The stability of reciprocity law failure in color print papers

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4-1-1982

The stability of reciprocity law failure in color print

papers

Victoria L. Carriero

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THE

STABILITY OF RECIPROCITY LAW FAILURE

IN COLOR PRINT PAPERS

by

Victoria L.

Carriero

A thesis submitted in partial fulfillment

of the requirements for the degree of

Bachelor of Science in the School of

Photographic Arts and Sciences in the

College of Graphic Arts and Photography

of the Rochester Institute of Technology

April 1982

Victoria L. Carriero

Signature of Author

-

~

, _.-.-.

~

.

Photographic Science

and Instrumentation

Edward M

0

Granger

Cert ified by

_

0 0 0 0 • o r ' 0 • 0 0 0 • • • • • • • • • • • • • • • • • • • • • • •

Thesis Advisor

Ronald Francis

ROCHESTER INSTITUTE OF TECHNOLOGY

COLLEGE OF GRAPHIC ARTS AND PHOTOGRAPHY

PERMISSION FORM

Title of Thesis The

_Stability

of

_Reciprocity

Law Failure in

Color Print Papers.

I,

Victoria L. Carriero.

hereby

grant permission to the Wallace

Memorial

_Library

of R.I.T. to reproduce _my thesis in whole or

in part.

_Any

reproduction will not be for commercial use or

profit.

THE

_STABILITY

OF RECIPROCITY LAW FAILURE IN COLOR PRINT PAPERS

by

Victoria L. Carriero

Submitted to the

Photographic Science and Instrumentation Division

in partial fulfillment of the requirements for the Bachelor of Science degree

at the Rochester Institute of

_Technology

ABSTRACT

A _study of _reciprocity law failure in Kodak Ektacolor 74

and 78 color print papers was carried out

_by

a series of equal

engery exposures.

_Using

a color _separating filter pack to dif

ferentiate the response of RLF of the individual emulsion layers

an acceptable color print is attainable

_by

_using these curves

to determine exposure and filtration changes.

ACKNOWLEDGEMENTS

The author wishes to extend her gratitude to Dr. Edward

Granger of Eastman Kodak

_Company

for his

time,

help,

and

guidence towards the success of this thesis.

A special thank you to Bob and Arlene Green from

_Sentry

Color Labs

_Limited,

who _generously supplied _equipment, materials

and Saturdays for the completion of this thesis. Another thank

you to their crew:

_Linda,

_Irene,

_Bob,

_Ray,

_George,

_Don,

_Peter,

Molly,

and Jane for their

_help

and tolerance.

A thank you to all _my classmates and friends for their

help

and encourgement_, which was _greatly appreciated.

A thank you is in order for the generous

_funding

from

the Central Intelligence Agency.

TABLE OF CONTENTS

PAGE NO.

la List of Figures

1 Introduction

3 Background

6 Hypothesis

7 Experimental

13 Results

25 Discussion

27 Conclusion

28 References

29 Appendices

30 Appendix A - Kodak Wratten Filters

32 Appendix B

-Reciprocity

Curves

la

LIST OF FIGURES

Figure 1. Cross section of Kodak Ektacolor paper.

Figure 2. Color separation filter pack.

Figure 3. Experimental curves compared to calculated curves,

Figure 4. 74 paper, aim densities.

Figure 5. 78 paper, aim densities.

Figure 6. Kodak

_70,

_98,

99 filter spectral sensitivity.

Figure 7. 74 _paper, Emulsion I.

Figure 8. 74 _paper, Emulsion II.

Figure 9. 74 _paper, Emulsion III.

Figure 10. 78 paper, Emulsion I.

INTRODUCTION

The _reciprocity law for photochemical reactions was

formulated

_by

Bunsen and Roscoe in 1862.

_"They

proposed as a

general law for photochemical reaction the condition that the

mass of the photoproduct from such a reaction is determined

by

the total exposure

_involved,

that

_is,

the product of the ir

radiance* _{and time, and is independent of the two} factors

2 separately."

Any

deviation from this law is called _reciprocity

law failure

(RLF)

.

It is of great importance to those who use color

phot-graphic materials under varied exposure conditions to be able

to compensate for RLF. In custom color _printing

_labs,

giant

enlargements and murals are common. When _making these _{enlargements,}

long

exposure times are

_frequently

used (over 30 seconds).

Hence,

RLF is a major problem.

There is no _easy solution to this problem as no information

ia available on RLF for color print papers that would

_help

make

3

corrections for

_long

exposure times. This means that to

obtain _quality color prints at these longer exposure

_times,

test prints must be made and repeated until the correct color

balance and

_density

is achieved. This can take _{many tries and}

*The term irradiance is used to describe the _{radiation flu*}

incident on a plan which also has been called

_intensity.

Tb< >

words for this paper are used

_{interchangabl}

and it consumes valuable time in manpower and throughput, not

to mention the costs of wasted paper.

The stability of RLF between emulsion batches of Kodak

Ektacolor 74 and 78 papers was investigated so to determine a

means of _correcting for

_density

loss and color shifts that are

inherent at longer exposure times. The ultimate intent here

is to determine if these corrections can be made and the _accuracy

BACKGROUND

When the _reciprocity law is applied to the photographic

process, it specifies _only the amount of direct photolytic

4

silver _resulting from an exposure. "A given mass of photo

graphic silver can have different effiencies in

_initiating

development of a photographic material

_depending

upon its

location,

its state of subdivion, and so on. That the amount

of developed

_density

in a processed photographic material should

also be independent of irradiance and time

_individually

is thus

a condition beyond that _originally intended

_by

the

Bunsen-5 Roscoe law."

This same

_terminology

however,

is used when

talking

about densities produced in developed photographic

emulsions.

In photographic emulsions, the exposure is the product of

irradiance and time

_(E=It),

but it is not independent of the

6

intensity

of _exposing light. For example, the

density

produced

by

an exposure of 100 meter-candles for 1 second and an exposure

of 1 meter-candle for 100 seconds is not equal even though

the exposures are equal.

The RLF of a photographic emulsion can be explained in

terms of latent image formation. It occurres

_during

either

high-intensity, short-time or

_{low-intensity,}

long-time exposures,

Actually,

RLF occurres at deviations from the "optimum" exposure

a certain exposure.

"With

_{low-intensity}

_exposures, the efficiency of

latent image formation is lowered. Because of the slow

release of electrons

_by

the _relatively scarce incident

photons of

_light,

the latent image can build _{up only}

very slowly.

_During

this initial stage of formation

the latent image is _relatively unstable and _may be

dis-ipated

_by

thermal disintegration or _chemically induced

action. This loss of latent image causes less

_density

to be produced than at more favorable exposure conditions.

The photographic emulsion is said to have suffered

low-intensity

reciprocity failure.

Exposures at

_{high-intensity}

are inefficient for

another reason the slowness of the migration of sil

ver ions through the crystal to the latent image site.

A

_{high-intensity}

exposure floods the crystal with

photo-released electrons. These electrons gather at latent

image specks, but the silver ions cannot reach the

speck in sufficient _quantity to neutralize the electrons.

The latent image speck becomes _{negatively charged,} re

pelling other _electrons, and the latent image formation

is limited

_by

the slow rate of silver-ion migration.

The repelled electrons may be captured

_by

the bromine

atoms formed

_during

the exposure. A large number of

the photoelectrons are thought to be captured

_internally

in the crystal. Such internal latent image sites are

usually unavailable for

_development,

_wasting the effect

of the exposure that released the electrons. Sites on

the surface _may not be built _up to a developable state

even though the sublatent image is stable. High inten

sity causes a loss in developed

_density,

because the

latent images are not built _up to sufficient size."

In this study, emphasis will be placed on the low-inten

sity RLF since this is most common when _making prints. Gener

ally, exposure times range from 5-30 seconds when making 8X10

prints. For this experiment, the time will range from .5 to

512 seconds.

In color _printing papers, RLF is made complicated

_by

the

fact that there are three light sensitive emulsion layers in

stead of _one, as in B&W emulsions. (Figure

₁₎

These are the

cyan, magenta and yellow

_dye-forming

layers which are sensitive

-~~^.

-Overcoat

Cyan

Dye-Forming

Layer

Interlayer

Magenta

_Dye-Forming

Layer

Interlayer

Yellow

Dye-Forming

Layer

Polyethylene Support

Paper Fiber Support

Polyethylene Support

Figure 1. Cross section of Kodak Ektacolor paper.

these emulsion layers suffer from

_RLF,

but the magnitude of the

Q

failure varies from layer to layer. When _making color prints

at different exposure

_times,

not only does the

_density

loss

due to RLF have to be accounted for,Aa color correction will

6

HYPOTHESIS

The purpose of this thesis is to show that color photo

graphic papers are

_largely

affected

_by

RLF and that this

failure differs from one emulsion batch to another.

_By

the

use of _reciprocity curves that represent the failure in each

of the three light sensitive emulsion

_layers,

it is possible

to account for the loss of

_density

and color shifts that are

EXPERIMENTAL

The evaluation of the _stability of RLF of color print papers

will require a series of exposures. The papers will be exposed

using a color filter pack _consisting of Kodak red, green, and

blue wratten color _separating filters with neutral

_density

filters

to produce

_high,

_medium, and low densities. To build the color

filter _pack, as shown in Figure

_2,

the color separation filters

used are Kodak Wratten #70 red

_filter,

_transmitting

radiation

from 660 - 990

nanometers; the #99 green

_filter,

_transmitting

radiation from 520 - 590

nanometers; and the #98 blue

_filter,

transmitting

radiation from 385 - 495 _nanometers. The

spectral

transmittance of these filters is shown in Appendix I . The red

color _separating filter was placed in the first _column, the

green in the second and the blue in the third. To produce the

high,

medium, and low

_density

patches a 0. 6ND filter was placed

over the bottom _row, a 0. 3ND filter on the middle row and zero NT)

on the

top

row. The medium

_density

will be called the aim

density. To achieve an aim

_density

between .8 - 1.0 _across the

filter pack, ND must also be placed down the columns because the

transmitted radiation through the color _separating filters is

not equal. The amount of ND used to achieve the aim densities

RED GREEN BLUE

AIM

0.6 ND

0.3 ND

0.2 ND 0.6 ND

9

To run an exposure series, a Super Chromega Enlarger with

a 150mm f/5.6 lens at a height of 46.2cm and bellows set at 4cm

was used. This set _up will be held constant for all exposure

series.

For the first exposure series Kodak Ektacolor 74 RC Paper

type 2524 emulsion number 109170 was used. The exposure of the

paper was held constant. One way of _calculating the exposure,

E,

is shown below:

Log

E =

Log

I +

_Log

t

-Log

D

For the exposures, the lens was set at f/5.6 and the first

exposure time was .5 seconds with no neutral density. Neutral

density

filters were used to change the

_intensity

instead of

using the aperture, therefore E and I were held constant and

t and D were varied _{proportionally} The

_intensity

was decreased

by

one _stop increments using

0.3,

0.6,

0.9....ND placed in a

negative carrier as the time was increased

_by

one stop

increments,

.5,

1,

2,

4,... seconds. A series consisted of 11 exposures

ranging in time from .5

-512 seconds. All 11 exposures were

run through a Colenta American 50 inch processor at the same

time. The densities produced were read on a MacBeth 924

Transmitt ion/Reflection densitometer.

In order to account for _variability of the enlarger and

in processing, this series was replicated 5 times. The average

and standard deviation of the densities were _calculated, then

10

green and blue light sensitive emulsion layers due to RLF.

A second exposure series is done with a different emulsion

using Kodak Ektacolor 74 RC _paper, emulsion number 954230 to

test to see if there is _stability of the RLF from one emulsion

batch to another.

_Again,

5 replicates were made and the curves

were plotted.

To test the _stability between the emulsion batches used,

the _reciprocity curves of one emulsion was normalized to the

other. This was done

_by

_taking

the difference in the densities

at each exposure

_time,

_adding all the differences and

_dividing

by

the total number of exposure times _used, which was 11. One

curve is then shifted

_by

this value at each point.

_Using

3

standard deviation error bars on each _point, the curves are com

pared. If both curves overlap, there appears to be no differ

ence in the reciprocity characteristics between these two emul

sions. If some of the points do not overlap, then the recipro

city characteristics are different for these two emulsions.

This was done for the red, green, and blue emulsion layers.

In order to account for any differences in speed of differ

ent emulsion

_batches,

a 4 point test was tried

_by

_fitting

a

third order equation to the _reciprocity curves.

_Using

the col

or filter pack and

_by

choosing four points _along the curve, a

best fit curve was generated

_by

_using program Fit on an Apple

computer. The times that were used were

_1,

_4,

_32,

and 128

second exposure times. The red, green, and blue curves were

tested for accuracy

by

using exposure times used in the expo

11

experimental densities.

The method

_finally

used to determine the change in exposure

and filtration is described below:

Start with a print of good color balance made at exposure

time,

T^. To produce the same print at another exposure time,

T2

, the reciprocity curves for that emulsion are used.

First,

obtain the

_density

values for _{red, green,} and blue at both ex

posure times. These will be

_R1

, B.. , and G.. for exposure time

T-. and R ,

B2

, and G for exposure time T. The delta change

in the red

_density

will correspond to the change in exposure.

When the AR is multiplied

_by

1/gamma of the paper, it yields

the change in exposure which is expressed in denominations of

stops, .3 equals a 1 stop increase in exposure.

To determine the yellow filtration _change, the difference

in shifts from one exposure time to another is calculated as

shown below.

AY =

[(R2"B2)J

"

[(Rl_Bl^

X/* x 10

The AY will be the number of cc units added or subtracted to

the pack used at

_time,

T.. .

The magenta filtration changes are determined the same

way:

AM =

[(R2-G2)]

"

[(Ri"Gi)]

Vtf

x 10

The AM will be the number of cc units added or subtracted to

the pack used at

_time,

T^

.

To test this method of _correction, a standard scene was

used to make prints. The scene consisted of a _grey card and

color scale held

_by

a

"Shirly"

12

time was used to make a reference print. Another print will be

made at a longer exposure time using this method to correct for

13

RESULTS

The _reciprocity curves for Kodak Ektacolor 74 _paper, Emul

sion

_I,

Emulsion

_II,

and Emulsion III are shown in Appendix II.

The aim curves were compared and all three emulsion have the

same shape and the three layers show the same trends. It should

be noted that the color filter pack was slightly changed when

the exposure series was run. A . 1 ND was placed over the blue

filter to

_bring

the aim densities in range. Therefore. the

blue sensitive layer in Emulsion III was _significatly faster

in speed than the other two emulsions tested.

In the Ektacolor 78 _paper, the two emulsions tested had

several points which did not overlap with the error bars. The

shapes of the three layers are the same but

_they

do not follow

the same trends.

_Also,

the speeds of the layer varysrquite ^a

bit.

Program Fit was tested _using the data from Emulsion I of

the 74 paper. Figure 3 shows the _accuracy of this program.

Four exposure times were used. The times used in the program

will depend on the size of the paper

_being

used. For 8x10 inch

paper, exposure times of

_1,

_4,

32 and 128 are a good choice.

For larger papers, the 4 points used should take into account

the probable times that will be used in actual printing. The

14

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23

extreme points that were not included within the time range.

If these points are critical _ones, then the 4 exposure times

used to fit the curves should be changed.

The results for the method suggested in

determining

ex

posure and color corrections are shown in Table 1. This Table

indicates the reference _print, a print at T without any cor

rections to demonstrate the _reciprocity

_failure,

a print at

T with exposure corrections _only, and a print at

_T?

with both

the exposure correction and color correction. The _red, green,

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25

DISCUSSION

The Ektacolor 74 emulsions do _vary in _speed, but for the

emulsions

_tested,

these variations are within a _stop to a _stop

and a half.

_They

tend to maintain the same characteristics and

the cross overs in the _red, green and blue curves are

_fairly

constant.

Five prints were made to test this method of correction.

The reference point was made at 4 seconds, the others were made

at 8 ,

16,

32 and 64 seconds. The results of the corrections

made are _{visually very} close.

_Comparing

the densities of the

4,

8 and 64 second exposure

_times,

the densities are within .02,

two

_density

units, which is the tolerance of the densitometer.

Careful consideration was taken as to the exact placement for

the measurement of these densities. For the 16 and 32 second

exposure

_times,

the densities are higher than the reference

print made at 4 seconds. This is due to the change in expo

sure needed to reproduce the print. The 32 second exposure

needed almost 1/3 stop increase of _exposure, and the 64 sec

ond exposure needed almost a 1/2 _stop increase. The exposure

was changed

_by

_using ND filters that come in 1/3 stop incre

ments. If the exposure change was not in these

_increments,

it

was rounded to the nearest third of a stop. Both the 16 and

in-26

crease of exposure.

The RLF in Ektacolor 78 paper is unstable for the two emul

sions tested. Emulsion I had aim densities made at the "optimum"

exposure time in the .8 to 1.0

density

range. Emulsion II

ranged from .45 to 1.0 at the same time. This signifies that

the emulsion layers vary greatly in speed and make switching

from one emulsion to another difficult.

_By

_using program

_Fit,

new emulsions can be tested easily.

Two prints, one made at 8 seconds and one made at 64 sec

onds, were used to test this method of correction. The cor

rected print was 10

_density

units lighter than the reference.

As explained

_before,

the exposure change was slightly larger

than a third of a stop. The correction was made

_by

_increasing

exposure 1/3 of a _stop, therefore the final print was slightly

lighter than the reference. The color corrections were off

by

about 2 cc units in cyan and magenta if the

_density

was

correct.

_Visually

the two prints were _{acceptable, noticing}

only a slight color shift.

One _way to reduce the error in exposure corrections would

be to use the aperture of the lens _along with a color transla

tor for _metering the _exposure, to determine the exact change

in exposure. This would improve the accuracy of the RLF cor

rections. When changing the filtration on the _enlarger, error

is also introduced in the exact _positioning of the numbers.

Other sources for error would be in the calculated _reciprocity

27

CONCLUSION

It was found that the RLF in different emulsion batches

vary.

_{By testing}

a new batch of emulsion with 4 exposure

_times,

the densities can be entered into a program to fit a curve close

to the actual _reciprocity curve. From the _{curve, red,} green

and blue densities can be determined for different exposure

times.

_{By doing}

the quick calculation either

_by

hand or

_by

a

programmed _computor, the exposure and filtration changes are

determined. The _accuracy of this method is dependent on how

precise the exposure correction

is,

also the precision of the

filtration and _processing variability.

According

to the results, a good to very good approximation

of the reference print is attainable

_by

this method. In actual

use, a final print with minor corrections of + 3 cc units for

color can be predicted. With a means of

_determining

exact

exposure _changes, the visual

_density

of the prints should match

28

References

G. Haist , Modern Photographic

Processing

Volume 1. John

Wiley

and

_Sons,

New

_York,

1979. p. 743.

2

Mees and James ,

Theory

of the Photographic Process 3rd

ed.

_MacMillan,

New

_York,

1966. p. 133.

3

Kodak Customer

_Service,

Personal communication.

4

Mees and

_James,

p. 133.

5

Mees and

_James,

p. 133.

6Haist,

p. 744.

7Haist,

pp. 744-745.

Q

G.

_Wakefield,

Exposure Control in Enlarging. Fountain

Press,

New

_York,

1972. p. 187.

9Wakefield,

p. 187-188.

Kodak Publications B3, Kodak Filters for Scientific

and Technical Uses.

R.

_Quattrini,

Program Fit .

12Kodak

Publications B3, p. 36.

29

30

APPENDIX A

Kodak Wratten Filters

Kodak Wratten number 96 neutral

_density

filters reduce

the

_intensity

of light _reaching the film without _affecting the

12

tonal rendition of the colors in the original scene. These

filters were used in the color filter pack to obtain aim densities

in the range of .8 to 1.0.

They

were also used to reduce the

intensity

of the exposing light while the time was increased

to

_keep

a constant exposure.

The manufacturing tolerance for NO. 96, 75mm square filters

13

is +.10% of the nominal diffuse density. For the filters

used in this

thesis,

the tolerance was found to be within

.06% of the nominal diffuse

_{density by}

direct measurement.

The Kodak wratten filters used in the color filter pack

were the 70 red, 99 green, and 98 blue. All three are narrow

31

CD o c n) p P

H

e CO fi m p H

"h"00 ' BuTS

'

8"uTT

wavelength

(nanometers)

200

Figure 6a. Dark red, number 70.

0)

fi 2 1. rd P P H

6

C 1

rt) p

"400

' 6u0 800

wavelength

(nanometers)

200

Figure 6b.

_Green,

number 99.

0) o c ft) p p H 6 CO fi m fn LP

200 400 600 800

wavelenght

(nanometers)

32

APPENDIX B

33

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VITA

Vicki was born in

_{Cherry Hill,}

New

_Jersey

and graduated

with honors from Delran High School in

_Delran,

New Jersey. She

began her studies in Photographic Science at Rochester Institute

of

_Technology

in Septmeber 1978. Between her junior and senior

year she was employed

_by

Digital Equipment Corporation as a

Process Engineer and plans on _returning for a permanent position