Considering Leather

The most utilitarian and multipurpose material ever readily available to early man came from the hide of an animal.  Making leather from hides or furs from skins might have been the first human industry.  Until the very recent dawn of plastics and synthetic fibers, leather and fur were nearly indispensable commodities.  Leather is a superior material for several applications like footwear, saddles and upholstery and still remains the material of choice over any synthetic alternative.  However, turning a smelly raw animal skin into usable leather is a difficult process.  Before certain procedural and chemical advancements in the previous century, commercial tanning was even yet a more laborious and time consuming pursuit. This post will endeavor to briefly separate and identify some of the varied techniques used in leather tanning, while perhaps empowering some readers with a few ‘do it yourself’ type leather tanning skills.

What is leather?

A mammal’s skin or hide consist of a thick center layer called the “dermis” or “corium” which is sandwiched between a thinner epidermis on the outside and a subcutaneous fatty layer on the inside.  The corium of a fresh hide contains between 60-70 percent water and 30-35 percent protein by weight.  Of that protein about 85 percent is of a special fibrous type called “collagen”.  These protein fibers are held together by chemical bonds.  Tanning chemicals (tannins, enzymes, acids, bases or salts) in effect alter these bonds between collagen fibers, remove water and dissolve natural fats within a hide.

If a fresh hide can be frozen, salted or quickly dried then it can be temporarily spared an otherwise inevitable decomposition from bacterial rot.  A fresh hide may have a few useful applications in raw form though, considering its tendency to shrink substantially upon drying.  However should dry rawhide be re-hydrated, it immediately becomes susceptible again to rot.  Raw hides have value and those destined for leather processing are soaked in brine or packed in salt at the slaughterhouse before being shipped to a tannery.  Should they desire, tanneries could preserve surplus hides for over a year by packing them in more salt.  Tanning is both a physical and chemical process that preserves a hide and converts it into leather.  The removal of membranes and subcutaneous fat from the underside and the optional hair removal on the topside entail just one or two physical processes.  The chemical processes reorganize some organic molecules, while often coating or replacing others with outright inorganic substitutes.

The leather industry has an odorous history and one accompanied by pollution. Today there are three distinctive methods to use for tanning a hide: by the ancient vegetable process, modern chromium process or novel aldehyde process.

Tanning liquors

Historically either alkali or acidic solutions have been used in tanning.  A Native American Indian might have soaked a deer hide in a potash solution for example.  Also called “lye”, this caustic alkali or base solution of potassium carbonate can be created simply by leaching water through wood ashes.  Lye (potash/potassium carbonate, sodium hydroxide/caustic soda & potassium hydroxide) or other alkali solutions like hydrated lime will remove the hair from hides.  Both sodium sulphide and sodium hydrosulphide will dissolve hair.   Even some weaker alkaline solutions like ammonia collected from human urine; have the effect swelling the hide, enlarging follicles and loosening hair at the root.

* Several centuries ago in urban areas like 16th century London, it was common practice for poor children to collect urine from private “chamber pots” and public “piss pots” to sell it for money.  Urine is a rich source of urea and decomposes into ammonia, which was an important source of nitrogen to factories that could not yet synthesize such a chemical independently.  At least three important industries required urine back then.  Textile manufacturers used ammonia for altering the color of vegetable dyes and adjusting pH in dye baths, gunpowder makers needed the nitrogen found in urine to make critical potassium nitrate and tanners also needed or favored urine to produce leather. 

* Even back in ancient Rome, urine pots were placed in the streets for the public to fill at leisure.  These pots were collected and used to wash laundry.  The laundry came out bright and clean and the practice was so popular that Emperor Vespasian taxed this urine in the 1st century AD.

* Today household ammonia (5 – 10% pure ammonium hydroxide) is still critically acclaimed for its general cleansing ability, including for laundry.  Just don’t mix ammonia with bleach (calcium hypochlorite) because that will create dangerous fumes.   

Two mildly acidic and astringent chemicals used to produce leather are alum and tannin.   Alum (or specifically hydrated potassium aluminum sulfate) is used as a blood coagulant in articles like styptic pencils, in underarm deodorants, as a dye-fixer or mordant for wool and plant fibers and in tanning solutions where the hair or fur might want to be retained.  Alum creates a less toxic alternative tanning liquor and for small jobs is being used more frequently now than it ever was in the past.  Tannin is easier to find as it occurs naturally in the bark and leaves of several different plants. This astringent polyphenol binds to and coats collagen proteins, making them less water soluble and less vulnerable to bacterial decomposition.  Tannin is but one type of polyphenol out of thousands, and these phytochemicals give vegetables and fruit both their color and beneficial antioxidant properties.

* Astringents taste bitter to the tongue, pucker up the mouth and tend to shrink or constrict body tissues in general. An astringent tanning liquor then can be expected to tighten its hold upon hair, as opposed to a lye liquor that would swell and loosen its hold. 

* Tannin from tree bark is far more traditional than tanning liquor from alum. By the early 17th century Industrial Revolution, large plots of the northern English countryside were being ravaged to mine alum rich shale deposits, which were then baked in bonfires using all the firewood from the surrounding landscape.  Probably more of that alum found its way into textiles than leather but by this time England was running out of trees too. 

In the past the commercial treatment of leather with tannin required massive amounts of tree bark (approximately an equivalent weight of bark to the weight of a skin).  In America, after the forest near early Boston and New York City were denuded, tannin harvesters ascended to the Catskill, Adirondack and Allegheny mountains to placate their ravenous need for tannin. Whole hemlock forests were flattened of trees, merely for the tannin in tree bark while the softwood was largely abandoned. The practicality of building tanneries closer to the source of tannin and then shipping hides long distance rather than tree bark was eventually realized.  Leather tanneries often formed the central economic hub of many new communities in American outward expansion.

The word “tannin” is derived from a German word meaning oak.  Several different plant species (including chestnut, eucalyptus, mangrove, maple, sumac, wattle, and willow trees or bushes) are high in astringent tannin and are commonly used in vegetable tanning liquors.  It would be possible to leach a tannin rich tea from the dead leaves of most any deciduous tree in the autumn.  Some people have boiled bran (the husk of wheat or rye kernels) to obtain tannin.   Hemlock tends to make leather reddish-brown while oak produces yellowish-brown and chestnut while famous for making thick Italian shoe-sole leather, turns collagen fibers dark brown.  Before introduction of chrome tanning solutions in 1858, most all leather produced was simply “vegetable tanned” leather.

Keith Weller acquired from USDA ARS (Website)

Keith Weller acquired from USDA ARS

So around the same time that the trans-American railroads were being constructed, Texas cowboys were driving cattle herds up to meet the railhead and jobless Civil War veterans were harvesting wild buffalo for meat; new chromium leather tanning techniques were suddenly gaining favor in Europe.  The new rails were soon used to ship cattle back east (notably to Chicago) and products like buffalo hides back further east to established tanneries perhaps in Boston or New York City.  The fact was that those eastern American tanneries relied upon much human labor and slow vegetable tanning chemistry.  Typically a cow hide might need to soak in a barrel of tannin liquor for six months to produce high quality leather.  Although not especially desired or in demand by American tanneries, a few bundles of Buffalo hides made their way to England; where they were enthusiastically received and thousands more were immediately ordered.  The decimation of the great American Bison herds is directly traceable to bovine diseases spread from domestic cattle and the commercial slaughter demanded by global economics.  In a twelve year period beginning in 1871, about six million buffalo hides from approximately nine million animals slaughtered – were shipped to Europe.

Chrome

Somewhere back in the middle of the 19th century, the effects of Chromium (III) upon a rawhide were discovered.  These solutions came from dissolving elemental chromium in sulfuric or hydrochloric acid. Two solutions, chrome alum (or chromium (III) potassium sulfate) and chromium (III) sulfate are noteworthy in tanning.  The latter of the two solutions is the simpler, cheaper form preferred today by the commercial tanning industry.  Not nearly as toxic as the hexavalent chromium (IV) variety of chrome used on shiny automobile parts, chromium (III) tanning liquors nonetheless contain heavy metals and should be disposed of carefully.  In the right pH environment chromium (III) can oxidize into undesirable and environmentally persistent chromium (IV).   Chromic acid which is different but related, is noteworthy for being a strong and corrosive, oxidizing agent that will attempt to consume organic compounds.

About 85 percent of all leather today is chrome tanned.  ‘Chrome tanned leather’ is thinner, more eaten away and more flexible than ‘vegetable tanned’ leather.  Chrome tanned leather is good enough though for most situations and may even be the preferred choice in a few applications; given its flexibility and better resistance to shrinkage caused by water.  Some chromium remains behind in the hide after tanning, as it is tightly bound to the collagen proteins.  The reason that chromium has become so ubiquitous in today’s tanning industry is because it allows great reductions in both time and labor.   Vegetable tanned leather which is more expensive, is usually reserved for quality items like belts, purses, wallets, shoe soles, horse bridles, harnesses and saddles.

Both vegetable but especially chrome tanned hides are tumbled and pounded around in rotating drums like the museum piece imaged above.  Once the desired level of chrome penetration into the hide is achieved (which takes about 24 hours) the hides will come out “wet blue”; not the tan color shown.  Several varied finishing techniques would follow next.

Whereas vegetable tanning might require grueling labor for fleshing and stretching the hide and long months of exposure to tannins inside a vat, chromium tanning creates a product in just days or weeks.  The substantial chore of fleshing is much simplified by virtue of these chemicals dissolving most of those unwanted fatty tissues. The details of temperature, pH and other chemical factors are more complicated, critical and caustic with chrome than with vegetable tanning liquors.  In this present day and age, one can no longer just buy U.S.P. approved chromium potassium sulfate crystals from the local drugstore either.  Chrome tanning on an individual basis is not practical, but vegetable tanning is.

Aldehyde Tannage 

While chromium (III) solutions leave tumbled hides a color that is referred to as “wet blue” a newfangled process leave the hides “wet white”.  The first and most notable, quick working base chemical used in “chromium-free” aldehyde-tanning was the water soluble gas, formaldehyde.   Not creating the pollution that chrome does, some small amount of toxic formaldehyde residues nonetheless remain within the clothes, shoes and car seats made with this leather.  A newer chemical called glutaradehyde is highly reactive towards proteins, but leaves aldehyde wet white leather comparatively ‘baby safe’ and allergen free.  Glutaraldehyde is more expensive than formaldehyde, it sterilizes or inactivates viruses and bacteria, it is used to remove skin warts and is occasionally used in hydraulic “fracking” fluids to unclog oil wells of microorganism buildup.

The American Indians and probably many other nomadic aborigines as well typically used the brains of an animal during the hide tanning process.   Boiling the brains with a bit water creates an oily soup that can either be used as a solution to completely submerge and soak a hairless hide or be rubbed into the underside of a fur.  Once the treated skin is smoked over a fire however, chemical changes occur and a mild aldehyde type tannage takes place. Almost any organic oil benefits the flexibility and durability of leather.  Some famous leather ointments like Neatsfoot oil however will darken leather while brain oil is less likely to.

*Neatsfoot oil (a brand name) actually comes from the tibia (lower leg –shin bone) of a cow; it doesn’t easily freeze and absorbs readily into leather.  Sulfating the Neatsfoot oil allows it to penetrate even further. 

Price of rawhide

The U.S.A. is only the eighth largest producer of leather in the world, with a total 669 million square feet produced in 2011.  The other top ranking leather producers superseding the U.S. that year were: China (3,913 M sq. ft), Brazil (1,832 M sq. ft.), Italy (1,573 M sq. ft.), Russia (1,460 M sq. ft.), India (1,397 M sq. ft.), South Korea (1,083 M sq. ft.) and Argentina with 715 million square feet of leather produced.

In the 1990’s the price of a wet nondescript cowhide in the U.S.A. was approaching $1.00 per square foot. Today’s price for a wet steer hide (over 53lbs.) from a slaughterhouse is about $70.00.  Because of its potential as leather, raw cowhide is generally more valuable than pig, sheep or goat hide.  However if the hair is to be retained then hair quality or unusual coloration like Angora goat or Holstein cow can fetch much higher prices.  There are authorities on this subject.

The price of meat influences the price of leather.  Tanneries must compete with food companies to get the hides because what is not converted to leather is immediately converted to gelatin instead.  Gelatin is made by boiling the collagen from skins, tendons, ligaments and bones in water.  Europe produces a large share of the world’s gelatin, supplying about 400,000 tonnes per year.  More pig skin is converted to gelatin than is cow, sheep or goat skin.  Gelatin itself is used in puddings, candies, marshmallows, ice creams, cakes, shampoos and miscellaneous cosmetics.

Removing the hide

 Flaying or “skinning” the hide usually takes one or more very sharp and slender knives.  These knifes generally dull quickly while skinning and need to be re-sharpened periodically.  The thickest skin on an animal is usually around the neck and shoulders.  The thinnest skin, which is more vulnerable to nicks by a skinning knife, is at the belly.   When removing the skin in one piece the starting incision is usually made from the chin, down through the center line of the belly, to the rectum.  From each foot, cuts running down the inside of the legs come down to meet the centerline.

Small the animals have thinner skins than large animals.  The most difficult skinning would have been preformed by a fur trapper that was compelled by market demands to tediously flay around the head, face and feet, or by a taxidermist who’s flaying gets even more intricate.  Furriers and taxidermist are rare these days but their profession still requires much more skill, patience and attention to the details of skinning than an average hunter would employ.

There is more than one way to skin a cat

Large industrialized slaughterhouses can remove a full grown steer’s hide in less than a minute.  Techniques differ but these factories usually employ moving assembly line division of labor or small teams working simultaneously on one carcass.  Skinners might use  pneumatic “roller skinners” or normal knives and a mechanized skin pulling apparatus.

factory skinner using a flaying knife

team using a hide puller

For small furs like rabbit and mink a commercial furrier might purchase or construct a hide pulling machine that quickly shucks the skin, leaving it inside out.  The only labor involved is making a few precise cuts beforehand, around the head and feet.

DIY Vegetable Leather Tanning

There are many, many books, pamphlets, magazine articles and YouTube videos detailing “do-it-yourself” tanning techniques.  The novice should focus on the overall intent of tanning and less upon one particular technique.  The intent is always to remove the natural water and fatty tissues from a skin and replace them with something else.  A novice should initially avoid tanning large hides and seek something smaller. The amount of labor required for a large hide (bigger than a deer or sheep) can quickly become discouraging or overwhelming for the un-initiated.  The first decision to be made is whether or not the hair should be removed.

Caustic lye, potash or lime would be normal choices for de-hairing solutions.  It is possible however to simply submerge and tie a deer hide perhaps in a cold mountain stream and leave it there for a week or two. Returning later one will find that the hair pulls out easily by hand, no caustic solution was needed.  Many sources are adamant that the first thing to do with a hide is to scrape the flesh from the underside.  Alternatively though other tanners might prefer soak a hide first, thereby loosening both hair from one side of the hide and softening those fatty flesh tissues from the other.  If the tanner of furrier decides to keep the hair then he skips the de-haring alkali bath and moves on to fleshing.

* Buffalo hunters in the past didn’t flesh their hides at all, but cured and preserved the hides for shipment by spreading on salt and drying them out in the sun.

The “Indians” native to North America were expert leather tanners.  Every bit of their clothing was made of leather and often their homes were as well.  For scraping the hide they used tools made of bone, rock, wood or antler.

Factories involved in vegetable tanning were also compelled to physically flesh the hide and they historically favored a fleshing knife and a beam.  The fleshing knife is simply a rather dull, flat strip of metal with two handles.  The beam was usually a short log angled from the workers waist, to the floor.  This provided a work surface that allowed the wet and heavy hide to be moved around easily, and provided a mechanical advantage by allowing the tanner to lean into the work with his weight.

polex3c

Once properly fleshed, either a de-haired hide or a fur with all its hair intact will undergo essentially the same processes afterwards.  While tannin will stain things brown it may be desirable for de-haired hides but an alum solution might be chosen for hairy furs.  Small animal furs might need to soak in a tanning liquor for just a few days whereas large hides might need to soak for weeks.   The judgment call of whether a hide has set in a particular tanning liquor long enough or not, is made by cutting through a small piece of hide and examining it in cross section.  If the sample cross section is the same consistent color throughout then this part of the procedure is finished.  The hide is now tanned from a chemical perspective but much physical labor remains.  Any pinkish-ness or fluctuation in color from the edge to the center is an indication to soak the skin some more.

At this point, should the treated wet hide or fur be simply tossed out upon the ground to dry, it would shrink, curl and stiffen into a very unusable product.  To get the strong but flexible leather we are familiar with that hide needs to be washed, rinsed, twisted or rung out like a towel and then thoroughly tortured as it dries.  A half dried skin can be laid over a tree stump and using a soft mallet, pounded over every square inch of its surface with short glancing blows .  At some point before all the moisture is gone, the leather is oiled.  It is this tedious but important, continual stretching, pounding and working of the skin as it dries, that produces flexible leather.

   Un-tanned rawhide can be preserved by drying it out.  If it is not to be tasked with some immediate purpose like being stretched over a hollowed out log to make a drum, then it can be saved for proper tanning at a later date.  Some rawhide might exist in a transition state, being only partially tanned.  Stretching a hide on a frame, or tacking one to a barn wall are popular methods of drying skins out.  Residual bits of fat or flesh can be scraped at leisure, either the suede or epidermis side can be attended to and once it’s flat & stiff the dried rawhide can be stored inside.

The novice or independent furrier has many options to improve his fur.   Furs can be washed in dish-washing detergent to remove oils and odor.  Vinegar and salt solution can be used to “pickle” the skin which helps “set” or lock in the hair.  The pickling solution is usually neutralized with baking soda before the fur hits the alum bath.  Once dry after the tanning bath, a fur might be rinsed in gasoline or naphtha (white gas used in camp stoves and lanterns) to remove any lingering oils or odor.  [Dry cleaners predominately used naphtha or another flammable petroleum fraction before 1911].  The flesh side of the fur might be sanded with sandpaper to remove high spots, making the suede uniform and level.  When finishing a fur it might be brightened by tumbling it in cornmeal, bran or sawdust which is then combed or brushed away.

Individual tanners working with a hairless hide might consider smoking it over a fire.  Some American Indian tribes once made the majority of their clothing from smoked deer hides.  After being fleshed, de-haired, cured in a bath of boiled tree bark tannin, worked to pliability and bathed in fat or brain oils, a deer hide was commonly draped over fire.  Being supported by a little tent like frame of green tree boughs the hide was rotated occasionally, collecting preservative chemicals and additional color along the way.

Once again, there are many sources and even videos of this topic available in the library or on the Internet.  Some of these sources have excellent information others do not.  The reader should be aware of several alternative vegetable tanning methods or recipes before religiously adhering to just one.

Other leather

   There are some schools that teach tanning and/or taxidermy and colleges or universities that offer chrome and aldehyde tanning curriculum.  There are products that disguise the origin of leather and some new organic products for vegans that imitate leather.  Often commercial leather is split, yielding at the least two different products; a “top grain” and one or more layers referred to as “split hide”.

Patent leather has a shiny, glossy finish and gets its name from a finishing and polishing process that was patented some two hundred years ago.  A satisfactory substitution or duplication of that process can be created by painting leather with layers of pigmented linseed oil (similar to oil painting on a sheet of canvas) and then with layers of varnish or lacquer.  Modern patent leathers (not vinyl or poromeric imitation leathers) usually have plastic coatings.

An “aniline dyed” leather refers to a very high quality ‘top grain’ leather that has been dyed clear through with a soluble dye.  A hide’s entire natural surface with pores and imperfections is visible with aniline dyed leather. No sealer, paint or insoluble dyes were used.  Should imperfections like scratches, blemishes or scars be sanded or disguised then the improved leather is referred to as “semi-aniline” dyed.  Most leather car upholstery is “pigmented” leather, meaning“semi-aniline” dyed leather with a heavy durable, protective, pigmented polymer surface coating.   Aniline is also a precursor used in the manufacture of polyurethane.

The Chinese were known to have boiled leather to make armor.  Probably many cultures over the centuries used leather armor but few if any examples exist in the historical record because they would simply biodegrade.   There might have been a lot of boiled leather armor back in medieval times but no one knows for sure now.  Boiling leather makes it shrink, thicken and harden.  Boiled in water or perhaps oil or tallow, the leather becomes mold-able for a short time and will freeze or set into shape as it dries. Overcooking makes it brittle and likely to shatter.  This site discusses making leather armor.

Authentic cheetah, giraffe, tiger and zebra hides are rare now but they were once fairly common.  Some leather producing outfits have taken to printing the hair of cow hides with ink, in patterns resembling these animals.   Even the hides of Holstein cows might be suspect.

As long as people continue to eat meat, there will be a continual supply of animal skins.  The rate of human population expansion is unsustainable and as a species we are soon to eat ourselves off this planet.  Nonetheless some vegans and or members of PETA (People for the Ethical Treatment of Animals) would have us believe that many animals are raised and slaughtered solely for the leather.  Aiming squarely for this demographic, companies like MuSkin, Myx and Mycoworks are actually growing, convincing leather substitutes by using mushrooms.   A substrate, matrix or mat of linen or hemp fibers actually gives this artificial leather its integrity and strength.  In essence either the chitin from the cap or the mushroom mycelium itself fills the spaces between mat fibers.   Apparently incubation and manipulation of fungus while growing can be controlled to a point where zippers can be incorporated without sewing.   Apparently members from the gilled Pleurotus genus and the non gilled Phellinus genus of woody mushrooms are producing the best mushroom leather  <images> or <other images>  results.

MISC informative LINKS

Some chemicals used in leather processing

Phenol

Hemlock history in New York

Buffalo destruction / global market

Ethnobotany of tannins

Leather furniture facts

World Statistical Compendium for raw hides and skins, leather and leather footwear 1993-2012   <PDF>

 

 

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5 thoughts on “Considering Leather

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