Defects and their Negative Impact on Leather Quality

by Rajayshree Reddy
Buckman Laboratories (Pty) Ltd.
Hammarsdale, 3700, South Africa
rjmoonsamy@buckman.com

Abstract
Leather defects are imperfections occurring in the grain surface or structure of
the hide or skin, which ultimately result in the unsightly appearance and / or
weakness of the resultant leather. Such defects may have arisen during the
life of the animal or during the many stages of leather production. There
appears to be a great need to identify and eliminate these defects which result
in devaluated leather. In several cases, it is possible to identify and remedy
the defects occurring, however, in some cases correction of the defects is
almost irreversible due to the severity of the damage caused on the leather
material. The aim of every leather manufacturer is to produce leather of
consistently high quality. The ideal situation in the tannery would be when no
defects are introduced as a result of beamhouse processes right through to
finishing operations.

Historical Perspectives
Leather making is one of the oldest trades of mankind. In earlier days, the
skins were smoked over an open fire to prevent rotting and putrefaction and
were then used as a fur garments to protect the wearer against adversities of
the weather. Over centuries later, it was found that the hair could be loosened
by wood ash and burnt limestone rocks, which then made the manufacture of
leather possible. A further discovery was that skins could be made more
resistant if they were treated with leaves and barks containing tannins, and
later the tanning effects of alum salts. Vegetable dyestuffs were used in
ancient history for colouring purposes. By the Middle Ages, it had developed
into a highly sophisticated craft.

Scientific research led to further advancements of manufacturing methods

and to the use of new products in leather making. Nowadays, leather
production is largely based on the utilization of raw hides and skins which
occur as a “waste” product in the slaughtering of domesticated animals that
are kept for meat. From an ecological point of view, the tanner is therefore an
“important utilizer” of putrescible matters which could otherwise contribute to
an immediate increase in the release of CO2 into the atmosphere and the
much discussed heating up of the earth’s climate.
 Possible causes of defects in the leather supply chain

Living Slaughter Tanning Finishing

Animal Flaying
& Curing

• loose grain • poor light fastness

• ticks
• putrefaction • pinhole damage • dye staining
• brands
• flay cuts • pebble grain • uneven spraying
• mange
• veininess • fat migration • uneven dyeing
• barbed wire
• delayed cure • uneven splitting • finish peeling
• growths
• heat damage • uneven shaving • water stains
• horn rakes
• folds
• warts
• grain cracks
• surgery scars
• lime blast
• scabies
• poor quality
• warble flies process chemicals
• acids & alkali burns

Pre-slaughter Defects
Damages caused during the life of the animal include scars, infestations and
infections. Scars resulting from scratches and cuts (when the cut is healing,
the fibres grow densely packed together, and the healed skin is often hard,
raised and lacking hair follicles). Scar damage is also caused by branding the
animal for ownership purposes, usually in the butt area, which happens to be
the best part of the hide. Infestations caused by ticks, warble flies and mange.
Ticks pierce the skin to suck blood, leaving holes that either look like pin-
pricks or minor scars in the grain of the leather. This defect occurs mainly in
the belly areas of the skin. Infections caused by e.g. ringworm, if it heals it
leaves no scars, but if the animal is slaughtered while still infected, the grain
appears coarse at the site of the infection.

Post-slaughter Defects
Damages caused after the death of the animal include flaycuts, putrefaction,
veininess and heat damage. Flaycuts cut into the fibres of the dermis (in thin
leathers they show through) and thereby spoil the grain. These cuts are
usually the result of careless or improper flaying. Putrefaction is a result of
bacterial growth, which starts almost immediately once the animal is dead,
unless the skin is properly cured. Bacterial degradation occurs especially on
the exposed flesh side. The first indication of putrefaction (aside from odour)
is hair slip, usually accompanied by a sensitive condition of the grain surface,
so that the grain layer tend to rub away during normal processing of the stock.
Slight rubbing gives a “dull grain” generally accompanied by blochy finishing.
Putrefaction also causes the general structure of the skin to become loose
and flabby.

Veininess is due to bacterial degradation of collagen fibres in the vicinities of

the blood vessels. Veininess usually result from the use of skins from animals
found dead of natural causes, from improper or delayed curing after flaying or
from some reason wherein the blood is not drained from the animal
immediately after slaughter.

Processing Defects
There are a number of defects that occur during the processing stages of the
raw hides and skins to finished leather production, of which a few are outlined
as follows:
Metallic stains – caused by nickel, iron, calcium, etc. which originate from
processing chemicals usually appear brown/black on the grain surfaces of the
leather and are very difficult to remove.
Harsh process conditions i.e. extremes in pH, high temperatures and
improper usage of acids & alkali can cause extensive, irreversible grain
damage.
Yellow stains, caused by migration of fat and grease onto the grain surface
of the skin, occur when the processing stages e.g. pickling is prolonged.
White blemishes caused by free sulphur solubilizing in the oils and
polymerizing onto the grain surface.
Lime blast damage causes white, calcium sulphate stains on the grain
surface of the leather.
Pink staining on game skins caused by organic dye coating on the hair
surface.
Sueded grain caused by the abrasive action of processing.

Case Histories

Nickle-sulphide stains:

Staining with a run-off appearance – 8x Irregular shaped particles

Staining in concentrated spots – 32x Macroscopic view of stain

The black stains appeared to be fixed to the grain surface of the wet blue
sample. Scanning electron microscopy indicated the presence of irregular
shaped particles in the stained areas. The run-off black staining is a typical
pattern of black nickel-sulphide stain. Nickel, silica and aluminium was
detected in the stained areas. A metal chelant was used to remove the stain,
but the stain appeared to be deeply embedded within the fibre matrix and
could not be removed. When nickel and other heavy metal stains occur, they
persist through processing and remain as stains on the full grain because
these metallic stains are insoluble in acid and alkali.

Calcium soaps – brown/black stains

Brown/black spot on grain surface – 8 x Enhance view of stain – 50 x

Ammonium sulphate crystals with Calcium sulphate crystals in the

impurities – 25 x defect area – rhombic shape

Positive iron spot test on impurity found EDAX analysis – high amounts of
in ammonium sulphate – 25 x Ca and Cl in the defect area

Brown/black stains appeared to coat localised areas of the wet blue surface in
tiny spot formation. Iron spot tests of the stains verified that the stain was not
caused by iron although some iron contamination was detected in the
ammonium sulphate raw material used in the processing of the wet blue.
EDAX analysis indicated the predominant presence of calcium and chlorides
in the stained areas, which were not present in the unstained areas. In
addition, scanning electron microscopy (SEM) isolated the presence of
calcium sulphate crystals in the defect areas. Complete stain removal was
achieved using 2.5% metal chelant for 24 hours of washing at 40oC. The
contamination appeared to be an organic/calcium species, or calcium soap. It
may be that localised concentrated zones of calcium reacted with the lipids
present, thus causing the small black spots on the grain surface of the wet
blue.

pH Shock causing yellow stains:

Wet blue samples with yellow stains on the grain surface – stain removal after stripping & retanning

Wet samples with yellows stains – chrome stains after repickling and tanning

Yellow staining appeared on the grain surface of the wet blue samples after
product application. The cause of the stain was due to a sudden pH shock.
Stain removal was achieved via a stripping process using a mild alkali (borax,
sodium sulphite or sodium bicarbonate). 1% Borax with 100% float yielded the
best results after retanning. Samples that were repickled and tanned
produced chrome stains.

Iron contamination:

Ostrich crust leather with Brown stain on grain surface Positive iron spot test – 12 x
staining – Macroscopic view 8x

Varying intensities of staining were visible on the grain surface of the ostrich
crust leather sample. Iron spot test indicated the presence of iron in the defect
areas which were not detected in the unstained / control areas hence
confirming contamination by iron. The contaminant appeared to be localised
concentarted zones of iron reacting with the lipids present.
Grain peeling – finished ostrich leather:

Epidermal layer peeling away from the corium Torn collagen fibre bundles
Mag: 8 x Mag: 16 x

Extensive, irreversible grain damage occurred on ostrich finished leather,

resulting in devaluated leather of a very poor quality. Grain peeling occurs
when the epidermis peels away from the corium exposing a looser, weakened
fibre structure. The defect is usually caused by harsh pH adjustments in the
leather process.

Oxidation of oils – yellow stains:

Yellowing on grain surface – Mag. 25 x Unstained grain surface – Mag. 8 x

Sample % Fat & Grease

Yellow stained area 2.18
Unstained area 1.34

Yellow stains occurred on the grain surface of ostrich wet blue. Chemical
analyses of the stained areas indicated a higher concentration of fat and
grease as compared with the unstained areas. Oxidation of oils is a possible
cause of the discolouration.

Yellowing of zebra skins:

Yellow staining of the hair on the zebra skin samples was found to be caused
by excess fat and grease content.
 Sample Control Defect
1 6.49 11.52
2 4.29 15.17
Average % Fat & Grease 5.37 13.34

The defect areas were found to have twice as much fat and grease as
compared to the control / unstained areas. A series of tests using degreasers
were conducted to remove the yellow stains from the zebra skins. From the
evaluation, it was found that 0.2% of degreaser X was used to remove the
stain.
If pickled stock is stored for long periods of time, the grain may become
discoloured or yellowish in colour. Yellowing of the leather is an effect, which
is undesirable in white or pastel shades. The long-standing time of the pickled
pelts, storage in warmth, humidity and exposure to air accelerate the oxidation
and polymerization of the fats onto the surface of the skin.

Acid burn damage:

Typical signs of acid burn damage are grain cracks, sueded grain, loss of fibre
strength and weakened grain, pinhole damage, staining and pitting. Acid
burns appear dark in colour, and the grain enamel is weak and often cracks in
the pattern of broken glass especially after the leather dries.

Pinhole damage & grain Dull, abraded grain surface – Grain cracks resulting from
cracks - Mag. 8 x “sueded grain” Mag. 12 x weakened grain – Mag. 8 x

Sulphur Spew – “bloom effect”:

Black finished leather with no Finished leather with whitish Panel sample with flowery
blooms – Mag. 8 x blooms – Mag. 8x bloom effect – Mag. 8x
White blemishes were visible on the grain surface of black finished leather.
SEM indicated the presence of irregular shaped particles on the grain surface
of the defect and panel samples, but not in the control sample.

EDAX spectrum of Contol EDAX spectrum of defect EDAX spectrum of panel

Element Control Defect Panel /Defect

CK 76.32 73.35 78.25
OK 18.97 18.30 16.47
Na K *ND 0.34 *ND
Si K 4.71 2.83 2.85
SK *ND 4.5 7.74
Al K *ND *ND 0.53
Cl K *ND 0.2 *ND
Total 100 100 100
*ND – not detected

Sulphur was detected in the defect and panel samples only. In addition, there
appeared to be almost twice the amount of sulphur in the panel sample as
compared to the defect sample, hence the flowery bloom presence. Free
sulphur is soluble in oils and it is via the oils that sulphur is carried to the grain
where it spews.

Lime blast damage:

Dark staining around hair follicles + shiny Cross-sectional view of stained area with
coating between follicles -–Mag. 50 x calcium sulphate crystals

Dark, grey stains were noticed on the grain surface of dyed crust leather. The
epidermal layer of the grain appeared to be slightly raised in the stained areas
as compared with the unstained areas. A cross sectional view of the leather
indicated the presence of crystals embedded within the fibre matrix. EDAX
analysis confirmed the presence of calcium in the stained areas, which was
not detected in the unstained areas.
 It would appear that the staining is a result of lime blast. When hides are kept
standing in liquors overnight, the air reacts with calcium hydroxide to form
calcium carbonate (lime blast). The calcium carbonate reacts with ammonium
sulphate or sulphuric acid to form calcium sulphate which gives the whitish
stains.

Lime blast exists in 2 forms. In the one form, prior to calcium carbonate
precipitate, lime blast can be removed by an acid wash. In the other form, the
precipitate is formed and it combines with the hide substance, which is very
difficult to remove. The acid wash must be done properly or else it will cause
uneven pH in the skins. Low pH not only kills the action of the enzymes in the
following bating process, but also produces acid-swollen grain, hence causing
roughened grain. Lime blast causes the surfaces of the limed skin to appear
shiny and interferes with the subsequent finishing operations. Since it is
difficult to dye areas affected by lime blast, the defect becomes prominent
after the dyeing operation.

Game skins (Springbok) with pink discolouration:

Defect hair with pink Control hair –

colour – some organic normal / white
dye coating the hair
surface

NaCl crystals present on the control hair No NaCl crystals detected with SEM/EDAX –
smooth even coating on the defect hair

The pink discolouration was clearly visible on the springbok defect sample.
Stereo-light microscopy indicated a shiny coating on the pink hair while the
unstained hair appeared to have a dull appearance. SEM clearly indicated the
defined, overlapping scale structure on the defect hair, which appeared to
have a smooth, even coating. The white, unstained hair had a fused scale
structure with a flat appearance while the defect hair had a more cylindrical
shape. The investigations conclude that the defect was caused by some kind
of organic dye coating the surface of the hair, hence giving the hair the pink
discolouration.
Seal crust leather with “sueded grain”:

Grain damage / sueded grain on seal crust leather – Mag. 10 x

The epidermal layer of the skin appears to be removed by the abrasive action
of processing. The slightly “eaten” grain is termed “suede” grain. The damage
is not due to chemicals, as there are no signs of chemical run-off marks,
peeling, cracking, etc. Also there are no localised lesions caused by bacterial
attack.

Parasitic damage:

Circular lesion in the grain caused by Localised area of grain peeling from mechanical
parasite – Mag. 8 x abrasion caused by parasite – Mag. 8 x

The grain damage in the wet blue sample was minimal. The lesions were too
few in number and localised to be caused by either chemical or bacteria, as
bacteria are known to infest an entire area of skin and not just few, localised
regions. In addition, microscopic examination revealed mechanical damage,
which is typical of parasitic behaviour.

Damages caused in the living crocodile:

Grain damage alongside the scales of the Grain damage in tail area
belly area of damage crust sample
Severe grain damage was noticed alongside the scales of the belly and tail
area of the crocodile skin. The pattern of grain damage appeared to be in one
direction, particularly around the belly area, thus suggesting the possibility of
mechanical / physical damage caused during movement when the animal was
alive. The pattern of grain damage is typical of the way in which the live
animal would have dragged itself on it’s belly along a rough surface / ground.
The possibility of the damage being caused by chemicals, was ruled out as
chemical damage would have occurred throughout the skin and not just
concentrated alongside the scales.

Summary:
Several factors negatively impact on the quality of the final leather produced.
The challenge to the tanner is to choose; good raw materials (i.e. hides and
skins and process chemicals of superior quality), proper quality control of
processes, root cause analyses and problem resolution.

Conclusion:
Problem identification and sound technical investigation can help in solving
and preventing leather quality problems from occurring in the future.

References:
1. TANCOUS, J.J, 1959, Skin, Hide and Leather Defects, Ohio
2. DEMPSEY, M, 1984, Hide, Skin and Leather Defects: A Guide to their
Microscopy, New Zealand
3. GERHARD, J, 1996, Possible Defects in Leather Production:
Definitions, causes, consequences, remedies and types of leather,
Germany
4. SHARPHOUSE, J. H, 1971, Leather Technicians Handbook, Britain