THE PHOTOGRAPHIC INDUSTRY

INTRODUCTION
 The first recorded use of a lens for image
formation occurred in the latter part of the
sixteenth century.
 The effect of light on silver salts was known to
the early alchemists, but it was Wedgwood, son of
an English potter, at the beginning of the
nineteenth century, who first successfully
reproduced images, as negatives, on paper or
leather impregnated with these silver salts
PHOTOGRAPHIC PROCESS

 Cameras.
The essential parts of a camera include
I. a light proof chamber,
II. a lens for forming the image,
III. a device for supporting the film or plate,
IV. a shutter for controlling the quantity of light
admitted,
V. a view finder for determining the area being
photographed.
MANUFACTURE OF FILMS, PLATES, AND
PAPERS.
 In the making of photographic films, plates, and
papers three distinct steps are carried on:
1) the preparation of the light-sensitive emulsion,
2) the manufacture of the base or support for the
emulsion, and
3) the coating of the emulsion on the base. The
flow sheet shown in the following gives a
general representation of the manufacturing
steps involved.
Fig. 1
 EMULSIONS
 The so-called photographic emulsion is in reality not a true emulsion but
rather a dispersion of tiny silver halide crystals in gelatine which serves
as a mechanical binder, a protective colloid, and a sensitizer for the
halide grains.
 Many different types of silver halide emulsions are manufactured, the
characteristics of each being dependent upon the silver halide used and
the details of manufacture. In slow positive emulsions for photographic
papers the bromide, chloride, and chloro-bromide are chosen.
 Chloro-bromide and pure bromide emulsions are also employed for
lantern slides and other very slow plates. All fast emulsions, usually for
negatives, contain silver bromide and small amounts of silver iodide.
 The iodide is essential for high-speed types but seldom exceeds 5 per
cent.
 The finished emulsion generally consists of 35 to 40 per cent silver
halide and65 to 60 per cent gelatine.
 The manufacture of the emulsion may be divided
into four principal steps:
 precipitation,

 first ripening,

 washing, and

 second or after-ripening.

 The following presentation will deal with Agar-

Agar emulsion and is further illustrated by Fig. 1.
PRECIPITATION
 The gelatine after soaking in cold water for about 20 min.
is dissolved in hot water. The requisite quantities of KBr
and KI are dissolved in this solution, which is then ready to
receive the AgN03 solution.
 In the case of the ammonia process a 10 to 15 per cent
excess of KBr is used and the amount of gelatine is 20 to
60 per cent of the total required in the finished emulsion.
For neutral or "boiled." emulsions a 2 to 5 per cent excess
of KBr is generally used and l0 to 20 per cent of the total
gelatin.
 In the ammonia process a silver nitrate solution is mixed with concentrated
ammonia until the initial precipitate of Ag20 redissolves.
 This solution is added slowly, with thorough mixing, to the halide-gelatine solution.
 The mixing temperature is usually about 40°C.; at 50°C. and higher, fog will
appear.
 For neutral emulsions no ammonia is used. A 10 per cent silver nitrate solution is
added to the halide-gelatine solution at 60 to 80aC.
 In this mixing operation an excess of KBr is necessary to produce large grain size
and to prevent interaction of silver ions with the gelatine.
 The KBr solution is prepared with a relatively Small part of the total gelatine, as too
much of the latter would interfere with grain growth during the ripening step.
 Moreover, the principal part of the gelatine is protected from the harmful influence
of heat and ammonia.
 However, care should be taken that AgBr does not set,tle out owing to the smaller
quantities of gelatine.
 Careful control of the mixing process is essential, as the concentrations of the
solutions, the temperature, and the manner in which the AgNOa solution is added
all have a pronounced effect on the character of the emulsion.
FIRST RIPENING
 The ripening or digesting process is essentially a continuation of grain
growth under the influence of heat, the temperature being about the
same as that of the mixing step.
 The excess of KBr in the emulsion increases the solvent capacity for
AgBr.
 The small crystals, being more soluble than the large ones, tend to
dissolve and reprecipitate upon the large crystals.
 Since the sensitivity of the final product is dependent upon the grain
size, the ripening step is an important one and warrants careful
regulation. If this process is carried too far, the finished plate or film will
be subject to fogging. After the first ripening, no more crystal growth
takes place.
WASHING
 At the close of the first ripening process, the balance of the gelatine,
previously soaked in water, is added slowly with thorough stirring.
 The emulsion is then cooled to about 10°C. ,to produce a firm jelly. It is
important to chill the emulsion as quickly as possible, so that the ripening
process is suddenly interrupted at the proper point, .
 In order to attain maximum solidity, the emulsion may be permitted to
stand over light in refrigerated rooms, or it may be chilled in silver-plated
metal pans cooled with brine. The latter method allows the next step to
proceed after 2 to 3 hr.
 The cold jellied emulsion is shredded into small" noodles," 2 to 5 mm. in
diameter. This is accomplished in the noodle press, where a piston
operating in a silver-plated cylinder of bronze or nickel forces the jelly
through a screen (see Fig. 1).
 The noodles are dumped into a wire basket set in a wooden or stoneware
tank, where they are washed for several hours in cold running water (less
than10°C.) to remove free NH3, KNO3, NH4NO3, and excess KBr. A
careful control of the washing process is essential, as a certain amount of
residual KBr is highly desirable in the emulsion to inhibit fogging during
development. Some hardness in the wash water is desirable, as bivalent
cations inhibit swelling of the gelatine. Consequently a solution of CaS04 is
used frequently for the wash water.
AFTER-RIPENING (CHEMICAL SENSITIZING)

 The emulsion noodles are freed as much as possible from mechanically

adhering water by drainage.
 They are next melted at about 45°C.
 Gelatine may be added to compensate for the water carried by the swollen
noodles.
 The noodles are digested for some time at 50°C. in the afterripening or
second ripening tank as depicted in Fig. 1. No crystal growth takes place
during this treatment, the chief effect of which is an increased sensitivity
due to the formation of minute activated centers of Ag2S by a reaction of
the halide with sulfur containing substances occurring in the gelatine.
 These are allyl isothiocyanate (mustard oil) and related compounds.
 In the case of the ammonia process the after-ripening may be omitted, since
most of the Ag2S centers are probably formed during the first ripe~ing,
presumably by the following reactions:
 If the after ripening[ process is carried too far, a decrease in sensitivity
begins to occur. Emulsions containing iodide can be ripened for a longer
time without fog formation than can pure bromide emulsions. For this
reason a much higher, sensitivity can be obtained with the former type.
Before coating the, emulsion on the support, it is customary to add chrome
alum or formaldehyde as a hardening agent.
 Phenol or thymol may be introduced to prevent the growth of mold or
bacterial attack.
 The addition of KBr at this stage is an aid in the prevention of fog.
 The introduction of amyl alcohol or saponin serves to depress the surface
tension of the liquid emulsion, facilitating uniform foam-free spreading on
the support.
 The sensitizing dyes for orthochromatic or panchromatic films are here
added to the emulsion. The warm fluid emulsion is filtered and is then
ready to be coated on the support.
PREPARATION OF THE SUPPORT.
 The support for the photographic emulsion can be of glass, paper, or cellulose acetate or polyester film.
 Glass plates are still employed for many scientific and commercial purposes, map making, and some copying and
color printing jobs.
 Glass has the advantages of freedom from distortion and not deteriorating with age. Glass plates are made from
high-quality, thin sheet glass.
 Their preparation for the emulsion includes preliminary inspection and automatic cleaning by revolving brushes in a
strong soda solution.
 They are coated with a thin substratum of gelatine containing chrome alum, dried in ovens, inspected, packed in
trays, and transferred to the coating room.
 The white flaky cellulose acetate for film has an acetyl content of 39.5 to 42.0 per cent. It is insoluble in chloroform
but dissolves in acetone. Chloroform-soluble acetate is not strong enough for photographic film.
 To decrease the tendency of cellulose acetate to stretch in water and shrink after drying, substances such as triphenyl
phosphate are generally added. This highly viscous solution is known as "dope." Filtration, aeration, and
temperature adjustment are necessary before sending the "dope" to the film base-coating machines .
 Each machine has a heated, rotating drum 20 ft. in diameter by 4 to 6 ft. wide. It is coated with silver. By the time
the drum has made one revolution the solvents have evaporated. The film is stripped off, wound into rolls, and
transferred to the cooling rooms. The solvents may be recovered by adsorption on activated carbon.
 The acetate film is given a thin undercoat or substratum (the "subbing") of gelatine and chrome alum to increase the
adhesiveness of the light-sensitive emulsion. The base for photographic papers is coated with gelatine containing
blanc fixe (precipitated barium sulfate) to mask the cellulose impurities from the halide salts. Sometimes china. clay
or satin white (a coprecipitate of calcium sulfate and aluminum hydroxide) is used instead of blanc fixe.
COATING
 Glass plates are coated on a traveling belt, the fluid emulsion flowing onto the
glass surface. The coated glass then proceeds onto a belt or rollers which are
kept wet with ice-cold water to set the emulsion.
 The plates are removed, dried, cut into requisite sizes, and packed. Inj coat5ing
both film and paper, the base moves on rollers into the coating trough
containing the liquid emulsion as represented in Figs. 1 .
 The excess emulsion draining off as the support leaves the trough uniform coat.
The coated base passes over a chill roll or into a cooling chamber to set the
emulsion.
 After leaving the chill roll or chamber, the film or paper is automatically looped
into festoons 5 to 20 ft. long, which are moved slowly through a drying tunnel
supplied with warm, filtered air.
 The finished film is spooled for use. Naturally the preparation of the emulsion
and its coating onto the base must be conducted in air-conditioned rooms,
illummated only with lights for the particular emulsion being manufactured.
COLOR PHOTOGRAPHY
 Natural-color processes can be divided into two classes:
1. additive and
2. subtractive processes.
 In the former the colored light reflected or transmitted by each
image is transferred directly to the observer's eye, independent
of the other images; in the subtractive processes the light first
passes through a number of the images in succession
 Each image subtracts or removes certain of the light
components, until the final transmitted total contains only those
components necessary to reproduce the original colors.
 The additive processes of modern importance are the mosaic-
screen ones, known as Agfa color, Autochrome, Dufay color,
and the Finlay process. In these processes the image plane
contains tiny differential areas, each of which acts as a color
filter. The sum total of light from all these areas produces, to
the eye, a colored image.

 In the subtractive processes, the final positive is the composite

sum of the effects produced by three (or more) transparencies
superimposed one upon the other on the same film. In the
reversal subtractive processes (Kodachrome2) the color
transparency is produced directly.
 Color film is also a multilayer subtractive or complementary type consisting of a
"pack" of three color-sensitized emulsion layers and a filter layer coated on acetate
film. The total thickness of the pack is only slightly more than that of most black-
and-white negative emulsions.
 The layers are in the following order, top to bottom: blue-sensitive .( furnishes
yellow dye record) ; yellow filter (screens blue light from lower layer); green-
sensitive (furnishes magenta dye record) ; red-sensitive cyan dye record); base;
anntihilation backcoating.
 Note that the of the dye records are complementary to the subject colors. When a
negative is printed on color-positive film, a positive print result reproducing he
color and range of light values of the subject. Kodacolor (Eastman color) film and
prints are similar to Ansco color, giving first a color negative from which any
number of color positives can made. In the remaining prosses, separation negatives
are made which be printed by one of the color-printing processes, all of which are
substrctive. These latter processes include

 (1) imbibition dye printing, man Dye transfer and Curtis Orthotone;

 (2) imbibition ink printing. ltJomoil Transfer;

 (3) tricolor pigment printing, Carbro process; and

 4 metal toning, Chromatone process.

PHOTOMECHAMICAL REPRODUCTION
 Photography finds one of its most important modem
applications in the reproduction of photographs on
the printed page by means of printing inks.
 These processes may be classi & ad as
 (1) relief printing (photoengraving),
 (2) intaglio printing (photo- gravure, rotogravure,
and metal engraving), and
 (3) planographic printing (lithography,
photolithography).
 relief printing the raised portion of a plate receives the ink for
transference to the paper. So-called line plates and halftone plates are
used.
 The line plates are prepared by exposing a negative against a zinc plate
coated with sensitive albumen and ammonium dichromate. The exposed
zinc positive plate is coated with greasy ink and washed with warm
water to remove the unexposed light-sensitive coating.
 Topping powder (dragon's blood) is next dusted on the remaining inked
areas and burned in to form an acid-resistant layer, after which the plate
is immersed in nitric acid to dissolve out the exposed areas, leaving the
image in relief upon the plate, to which the ink adheres in printing.
 intaglio printing, the procedure is reversed from
relief printing, the hollow regions of the plate
holding the ink.
 In photogravure intaglio printing, a positive
transparency is made and brought in contact with a
sheet of dichromated gelatine and exposed to light,
insolubilizing the gelatine in the light areas of the
photograph. Meanwhile, a copper plate has been
coated with finely powdered resin, which is burned
onto the plate.
PLANOGRAPHIC PRINTING, OR
LITHOGRAPHY,
 makes use of the inability o( a water-wet surface to take
ink.
 A zinc or aluminum plate is roughened in order to make it
capable of retaining water and coated with dichromated
albumen. A line negative, or halftone negative prepared as
described above, is exposed in contact with the plate, after
which the insolubilized image is coated with a greasy ink
and the whole soaked in warm water to remove the soluble
albumen. Subsequent etching with acid gum arabic renders
the exposed surface repellent to ink but does not attack the
metal.
BLUEPRINTING
 This widely used reproductive process is dependent on
the fact that ferric ions are reduced to ferrous ions in the
presence of organic matter and under the influence of
strong light. Paper is coated with a solution of ferric
ammonium citrate and potassium ferricyanide.
 If a line drawing is placed over such a prepared paper,
exposed to strong light, and treated with water (as both a
developing and fixing agent), the blue image appears
wherever the light reduced the ferric ion. The image is the
insoluble blue ferrous ferricyanide, Fe3[Fe(CN)6]2.
Surface coating
industries
Surface
Coating
Industries
SURFACE-COATING SUBSTANCES

 refer to any mixture of film-forming

materials with the addition of pigments,
solvents, and other additives, which
when applied to a surface and then
dried, will yield a thin film that is
functional and decorative in sense.
SURFACE-COATING SUBSTANCES: RAW
MATERIALS
There are four basic raw materials necessary for the
production of coating substances:

1. Pigment
2. Resin
3. Solvent
4. Additive
PIGMENTS

- are colored, organic and inorganic

substances that are widely used in coating
industries as well as in ink, plastic, rubber,
ceramic and paper industries whose main
function is to impart color of desired tint and
shade.
WHITE PIGMENT
LITHOPONES

 is a mixed zinc sulfide- barium sulfate pigment that contains

about thirty percent zinc sulfide.
 are used in water-based paints because of their excellent alkali
resistance.
 The synthesis involves the following reactions:

BaSO4 + 4C BaS + 4CO

BaS+ ZnSO4 ZnS + BaSO4


TITANIUM DIOXIDE

 is regarded as the most important white pigment being

utilized by majority of industries today
 is marketed in two crystalline forms, anatase and the
more stable rutile.
 Anatase can be converted to rutile by heating to 700-
950°C. TiO2 is widely employed in exterior paints and
also in enamels and lacquers.
TITANIUM DIOXIDE

 It is manufactured via the following processes:

 Sulfate Process

 Chloride Process
CHLORIDE PROCESS IN TIO2 MAKING
SULFATE PROCESS IN TIO2 MAKING
WHITE PIGMENT

Natural Black Oxide Black Iron Oxide Lampblack

INDUSTRIAL RESIN

- these are synthetic polymers that have

adhesive, film-forming and useful reactive
properties.
- bind with pigments in order to form a
continuous film that is important for
aesthetic and protective purposes.
INDUSTRIAL RESIN

 Shellac
 Phenolic Resin
 Alkyd Resins
 Unsaturated Polyester resins.
 Formaldehyde resins
 Amino Resins
 Epoxy Resins
 are stable mechanical mixtures of one or more
pigments.

 Pigments and extenders are carried or

suspended in dryings oils or solvents.

 solvent serves as the drying material to which

other ingredients might be added
TYPES OF PAINT

 Solvent based

 Water based
1. Emulsion based
2. Latex based
MANUFACTURING
PIGMENT VOLUME CONCENTRATION (PVC)

𝑃𝑉𝐶
volume of pigment in paint
=
vol. of pigment in paint + vol. of nonvolatile vehicle constituents in paint
Flat paints 50-75% Exterior house paints 28-36%

Semi-gloss 35-45% Metal primers 25-40%

paints

Gloss paints 25-35% Wood primers 35-40%

TABLE 1. RANGE OF PVC FOR A GIVEN

PAINT
SAMPLE PROBLEM 1

It is desired to make an exterior house paint of color blue with

a reddish undertone. The manufacturer decided to use a mass
ratio of 2:3, a combination of pigment to resin (polyvinyl acetate,
PVA). Solvent will then be added to about 25% utilized PVA at a
flow rate of 100 kg/h. Determine if this combination will qualify as
an exterior house paint.The following empirical data are available
as follows.
SAMPLE PROBLEM 1.0

Substance SG, @ 25 ℃
Ultramarine Blue 2.35
Phthalocyanine Blue 1.62
Prussian Blue 1.8
Polyvinyl Acetate 1.19
SOLUTION
Basis: 1 hr operation
Identify:
Solvent—water (latex, PVA)
Pigment—Ultramarine Blue (reddish undertone property)
100.0 𝑘𝑔
mH2O= 100.0 kg VH2O= 𝑘𝑔 = 0.1 m3
1000 3
𝑚

Solve for Pigment and Resin mass and corresponding volume used:

2
mresin= 0.25(100)= 25.0 kg mpigment= × 25 = 16.667 𝑘𝑔
3

25.0 𝑘𝑔 16.667 𝑘𝑔
Vresin= 𝑘𝑔 = 0.02101 m
3 Vpigment= 𝑘𝑔 = 0.00709
1.19 (1000 2.35(1000
𝑚3 𝑚3
m3

0.00709
PVC= 0.02101+0.00709+0.1 × 100= 5.54%
B. VARNISH

- refers to a preparation consisting of resinous

matter such as copal or lac, dissolved in an oil
or in alcohol or other volatile liquid.
EXAMPLES

 Spirit Varnishes
 Oleoresinous Varnishes

 Japans
C. LACQUERS

- defined as those non-convertible coatings

and principally as a coating composition
based on a synthetic, thermoplastic, film-
forming material dissolved in organic solvents
that dries by solvent evaporation or a curing
process that produces a hard, durable finish.
D. ENAMELS

- It is used to get a good gloss because after

drying, the enamels will form a very good
lustrous and glossy finish.
BRUSHING

- This is the simplest method and also the

slowest and most expensive.

- Promotes better wetting of the surface and

can be used in restricted spaces, be useful
for small areas, with less wastage and
contamination of surroundings.
ROLLER
AIR SPRAY
AIRLESS SPRAY
ELECTROSTATIC SPRAYING
AUTODEPOSITION
BOYSEN’S KNOXOUT TECHNOLOGY
ANTI SCRATCH/ SELF HEALING PAINT