Metallographic Printing Methods

Sulphur Printing

Aim:
Determination of sulphur in iron and steel
Introduction:
Impurities may exist in steel products. It is desirable that their amounts should be minimal and
homogeneously distributed within the product. These impurities degrade the mechanical
properties of the steel; especially sulphur content in steel makes it brittle. Sulphur may exist
chemically in steel in one of two forms, either as manganese sulphide or as Iron sulphide.
Experimental Procedure:
Sulphur printing detects and permanently records the distribution of sulphur in Steel. The surface
of interest to be tested for distribution of sulphur should be reasonably smooth and free from
foreign matter such as dirt and grease. Grinding the surface on papers, numbers 400 to 1200 and
subsequent thorough washing will generally produce a surface satisfactory for the purpose.
Photographic bromide paper is soaked in a 2% aqueous solution of sulphuric acid for
approximately 3 or 4 min.
The paper is removed from the acid solution and allowed to drain free from excess solution. The
emulsion side of the paper is then placed in direct contact with the prepared specimen surface
and allowed to remain in contact under moderately applied pressure for 1 or 2 min.
Care must be taken that all entrapped air bubbles between the paper and the specimen surface are
eliminated.
The reaction of the sulphuric acid with the sulphide regions of the steel produces hydrogen
sulphide gas, which reacts with the silver bromide in the paper emulsion, forming a characteristic
brown to gray-black deposit of silver sulphide. These reactions may be expressed as follows:
+ 2 4 4 + 2
Or
+ 2 4 4 + 2
2 + 2 2 + 2
When the reaction has proceeded for approximately the recommended length of time, the
photographic paper is removed from the surface of the specimen, rinsed in clear running water,
and then fixed permanently by placing it in a photographic fixing solution for about 15 min.
When fixation is completed, the print is again washed in running water for approximately 30
min. and subsequently dried in the usual manner.
Fixing Solution composition:
600 mlWater
240 g Sodium Thiosulfate (hypo)
15 g Sodium Sulfate
45 ml Acetic Acid (28%) *
7.5gBoricAcid

15 g Potassium Alum
Enough water to make one liter
*To make 28% acetic acid from glacial acetic, dilute 3parts glacial acetic to 8 parts water. Store
unused fixing bath in a dark place.
Result:
The examination of properly prepared sulphur print will disclose quite clearly, because of the
presence of darkly colored areas of silver sulphide, the precise location of sulphur inclusions on
the prepared surface of the metal. A grouping or gathering of such silver sulphide areas indicates
the presence of sulphur segregation, whereas a random dispersion of the spots denotes a more
uniform, distribution of the sulphur inclusions.
Oxide printing:
First method:
A technique for showing the distribution of oxide inclusion containing iron was developed by
Niessner. Gelatin paper is moistened in an aqueous solution containing5 % HCL acid for about 5
min. The gelatinized side of the paper is blotted dry and placed on to the polished surface of steel
sample for about 5 seconds.
The paper is then removed and place in the aqueous solution containing potassium ferrocyanide
(20 gm 4 ()6 to 1000 ml of water). This solution develops the image. The print exhibits a
light blue colour over the contact area. Dark blue spots are present at place where iron containing
inclusions are present.
Second method:
Soak the photographic paper in the solution of 15gm of sodium chloride to the dilute
hydrochloric acid solution. The rest process is same as first method.
Third method:
Cellophane 0.025 mm thick is soaked for few minutes in water. After the cellophane dries, a few
drops of 20 % aqueous solution of quinoline-Etl are distributed over the surface of the film. After
about a minute, the solution is wiped off. The film is placed in the polished sample, and an
etching solution consisting of equal part of a 1.2 % ferrocyanide solution and a 0.25% HCL acid
solution is applied. After 2 to 3 min., the etching solution is washed off and the film is removed
and developed in a 2.5% solution of potassium ferrocyanide in water and then rinsed. The film
image is then oxidized in a solution containing 1ml of 3% H2O2 in 100 mL water.
Phosphorus printing:
A sample with a ground surface is immensed in a solution consisting of 5 gm Ni(NO3)2 and 1.5
gm CuCl2 dissolved in 12 mL hot water, 6 gm FeCl3 and 150 mL methanol(a few ml HNO3
may be added.). After 11/2 to 3 min, a coloured surface began to form. This layer can exhibit a
wide range of colours from pale brown to purplish red. Segregation shows as white strikes and
spots. This pattern can reportedly be transferred to photographic paper. A sheet of photographic
paper is soaked for several minutes in a 5 % solution of potassium ferricyanide inwater
The paper is placed face up on the blotting paper and the coated steel surface is placed against
the paper for about a minute. The paper is rinsed and fixed. The segregated areas should show up
as a blue colour.

The filter paper is soaked in an ammonium molybdenum and nitric acid solution (5 gm
ammonium molybdenum dissolved in 100 mL of cold water, which is then added to 35 mL nitric
acid). The excess solution is drained off, and the paper is placed on the surface of polished
sample. After a contact time of 3 to 5 minutes, the paper is removed and placed in the developing
solution. The paper is immersed in this solution for 3 to 4 minutes. Initially the print should
appear yellow but after 45 seconds, a blue colour is observed where phosphorus is present.
Because the filter paper is attacked by the solution of SnCl2 and HCL, a pinch of alum is added
to the developer to harden the paper. After development, access acid is washed off in flowing
water and paper is dried.
Developing solution composition:
By Niessner and Feigl
50 mL SnCl2
50 mL HCL
100mL H2O

Enos and khel

5 mL of saturated SnCl2 solution to a
mixture of 50 mL HCL and 100 mL
H2O