it
from D260 explains the difficulties which have been con-
tinually encountered in preparing photograd-e D260. There
is still the possibility that other detrimental impurities
are present`-and'so work continues 'in`addressng this problem.
ChemSampCo has been kept informed of all chemical develop-
ments and is now following closely all their work by TLC.
In addition, a benzene-petroleum ether recrystallization of
Mi.chler's hydrol was optimized during January and the details
of the purification were transmitted to ChemSampCo. A
double recrystallization from-the medium serves to remove
TMB completely .(by TLC) as opposed to a double recrystallization
from cyclohexane which leaves a small amount of TMB in the
hydrol. Finally, ChemSampCo's most recent run has been fol-
lowed closely by the project, by frequent phone conversations,
and it appears to be coinciding very closely to our synthesis
in the criteria of appearances, yields and TLC data.
1.1.1.2 Michler's Hydrol Purification
The troublesome impurity in D260 was identified this
month as N,N,N',N'-tetramethyl benzidine (TMB). Successful
synthesis of clean D260 will be attained most easily by the
use of Michler's hydrol free of TMB, rather than carrying
the contaminant onto the D260 and attempting to separate it
from this sensitive leuco compound, which is not easy and
results in poor yields.
The commercial synthesis of Michler's hydrol is,by the
lead oxide oxidation of Michler's hydride:
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(CH3) 2N
CH(OH)
N(CH3) 2
The literature (Ref. 2) shows that TMB arises from the
oxidation of dimethylaniline and of many other compounds
containing a p-dimethylaniline moiety, such as Michler's
hydrol and Michler's ketone. This leads to the postulate that
Michler's hydrol prepared by an oxidation procedure would
likely be contaminated with considerable quantities of TMB,
easily confirmable by an examination of the crude Michler's
hydrol purchased from Hilton-Davis.
Purification of this crude Michler's hydrol from ben-
zene by precipitation with petroleum ether has been demon-
strated to give product free of TMB (by TLC). The hydrol
can be oven-dried or dried by azeotropic distillation from
benzene. Either way it can be purified by two precipitations
in 650 overall yield.
Studies with "pure" D260 and pure TMB have demonstrated
that TLC is capable of detecting as little as 50 ppm TMB in
D260. This level falls between the film evaluated levels of
10 ppm (1 gg - no noticeable effect) and 100 ppm (10 pg -
significant detrimental effect). Since all D260 to date has
been made from purchased Michler's hydrol it is reasonable to
expect that even "pure" D260 contains some amount of undetectable
(less than 50 ppm) TMB. Thus even "pure" (photograde) D260
may be less than optimum. To test this possibility D260 must
be synthesized in such a manner that no presence of TMB is
possible. Two approaches are envisioned: one, the synthesis
of Michler's hydrol by reductive rather than oxidative con-
ditions; and two, the synthesis of D260 by an entirely dif-
ferent route which circumvents the use of Michler's hydrol.
This approach should yield D260 containing at least some
impurities different from those produced by the current syn-
thesis. Comparative evaluations of D260 from two different
routes will thus provide evidence concerning the relative
importance of impurities other than TMB.
--~
N(CH3 )2 + Pb02
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1.1.1.3 Michler's Hydrol Synthesis
A clean synthesis of Michier's hydrol would be an accept-
able alternative to the purification described above.
We have found that Michler's ketone can be reduced by
sodium amalgam to the hydrol in 80% yield. The crude
reaction product is white and dry and contains no TMB by
TLC.
(CH3)2N-\ ))-N(CH3)2 + Na(Hg) ----~
WHO 2N -~ ) r ~H - )r N(CH3) 2
OH
Reduction of Michler's ketone with NaBH4/AlC13 was unsatis-
factory. A 3.5% yield was obtained but it was contaminated
with Lewis acid which caused the product and filtrates to
turn blue, even when handled in the dark at cold. temperatures.
The synthesis by lead oxide oxidation of Michler's
hydride (the commercial route) in progress last month led,
as expected, to considerable contamination by TMB.
Attempted reduction of Michler's ketone with zinc and
potassium hydroxide was ineffective, but the recovered ketone
was extremely pure.
1.1.1.4 Alternate Synthesis Route to D260
In another approach to the problem of dependable source
of D260 of adequate purity, an alternate route was undertaken.
This will be called the "Anthrone Route to D260." The entire
sequence has been described by C. Aaron and C. C. Barker
(Ref. 3).
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 WHO 2N
WHO 2N-(( ))- + HCHO + H2N-(( ))--SO3H
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CH2NH
N-p-dimethylaminobenzylsulfanilic
acid
> (CH3) 2NYn\7 n~'N(CH3) 2
H,SO4
N(CH3)2
5
L~Oj
(CH3) 2N
reduce
N(CH3)2
D260
-5- 25X1
KO-t-Bu,benzophenone
(CH3) 2N
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During January this route was carried to D263. About
100 grams of this intermediate were being purified at the
end of the month.
Although multi-step, this route should be comparable to
our present route. If the D260 formed is free of TMB, this
route could be superior.
Synthesis of the anthrone would also give an intermediate
which, using other metalaryls, would make available many
other leuco anthracenes analogous to D260.
1.1.1.5 D260 Decay Properties
The proposal for 325B (Ref. 1, p. 48) discusses the pos-
sible role of 4-dimethylaminophenol (4-DMAP) in speed decay.
It should be remembered that 4-DMAP is a possible, degradation
product of D260 hydroperoxide and has been detected by mass
spectrographic analysis in several samples of D260. 4-DMAP
is not available commercially and was.therefore prepared
according to the following scheme.
CH3I ---'>
HNCH3 HN-1CH3 I-
.1
CH
ik1
CH3 CH3
N(CH
I
3
+ HI + CH3I
For comparison, the three-isomer (3-DMAP) was purchased
and purified. These materials are currently being evaluated.
1.1.2 Other Leuco Dyes
Some preliminary film studies were begun with various
samples of leuco crystal violet (LCV), leuco malachite green
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(LMG), several LMG analogues, and D179, the leuco xanthene
analogue of D260.
The results of these studies are too inconclusive to
warrant discussion at this time.. Further studies are planned
for February and if the work is completed, the results will
be discussed next month.
1.2 CBr4
No CBr4 purifications were carried out in January, but
a 5 kg sample Qf CBr4 was received from BDH. This material
will not be opened to ordinary laboratory air, but will
be handled exclusively under controlled environmental condi-
tions.
A high vacuum line was put into operation for the subli-
mation and vacuum storage of CBr4. It was discovered that a
number of modifications of this line were necessary and these
were completed in January.
A sample of hexabromoethane was purified in January and
turned over to film evaluation.
The purification and deterioration studies with Freeman
and BDH CBr4's are expected to commence in early February.
1.2.1 Film Additions of Halogen and Halogen Derivatives
1.2.1.1 Hexabromoethane
Attempts to replace CBr4 by hexabromoethane (523 mg and
311 mg) gave films which had no developable sensitivity (no
image or fog produced after 15 minutes development time).
Printouts of film containing 311 mg give a blue dye (maximum
density 0.98, fog density 0.07). This suggests that the
mechanism with C2Br6 for printout image formation is different
than CBr41 since apparently little or no D7 dye is produced
to afford the usual deep magenta image. The result may be
due only to the lower amounts of C2Br6 used, however, and
this possibility will be explored further by comparing with
lower concentrations of CBr4.
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Addition of 10 mg and 100 mg to the standard 5/D7 benzene
system gave films with lower maximum densities and longer
development times than standard.
1.2.1.2 Hydrogen Chloride
Addition of trace amounts of hydrochloric acid to the
standard control gave a film which was completely blotched
(red background) with no image after 240 seconds development
time..
1.2.1.3 BF3'OEt2
Addition of trace amounts of boron trifluoride (a strong
Lewis acid) to the standard control gave a film which was
completely blotched (red background) with no image after
180 seconds development time.
Addition of trace amounts of bromine (10 rig) gave a film
identical to the standard control. The 10 micrograms represents
8 ppm by weight of CBr4. If CBr4 decomposes by dispropor-.
tionation to give bromine and t.etrabromoethylene (C2Br4)1
the 10 pg represents about 17 ppm decomposition on a molar
basis. Thus, if the appearance of speed decay is due to the
formation of bromine, then CBr4 must be decomposing to an
extent greater than 17 ppm in less than an hour. Additional
experiments are planned to determine the maximum amount of
bromine which can be tolerated and to determine the effect of
tetrabromoethylene.
The behavior of hydrochloric acid and boron trifluoride
etherate indicate that rapid and extensive blotching may
indeed be due to the presence of acid, by formation within
the film (e.g. the decomposition of CBr4 to give hydrogen
bromide - HBr), or introduced either with the ingredients or
by atmospheric contamination.
Positive proof that acid contamination from the atmosphere
can cause rapid and total fogging (total blotch) occurred
several months ago. A darkroom was accidentally contaminated
with acetic acid vapors. A film run immediately prior to con-
tamination was normal with an AEI well above 1.0. Subsequent
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to the contamination the film fogged totally and immediately
on attempted development, no image was discernible.
1.2.1.5 CBr4- DABCO Complex and DABCO
DABCO is 1,4-diazabicyclo[2.2.2loctane. It has found
great utility as a fog retardant in Horizons' duplicating film
when used in very small quantities. It is a comparatively
strong organic amine and apparently retards acid-caused fog
by scavenging trace acids. Last year DABCO was found to pro-
vide acceptable photograde CBr4 when present during the
recrystallization, and during the period when the normal
procedure failed to afford acceptable CBr4. Its use was soon
abandoned, however, since no two batches of CBr4 were identical.
DABCO forms a yellow.crystalline, 1:1 complex with CBr4.
An attempt to replace CBr4 in the standard 5/D7 (benzene).
system with an equivalent amount of this complex failed because
of its insolubility.
Addition of less complex (85 mg which equals one-tenth
as much) produced a slight blue image with a heavy blue
fog after 360 seconds development. A printout gave the
same blue image and blue fog. Decreasing the amount to 5 mg
gave a maximum density (1.81) lower than the control and. with
a development time increased to 350 seconds. Printout gave
a black image with blue fog. The maximum amount of.complex
that can be added to the 5/D7 system without changing its
photosensitivity is 1 mg. Speed decay was not affected at
this level.
Addition of 5 mg of DABCO to the 5/D7 system produced
a blue image whose maximum density (.88) was much lower than
normal with a much higher development time (600 sec.).
.Decreasing the amount to 100 ?g also produced a film with
lower maximum density (1.71) with slightly greater development
times. S.pee.d decay was not affected.
The formation of blue image in contrast to the usual
deep magenta is easily explained in this case. DABCO, at
least in larger concentrations, is scavenging acid, thereby
preventing the formation of the red D7-dye. That DABCO is
preventing the formation of D7-dye by some means other than a
simple acid-base reaction cannot be excluded.. It could
be circumventing the normal mechanism(s) for image formation
involving D7 by some means other than scavenging acid.
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1.3 N-Oxide Program
During January six amine oxides (N2, N3, and N32-35)
were eit}pr purified, or prepared and purified for screening.
Th.irt.y--o.ne. compounds of the N-oxide class (aromatic
and aliphatic N-oxides, heterocyclic. N-oxides, azo and azoxy
compounds) have been tested photographically. Because of
the large number of films to be evaluated, a special report
of this study is currently being prepared and will be included
in a future summary report.
1.4.1 Pressure Chemical Standard Polystyrenes
Three polystyrenes (mol. wt. - 110K, 200K, 390K from
Pressure Chemicals, Pittsburgh, Pa.) were investigated as
replacements for MX4500. The molecular weight 200K was found
to resemble MX4500 most closely with respect to handling,
development time and photosensitivity (y and AEI speeds were
the same). The higher molecular weight (390K) gave too thick
a coating and developed too quickly while the lower molecular
weight (110K) polystyrene gave too thin a coating and developed
more slowly with less maximum density than control.
The 200K material will therefore be used for comparison
to MX4500 in evaluating the effects impurities and end groups
are having on photoproperties, particularly speed decay.
1.4.2 Commercial Grade Impurity Studies
Past experiments with various commercial grade poly-
styrenes showed in several instances significant. differences
in photoproperties in comparison to MX4500. Borden's 230,000
gave slightly poorer films and Lustrex showed significantly
poorer films. These two, along with MX4500 were sent to
Waters Associates for separation of the low molecular weight
(containing additives, impurities) fractions. These-fractions,
as benzene solutions, have now been received. The effect of
these fractions will be evaluated using the Pressure Chemical
200K material.
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In future work, it is. also planned to investigate more
closely the differences manifested by-other molecular weight
polystyrenes, particularly any differences in speed decay.
1.5 Environmental Studies
The control studies as outlined in the 325B proposal
(Ref. 1, 3.3.6, p. 62) are not scheduled to begin until
March.
1.5.1 Air Sampling
The air sampling program (cf. ibid) for the identification
of suspected air contaminants was begun in late December,
1971, and continues to date.
Some results are now available and are shown in Table 1.
Results have been reported for oxidants., oxides of nitrogen,
hydrogen halides, and arsenic. Of these, there is a positive
correlation only for oxidants. The values quoted in the
table are calculated for ozone, but the actual chemical form
of the oxidant is not known. It could also be a radical or
a volatile organic peroxide or hydroperoxide.
On the basis of the results so far reported, further
testing for oxides of nitrogen and for arsenic has been dis-
continued.
Data on halogen acids, hydrogen selenide, and hydrogen
telluride are still being awaited.
Although the results to date are incomplete and more data
,is certainly desirable, the correlation between "bad" films
and oxidants is quite good, with only samples 18, 23 and
possibility 26 being out of agreement. It is interesting
that the worst films (nearly always totally fogged with little
or no image formation) are obtained in a darkroom quite apart
from the main film research area. This dardroom is adjacent
to a lab where .electrophotographic research is being conducted
and where the equipment is known to produce ozone. The possi-
bility that ozone is itself the major culprit is thus being.
investigated and it is hoped that February will see considerable
clarification of the air contamination problem.
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AIR SAMPLING RESULTS TO DATE
Includes results reported to us by National Loss Control
through January 31, 1972. Samples corresponding to bad
films are indicated by asterisk.
Sample
Number
NO2,
ppm
Oxidants
mg/M3
X2,
mg/M3
Arsenic,
mg/M3
0.027
0.0004
007
19
04
04
10
07
007
16
08
007
-6-7-
29
02
05
-
11
<
007
12
25
13
06
14
17
23
12
<
007
15
05
03
13
16
14
26
44
<
.007
17
10
23
13
(
007
18
07
46
15
04
19
12
17
14
<
007
20
07
10
18
< .
00 7
21
07
13
22
<
007
22
12
*23
10
21
20
<
007
24
12
49
08
<
007
25
<
007
*26
18
31
09
<
007
*27
12
65
11
<
007
*28
12
74
14
'(
007
(continued)
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TABLE 1 (continued)
Sample
Number -
NO2,
ppm
Oxidants,
mg/M3
X2,
mg/M3
Arsenic,
mg/M 3
*29
0.008
0.095
0.012
<
0.00007
*30
52
10
04
*31
12
77
11.
<
007
*32
74
01
*33
*35
84
14
K
007
*36
58
I9
e.
007
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1.6 Other Film Systems
No work has yet begun nor has any been scheduled until..
March. However, it would be desirable to compare the results
being. obtained with the 5/D7 system with the 5/DPA system.
The 5/DPA system has been discussed on numerous occasions in
the past (cf. Ref. 1, 3.3.3, p. 57). It will be remembered
that the- mec.han.isms of image formation with DPA, which is not
a dye base, must be different than that with D7.
Interpretation of experimental results from 5/D7, such
as have already been discussed in this report, would be
considerably more meaningful if results could be compared
to those from the 5/DPA system.
At present only one darkroom, the one which is environ-
mentally controlled (cf. Ref. 1, 3.3.6, p. 62), is reliable
and it is being used to capacity with studies on 5/D7. The
adjacent darkroom provides much poorer and very inconsistent
film results. It has been shown by numerous control and
cross-over experiments with the adjacent, controlled room,
that this is due to some form of atmospheric contamination.
An attempt is being made to correct this situation. When it
is corrected, plans are to begin immediately the standardi-
zation of the 5/DPA system.
1.7 Film Analysis of Decay Products
Due to the current manpower shortage in the chemistry
group, little work has been done in this area. Some attempt
was made to detect the presence of TMB in decayed film, but
to no avail (cf. Section 1.1.1.1).
1.8 Dye Identification
Work is not scheduled to begin until May.
1.9 System Nonuniformities
1.9.1 Silicone Oil Addition (1807-30, 31, 35)
Eleven silicone oils were added to.the 5/D7 system at
various concentrations for evaluating the elimination of
-14-
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"orange peel" (cf. Ref. 1, 3.3.10, p. 69). All but one,
R631 (Union Carbide), behaved as DC510 (Dow Corning) and
offered no advantages as a substitute. R631 silicone oil,
however, eliminates "orange peel" and gives no significant
difference photographically from the standard control. DC510,
in contrast, gives higher 's,,. lower Dmax r s and. longer
development times.
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2.1 Calibration and Maintenance
All.equipment used by 325B personnel continues to be
calibrated and maintained on a regular basis so as to detect
and correct any changes. There have been no major break-
downs or changes in any of the operational lab equipment
during this reporting period.
2.2 Mechanical.
The HID-2 red light development units are in final
stage of either test or assembly. Three units have been
completed and are undergoing tests; three more remain.
The HID-2 has proven to be an effective laboratory red
light development unit. The operational controls are sim-
plified and the unit is greatly reduced in size. Preliminary
testing of the three units indicate there is remarkable
repeatability between units. It now appears that the develop-
ment parameters of all six units will be identical.
2.3 Shelf Life
The first shelf life program to be undertaken is
reactivation. Preliminary investigations of equipment,
chemicals and mechanisms is underway. It is expected that
reactivation studies will start as soon as a laboratory is
available (see "Problems").
The darkroom presently being used by engineering to
conduct sensitometric and equipment evaluations has suffered,
a catastrophic contamination problem. At present the dark-
room is useless for mixing, coating, exposing or developing
325B films. A test matrix has been completed whereby all
steps of the process have been conducted in the engineering
darkroom and the special environmental darkroom used by the
chemistry group. It now appears that any of these steps
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conducted in the engineering darkroom leads to a complete
or partial failure of the- s-ystem.
The chemistry group, being interested in defining the
contaminant, has made a series of tests to determine if any
correlation can be made between bad films and certain air-
borne contaminants. There have been. no definitive results
at this time. The darkroom has been sealed, has its own
air conditioning unit and has been continuously cleaned by
a Barnebey Cheney charcoal filtration device. There has .
been no improvement at this time. Although a number of theories
have been put forth, none have proved to have good correlation
with the film results. Engineering is attempting to circum-
vent this problem by construction of small isolated test
chambers to be operated in various parts of the building to
determine if without knowing the cause of the contamination
laboratory work can continue. No shelf life studies in
the form of reactivation or overcoating can be started until
the contamination has been overcome; therefore, any engineering
shelf life work must wait until a suitable chamber can be
built and tested. It is anticipated this chamber will take
no more than two weeks to build and occupy. Testing will
probably take an additional week; hopefully reactivation
work can be started before 1 March 1972.
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3.0 PERKIN ELMER INTERFACE - QC/QA
3.1 Supply of Film and Equipment
3.1.1 Delivery of 325B Film
The first shipment of unexposed, sensitized, hand coated
film cut to sample size was successfully delivered to P. E.
on the 17th of January. The film speed and other aspects of
film performance were essentially undiminished in the shipment.
The hand coatings were made at on Friday, 14 January 25X1
and checked out at an approximately 0.5 AEI. The only AEI check
on 18 January at the P. E. facility was roughly 0.1 AEI. The
deviations from the control samples run at if any- 25X1
thing, indicate improved performance at the P. E. facility.
Using the same processor at both facilities, the development
times were 20 to 25% longer at P. E. with comparable fog and
blotch. Dmax apparently was also better.
The shipment consisted of 60 1/2" wide strips of-film
with sufficient coating for exposure on a 21 step tablet.
The samples were cut from 15 typical hand coatings, which used
approximately one gram of the key compound, D260. The standard
325 formula 5/D7, was used and in every other respect the
coatings are standard coatings, i.e., unsubbed on 5 mil Mylar,
unfiltered, no silicone oil, and the typical film coating
thickness in the .3 and .5 mil range. Because the shipment
was to be used for setting up the P. E. lab, the best photo-
grade quality of material was not used. At a later date the
materials that would routinely give AEI's of 2.0 will be
shipped. When necessary, especially for image evaluation,
the cosmetic defects of undissolved D7 and streaking will be
eliminated. The only other obvious defect in the first ship-
ment, blocking of the image when used in the high speed mode,
could not be corrected. Plans are being formulated for
P. E. to investigate this effect.
In preparation for the second shipment, an.effort was
made to use ultrasonics to dissolve the D7 in the stock solu=
tion. The testing with appropriate size samples of D7 and
polystyrene/benzene solution on a jewelry-equipment ultrasonic
cleaner and on an industrial sized unit that delivers 600 watts,
yielded no practical improvement. A marked improvement was
made with a mechanical stirrer used at high speed for a longer
time.
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The second shipment was prepared on 31 January and was
sent by airborne freight. Cosmetically this shipment will
look better than the first. Sufficient controls were.not
run to identify the AEI speed. Indications are that it will
be as fast or faster than the first shipment. In the printout
mode the blue-..density AE.I speed is approximately 1 x 10-4,
which. is typical of our best materials. Since the P. E.
testing program to begin with is concerned primarily with
printout tests, attempts to produce higher speeds were not
carried out. The shipment consists of. ten (10) sheets,
7 x 7-1/2" with approximately 30% of the area coated. Suc-
cess of the transfer of this film has not been determined, as
P. E. had not evaluated the films by the time of the prepara-
tion of this report. A delay had been experienced in shipment
as the air freight company shipped to the wrong airport.
3.1.2 Delivery of Solvent Rinse
One gallon of solvent rinse was mixed atl and
delivered with the first shipment.
3.1.3 Delivery of Red Light Development Units
The older 4B unit with the-650 watt Sungun was delivered
the 17th of January, in lieu of one of the HID-2 units, which
will be completed in the beginning of February. The 4B unit
was used for checking the first film shipment at
delivered to P. E. with the film, and used for checking the
film there. Three people were instructed and trained in the
use of this processor.
Along with the equipment and film, instructions included
updating them in the latest technology with particular emphasis
on the technology of interpretation of results since the film
is in the experimental stage and not a final pilot coated
product. Evaluation of the many subtle effects are as important
as the straight forward readout of the sensitometry.
Since the first shipment of film included a processing unit,
the same processing unit could be used for quality control of
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the materials before and after the coating run, as well as
at the P. E. facility after delivery. In practice, QC of the
development of the film is as important as QC of the grade of
materials for the high speed node. The HID-2 unit to be
delivered will. be one of a series of six which will have been
made as identical as the state-of-the-art will allow. The
six units will be thoroughly checked out and cross calibrated
before the one is shipped. The same care will be taken for
shipment of lamps for replacement.
25X1
The first significant discrepancy in photographic response ,
between and P. E. to be identified, was in densito- 25X1
metry. This was first identified when the two samples brought
with the first shipment were read on the P. E. densitometer,.
which is a TD-102 the same model as used in the 325B project
area at Reading the standard calibration tablets 25X1
supplied with each TD-102 does not reveal any discrepancy
between the two densitometers. The cross calibration using
a 325 step tablet processed at and oneprocessed at 25X1
P. E. shows that the densitometer is reading con- 25X1
sistently lower than the unit at P. E. The use of an.Ektacolor
color tablet also indicates that the P. E. densitometer is
reading higher, but this tablet does not show as great a
discrepancy. That the reading of density of 325B films is so
dependent on the color filter of the densitometer has been
proven before in studies with a radiometer, with a series of
light-table colors, and with a series of source colors for
dupping onto PH Type 2000 film. Because of this, a special
standard with sharp color cut-ons and relatively narrow wave-
bands may have to be setup for calibrating densitometers for
325B film. Dmax's at P. E. are being read at the 3.5 range,while
the Dmax's at Horizons are typically 2.5 and on rare occasions,
2.7. As of now the two noteworthy factors are: one, the real
densities produced at their facility apparently are higher than
here; and two, if their densitometer is found to be incorrect,
the filter color that is used to read these high densities
should become the established one, even though it isn't the
standard MacBeth product.
3.3 Evaluation of Production, Shipping and Contamination
The use of hand coatings for the test film is tedious
and expensive. The procedure worked out for the.first ship-
ment apparently was successful. Particular care was made in
weighing, mixing and production of a film in the one room that
has consistently low levels of airborne contamination.
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Attention was also given to packing the film in dry ice as
quickly as possible after coating. For the case of the first
shipment, the time from coating to freezing was on the average
4 to 4-1/2 minutes. For the second shipment the time was
reduced to 1 minute and 45 seconds on the average. As the
shelf life studies proceed, it should be possible to relax
this. requirement. The film strips were placed in individual
thin cardboard boxes. This type of box has fairly good heat.
transfer properties. About 15% of the samples were used for
test purposes the first two days, all of which were satisfactory.
In the two weeks that it took to use the rest of the supply,
about 10% were found to be fogged. This may be an indication
of the problem of CO2 from the dry ice replacing the air during
storage. Experiments will be carried out to definitely prove
this. It may also indicate that one condition for providing
required shelf life is to place the film in a special atmosphere
such as a higher concentration of oxygen. The second shipment
was not cut to sample size because the user can achieve
greater efficiency by cutting the sheets to smaller sizes to
fit their particular exposure requirements. Because of the
problem of air contamination in some of the labs, 25X1
the air at the P. E. facility was another concern. Based upon
the first experiments, the air at P. E. is not contaminated
with respect to our film. In fact, the better performance at
P. E.., if that is the case, may be due to the reduced contami-
nation in the P. E. air system. When all the air sampling
data at is in and reduced, the knowledge gained will 25X1
be used to sample and check the contamination level at the
P. E. facility.
3.7 QC/QA
The supply of quantities of photograde materials has been
fairly reliable over the last several months. Although the
quantity of materials on the shelf has never been great, they
have been consistent with the lead times now needed for produc-
tion of more material. The quantity and quality of the D260
supplied by ChemSampCo has not been good, although the solutions
to their problems seem near at hand.
The achievement of analytical techniques for quality
control has shown considerable progress. -The thin layer
chromatography experience has reached a point at which the
photograde quality of the material can be determined before
testing in the coating lab. The "yellow spot" on the TLC
(thin layer chromatography) samples which has been correlated
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with poor performance, has now been identified. It is
described in the chemistry section of this report. The-
TLC technique is now being used at ChemSampCo for control
of their intermediates and products before shipment. We
have had to-accept less than quality grade material from
ChemSampCo in order to keep our supply ahead of needs. The
resulting loss to us was lower yield of final photograde
product after passing through the purification column.
Air contamination has been identified as a separate
problem from the synthesis and purification problem. A
film produced in an "uncontaminated" room and stored for
later use can eventually go "bad" if taken out of storage,
exposed and processed in a "contaminated" lab.. The progress
in identification of the impurity in the air is reported in
the chemistry section. The means for controlling the problem
with the one room that has been consistently good is described
in the engineering section. The room has been controlled to
a constant humidity and temperature, the air flow from out-
side the room has been restricted, and the air: within the
room is filtered with a Barnebey Cheney activated charcoal
filtration system.
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PROBLEMS
1) As of January 31, no official verbal approval to proceed
on this program had been received. Several large labor-
atory items required for the shelf life investigations
.have not been ordered awaiting this approval.
2) Three new hires for this effort have not been secured
pending the verbal go ahead. Further delay in securing
manpower and equipment will seriously reduce project
performance on the items listed in the detailed Work
Statement contained in the proposal and effect performance
vs. schedule times.
3) The engineering darkroom used for coating and reactivation
studies reached a prohibitive contamination level. The
air conditioning and filtration system was in continuous
operation 24 hours per day. This has necessitated a
major cleanup of the room and construction has started
on a separate sealed room as backup for the main engineer-
ing darkroom.
Continue to work according to the detailed Work Statement
within the constraints as given in problems section.
Require official verbal go ahead on this project.
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1) ' Free Radical Camera Speed Film Proposal,
x tension of Shelf Life and Reductic
Nonuniformities," Proposal No. 1185,
January 1, 1972 through December 31, 1972.
Rosenstiehl, Bull. Soc. Chim. France (3) 13, 273 (1895).
3) C. Aaron and C. C. Barker, J. Chem. Soc.1963, 2655.
25X1
25X11
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