The effects of polyethylene oxide on DMAAC's "B" type developer

Rochester Institute of Technology

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5-24-1979

The effects of polyethylene oxide on DMAAC's "B"

type developer

Harold McCullough

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Recommended Citation

To the Rochester Institute of

Technology,

Department

of Photographic Science

and Instrumentation

Senior Research Thesis

The Effects of Polyethylene Oxide on

DMAAC's "B" _Type

Developer

by

Harold M. McCullough

May 24,

1979

s-

nsw

Abstract

This report describes the results of a _study com

paring

ASA _speedy contrast

index,

and resolution from

a developer time series. The time series was made on

six levels each of

PEO-4-00,

_{-600, -1000,} and -1500 add

ed to DMAAC's "B"

developer. Kodak's

SO-277,

low

contrast, and

S0-243,

high _contrast, aerial duplicat

ing

films were used. Results show that

PE0-400,

at a

concentration of

30ml/l,

can be a material

help

in

get-ing

higher speeds and contrast index from SO-277 aerial

The Effects of Polyethylene Oxide on

DMAAC's "B" _Type

Developer

Introduction

Polyethylene Oxides* _{have been shown to act as both}

development accelerators and inhibitors. Several factors

seem to effect the results obtained when PEO is added

'to developers. A few of these factors are: type of emulsion, developer agent _used, what is the combination if a com

bination of developer agents are used. p

" _' ^-5,b -

-PEO compounds of the general

formula;

H0~(CH2-CH?~0--CH2-CH2.)n-0H have been studied. T It has also been

shown that the PEO effect depends some>-what on the

level of illuminance when a photographic emulsion is A 2

exposed.

Emulsions _containing PEO offer _{the possibility} of

higher speed for camera films without the loss of

Q

resolution. Developers _containing PEO offer methods

* _{PEO will be} used throughout as a generic abbrevia

tion for polyethylene oxides

(glycol).

Types of PEO

refer to chain length.

** n

being

such that the molecular weight

is

in

the

range of 150 to₍ 20,000.

(The

numbers stand for approxi

of

altering

ASA speed and contrast index

characteris-1 fl tics of film emulsions not _containing this compound. '

Much work has been done on the addition of PEOs

1 and allied compounds to both emulsions and developers.

Wood has theorized _extensively on the development

mechanism with reference to PEO..4*5'10

How8Ver

the

justification of this

theory

was not within the scope

of this study.

The Defense

Mapping

Agency

Aerospace Center has

had some success with the addition of PEQ-400 to its

"B"

type developer. It has offered a method of

increasing

the contrast index of low contrast aerial

duplicating

films without the unwanted side effects

of other methods.

It is known that _raising the

temperature,

one

method of

increasing

contrast, has the side effect

of

increasing

base-plus-fog,. This destroys resolution

in the toe portion of the image in films like Kodak's

30-277 and S0-243.

The Purpose of this _study was to determine an

optimum amount and chain length of PEO to be added to

the "B" developer.to maximize, speed and contrast index for

SO-277,

and hold to a minimum the change in contrast

S0-243-Method

Equipment:

A Kodak model 101 sensitometer was used to expose

sensitometric strips. The head was set _up with a

continuous _gray wedge and the Quanta-Scan Automatic

Densitimeter was used to trace the characteristic

curves after

development.

RIT's

dip

tank processor

with

intermittant,

nitrogen burst agitation was used

to

develop

the strips. A 100X microscope was used to

read the resolution targets.

Procedure:

Processing

conditions were set as close as possi

ble to simulate _processing with a Kodak Versamat

continuous roll-film processor. Developer temperature

was held at 90 F for all experiments. To duplicate

reasonable times available on the

Versamat,

a time.

series of

15*,

30,

60,

120,

and 190* seconds was-run

on each concentration level.

* _Fifteen seconds represents the fastest speed prac

ticable through one rack of the Versamat.

One-hundred-ninety seconds is the slowest, repeatable speed through

Levels of concenteation were varied for each PEO.

When concentration level started

causing

excess base

plus-fog,

the level series was

terminated.

PE0-400

was added at four levels?

15,

30,

60,

and 120 ml/l.

PE0-600 was added at five levels:

5,

10,

20,

30,

and

40 ml/l. PE0-1000 required three levels to reach ex

cess

base-plus-fog:

4,

8,

and 16 ml/l. PE0-1 500 re

quired three levels also:

3,

6,

and 12 ml/l.

A pH change series was made to see if this could

be considered as an$ alternate method of

increasing

.

the speed and contrast index of SO-277. For this method

to be _acceptable, it must not increase the contrast

of

S0-243

too much, The series tested wasrpH

10.04

(basic developer)

,

10.25,

10.50,

10.75,

and 11.00.

The correct

density

of the original continuous _gray

wedge was determined

by

tracing

the edge where nicks

were cut. When a nick was _encountered, . the

Quanta-Scan gives a _sharp

dip

in the trace. The nicks

corre-sponded to

density

increments of . 'SO _j^ 01 The

log

H scale was _easily determined this way. The

log

H at

the film plane of the sensitometer was 2.53.

Five-hundred strips each were cut from rolls of

SO-277 and S0-243-

They

were then exposed on the 101

sensitometer, aged for 24

hours,

and then placed in the

DMAAC's "B"

type developer

formula

is listed in

Table 1 . A time series on the basic developer was rep

licated

four times to be used as a comparison for the

pH and concentration level changes. Changes in pH

v/ere achieved

by

_adding sodium carbonate and/or sod

ium

hydroxide.

The PEOs were introduced to the

basic developer before final H2O was added. Develo

per temperature was controlled

by

_placing the

dip

tank in a water

bath.

The water bath temperature

had to be high enough to offset the _cooling effect of

the nitrogen burst agitation.

Table 1 . Developer Formula

-11.0

DMAAC "B" _Type

Hq

The basic formula

Phenidone 0,8 should have a pH

Sodium Sulfite 45.0 of

10.04.

The

Sodium Carbonate 35,0 concentration of

KBr 3.0 PEO-400 used at

'

Benzotriazole 0.2 DMAAC is 26.6 ml/l.

HoO to make. .... . , , . 1

/liti

er

After normal

fixing,

_washing> and

drying,

the sen

The zero

(0)

,PEO-ml/l _, plot represents the data

for the basic

developer.

It was connected to the

PEO-400 plot as a representative _trend.

Resolution was graphed for the PEO-400 series

only. Resolution _ususlly deteriorated because of

base-plus-fog

getting too high. R = _{Resolution/100} on the

chart.

One standard deviation

(s)

of the ASA speed and

contrast index was plotted on the one minute PEO-400

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Discussion

PEO-400 proved to be best suited for this developer

and two film combination,, At two minutes

development,

the

SO-277

had an

increase,

in the contrast index of

-95. At this _same time

S0-243

had _{an acceptable de}

crease in contrast index.

Generally

the best speed

increases were achieved with the PEO-400. A PEO-400

concentration of 30 ml/l was the cut off point for both

films.

After this

level,

resolution fell to an un

acceptable _level.

PEO-600 gave the poorest results. In most cases

the contrast index and speed was lower than that

gained

by

the other PEOs.

AT low concentrations PE0-1000 and -1500 gave a

higher contrast index than the PEO-400. When their

maximum concentration level was reached

(because

of

base-plus-

fog)

_PEO-400 surpassed them with

higher,

contrast index values. A loss of resolution also

occurred at the second level of concentration for

PEO-₁₀₀₀ and -1500.

Some general observations were:

0

Some

PEOs do increase speed and contrast

index,

but inhibits, development in high

density

areas at the

same time.

2)

An excess of PEO produces fog.

3)

At longer development times a _sharp break appears

in the sensitometric curve where retardation takes over

in the high

density

end.

4)

Only

PEO-400 is suitable for DMAACs type oper

ation. At DMAAC the developer replenisher is stored

at room _temperature and the PEO added at that tempera

ture.

PEO-600,

1000,

and 1500 have to be melted and

held at a temperature above 90 F. When

they

are added

to a solution at room

temperature, they immediately

return to a solid state.

5)

The contrast index of

S0-243

was not _adversely

affected with PEO-400.

Raising

the pH of the basic

developer caused the contrast index of _S0-243 to

climb higher than acceptable. See chart

#

Recommendations

There are _many questions of interest left in-'the

subject of PEOs.

Raising

the level of phenidone in DMAAC s "B"

type developer should be tested. This could give

completely different results. At times the developer

acted like a pure He- developer. Other researchers

have

found

that PEO decreases speed and contrast with

Hq

as the _only developer agent. ''

Micro-densitomete--traces could be run to check

resolution

better.

Granularity

and acutance tests

could also be performed.

Acknowledgements

I would like to express _my gratitude to Dr. Burt

H. Carroll for his

help

and guidance in this research