Angina

How to make sulfur liver. Artificial patina

The oxidation of iron is called rust. Oxidation of other metals - patina. They are fighting with the first one. They are chasing the second one.
They are persecuted not to drive them out, but on the contrary, to keep them. Coin collectors, for example, say that “the patina on coins is a lifetime experience of banknotes.” The plaque testifies to the antiquity of the exhibit and the careful treatment of it by the previous owners.

However, in addition to the natural patina formed during the interaction of metal with the atmosphere and environment, there is also an artificial one. The main purpose of man-made film is decorative.

It is created using various acids and oxidizing agents. They are included in special mixtures.
On some metals the film is green, on others red, on others black. The tone of the plaque also depends on the conditions in which the item was stored and used.

Bronze statues standing on city streets have a greenish patina. But, there are metal figures with a touch of other colors.

But the madness of the blasphemer
Apparently he already owns me.
Unable to restrain myself,
I say shamelessly:

Monument, why do you need such big ears?
- TO HEAR BETTER!
- Monument, why do you need such big hands?
- TO HUG YOU!
- Monument, why do you need such big teeth?
(doesn't answer...)

Mikhail Shcherbakov “I Erected a Monument”

In the practice of a technical homemaker, the need for patination often arises during the decorative etching of pieces of copper and its alloys; these two techniques are practically inseparable. Indeed, having obtained a certain relief image using chemical etching, for greater contrast, you should fill the recessed areas of the piece of iron with dark. This allows you to see the drawing from any angle and under any reasonable level of lighting. In addition, the finished piece of iron, after patination, takes on a spectacular “antique” appearance. Considering the simplicity of the process, it is simply unreasonable to neglect this decoration technique.

Compared to filling cavities with paint, artificial patina has a number of advantages - less toxic fumes and, in most cases, greater film strength.

The process is really simple, you just need to stock up on the necessary simple reagents.

The patination itself looks something like this: a layer of protective varnish is washed off from the etched piece of metal with a solvent (acetone). The entire piece of iron is patinated and covered with a dark layer. After drying, it is carefully sanded with “zero” sandpaper, while the patina layer on the surface of the workpiece is sanded off, and the patina in the recesses remains intact. The drawing “appears” in all its glory. Afterwards, it is advisable to polish the surface with a piece of felt with GOI paste and cover it with nitro or acrylic varnish. And you can admire it, squinting with pleasure.

This can be a scale of an instrument or device, a dial, a tag, a nameplate, a decorative panel or an overlay on the case. All this makes our finished device unique, and I daresay, beautiful or at least cute.

What was used in the work.
Tools.
Actually, some kind of measuring container, a container that you don’t mind throwing away, a larger one, for sintering sulfur liver, for a small amount, a tin jar is good, a portable gas burner for the same sintering. Container for the patination itself. To “patina” with coffee solution you will need a gas burner for soldering.

Materials.
Access to water (dissolving, washing), necessary chemicals, solvent, rags, GOI paste, cloth or piece of felt. Nitrolac.

Well, let's move on to recipes patination solutions.

A hypertensive person is secret from the doctor
I brewed very, very strong coffee at night
He ran around the hospital laughing,
Waking up the sick - this is a real source of pleasure.

Mango-mango “Source of Delight”.

A method learned from steampunkers - blackening saturated solution of instant coffee. Strictly speaking, the method is not entirely chemical - no reaction occurs, but a layer of dark soot-like substance is formed, which is tightly baked into the pits and recesses of the workpiece.

So, more details. A saturated solution of instant coffee is prepared in warm water. Bring to syrup consistency. Then, the etched blank of our piece of iron is smeared with this paste, from the drawing side, of course.

You can use a brush, you can just use your finger, using small circular movements, rubbing the coffee paste into all the indentations. Afterwards, without drying, we burn the workpiece in the flame of a gas burner.

Here, it is important to more or less accurately maintain the temperature. It should be such that the workpiece almost begins to glow. That's it. At the same time, the coffee paste on the surface turns into ash and soot, but in the recesses it still does not have time. If you don’t heat it up enough, the coffee won’t burn even on the surface and looks like a sticky, difficult-to-clean filth.

After the workpiece has cooled, the surface is ground with a zero grade, polished, and varnished.
The best way to heat it is with a gas burner; I tried placing the workpiece on burning coals - the heating was too fast and difficult to control. An extra moment and everything would burn.

Yes, sometimes the blackening in the recesses, for some reason, turned out not black, but gray. After coating with nitro varnish, the filling darkens and becomes coal black.

The method of “patination” is wonderfully good - the blackening comes out very dense and contrasting, the reagents are simple and accessible, the “patina” is not afraid of nitro varnish - you can rustle it with a brush without any special ceremony. However, in some cases, a method that requires high heating of the workpiece is not applicable - for example, a large and/or thin workpiece (possible warping) or inseparable melting or burning parts. In this case, we turn to traditional, chemical patination. Yes, chemical patination, in addition, looks more “authentic”, more similar to the natural patina so valued by antique lovers.

I'll bring you several recipes for solutions for artificial patina from available components.

- Sulfur ointment

Colours: From light brown to black.

Sulfur ointment is applied in a small amount to the workpiece and rubbed in a circular motion until the desired patina color is achieved. In the open air, the patination process occurs quite quickly and some copper alloys instantly acquire a black tint. This patina is unstable and can be easily rubbed off with your fingers. It is recommended to apply the ointment to the workpiece completely immersed in water, after lubricating it with Vaseline or vegetable oil. Then the patina lays down more evenly and less intensely.

If during the patination process the workpiece or its area becomes excessively black, it can be washed off. soap under running warm water.

A golden-brown patina with a slight crimson tarnish and moderate shine is obtained using a solution of the following composition, g/l:

Copper sulfate СuSO4 5Н2О_________________________________20
Potassium permanganate KMnO4__________________________________________5

A solution at room temperature is applied with a brush to the prepared surface of the product, after a day it is washed with hot water, dried and the operation is repeated 3-4 times. Upon completion of the film formation, the surface is polished with a dry cloth. The same result can be obtained by keeping the product in a solution of the given composition for 4-5 minutes (subsequent processing is the same). When immersed in this solution, heated to 95-99°C, a uniform dark brown film forms on the surface of copper and copper alloys.

To obtain a patina from light to dark brown, use a solution of the following composition, g/l:

Potassium permanganate KMnO4___________________________20
Sulfuric acid (density 1.84 g/cm3)___________________7

A solution at room temperature is applied to the surface of the exhibit; after drying, the surface is washed with hot water and dried. The treatment can be repeated 2-3 times to obtain a uniform and dense layer of patina. The film must be compacted by polishing with a dry rag or bristle brush.

A beautiful olive-brown patina can be achieved using copper oxychloride solution(HOM). . This substance is used as a fertilizer and is sold in the appropriate departments of stores under the abbreviated name HOM. A popular and widely used fertilizer.

For ~600 ml of water, two heaped tablespoons of oxychloride. After dissolution, pour in 100 ml of ammonia, pharmaceutical grade. For a more uniform result, it is recommended to stir the solution, or hang the product on a wire and dangle it in the solution. If the product was overexposed in the solution and it became completely black, then it can be returned to its original state with a solution of Trilon B. Just keep in mind that Trilon corrodes zinc faster than copper, so the surface will become a little more porous and susceptible to further coating.

For patination of copper you can use sodium thiosulfate in ampoules, which are available for sale in almost all pharmacies.

And finally, a classic of the genre - "liver of sulfur". A simple, fast and convenient reagent for applying a durable, beautiful patina. It stores well in dry form, the components for production are easily accessible and not expensive. The only negative is that it should be cooked (liver from the word “oven”) in the open air.

To prepare sulfur liver, you need to mix one part of powdered sulfur with two parts of potash in a tin can and put on fire. After a few minutes, the powder will melt, darken and begin to sinter, gradually acquiring a dark brown color. During sintering, sulfur vapor may ignite with a weak blue-green flame. Do not knock down the flame, it will not deteriorate the quality of the sulfur liver. After about 15 minutes, stop sintering.

For long-term storage, crush the sulfur liver into powder and place it in a glass jar with a tight lid. When making a solution in one liter of water, add 10–20 g of liver sulfur powder. The patina obtained on metal in a solution of sulfur liver is durable and beautiful.

Sulfur is easy to obtain at hardware stores, garden stores, and similar stores. It is presented as an additive to animal feed. In addition, you can ask at pharmacies that have a medicine preparation department.

Potash - potassium carbonate (K2CO3), is not so easy to obtain now, but there is a completely acceptable substitute. Soda ash (Na2CO3). Great fit - also an alkali metal, the same acid residue and the same amount. You don't have to count anything. Sold in hardware stores, next to washing powders.

Homeopathy Classic Encyclopedia of Home Medicine by J. Laurie

SULFUR LIVER (GEPAR SULFUR)

Related drugs . Spongia, Dulcamara, Sulfur.

Specific action. On the mucous membrane of the respiratory tract; on the skin and glandular apparatus; for absorption and excretion; to the salivary glands.

Application. Persistent and inflammatory skin diseases, especially on the head and face; mercury abuse disorders; persistent ulcers, boils and abscesses, inflammatory lesions of the respiratory tract; bronchitis; gum disease from mercury; croup; inflammatory and chronic cough; inflammation and drainage from the ears; inflammation of the glands, predisposition to suppuration; inflammation of the tonsils; toad; erysipelas; pustules on the connective membrane of the eyes; ulcers on the cornea; diphtheria.

Symptoms

External surface. Inflammation of the skin with redness, heat, swelling and tenderness; pimples between the roots of the hair, very sensitive and painful; unhealthy skin with a predisposition to ulceration; enlarged glands with inflammation or suppuration, ulcerative or rash diseases of the skin with foul-smelling discharge; severe itching, itching and fever; skin cracking; nodular swelling of the joints, very painful and sensitive, sweat easily caused; dry heat throughout the body; hot flashes, accompanied or replaced by sweat, burning redness of the face, or inflammation, or erysipelas; hives; hard breast swelling; foul-smelling sweat under the arms; heat, redness, and swelling of the ankles; weeping scabs on the head; scabs behind the ears; red hot swelling of the joints; sticky, sour sweat, especially at night and in the morning; the hair comes out and the head remains completely bald; redness and swelling of the nose; lips are swollen or ulcerated; pimples on forehead; swelling of ankles, feet and knees; cracking of the skin of the legs; yellowish complexion, blue circles under the eyes.

Breath. Weakness in the chest; partial or complete loss of voice; whistling, rapid, hoarse, anxious breathing; shortness of breath, cough and profuse sputum; severe suffocating cough ending in gagging; deep, suppressed cough with difficulty breathing; persistent hoarseness; rough voice; habitual fever at night; soreness of the upper respiratory tract; deep sharp sighs after coughing; constricted breathing, with the head thrown back to facilitate air access; cough appears immediately after swallowing liquid; dry cough with convulsive gagging and vomiting; or wet cough with rattling of mucus in the chest and suffocation when lying down.

Stomach, intestines and feces. Indigestion; heaviness, bloating of the stomach even after the lightest food; belching with stomach contents and heartburn; strong thirst; changeable appetite, sometimes gluttonous; greenish, bilious or sour vomiting with mucus; urge to go down with veining; loose, dry, or lumpy stools; or very thin, bloody, clayey and sticky, or whitish with a sour odor; very hot and dark urine, mostly at night; or copious cloudy and whitish urine with sediment of the same color.

Pain. Drawing, tearing, stitching in joints and limbs, especially when touched; tickling in the throat, as if there was a fish bone stuck there; piercing digging or boring headache and forehead, as if it were crushed or opened; pain in the eyes, as if they were being pressed into the brain; tugging, gnawing pain in the teeth; tearing, jerking pain in the bones of the face, jaws, ears and temples; stitching or cutting in the liver and spleen; pain or constriction in the intestines; aching legs; shooting or pain in the lower back, as if bruised, or shooting, cutting, stabbing in the chest; pain when moving the eyes.

Eyes and ears. Chronic inflammation of the eyes, eyelids and ears; eyes red, hot, inflamed; offensive drainage from the ears; itching in the ears; ears are red and swollen on the outside; overnight glueing of eyelids; protrusion of the eyes or convulsive closing of them; lacrimation at night or towards night and sensitivity to light during the day.

Nose, mouth, throat and gums. Drainage from one nostril; nosebleeds, predominantly in the morning, with dullness or exacerbation of the sense of smell; profuse drooling; whitish, curdled ulcers in the mouth; swelling, heat and redness of the tonsils; Gums are hot, swollen and painful.

From the book Cleansing the body and proper nutrition author Gennady Petrovich Malakhov

Liver After cleansing the large intestine according to Walker, you need to start cleaning the liver. Personally, I consider these 2 cleanings to be mandatory and most important. Further cleansing and restoration will occur on their own with proper nutrition. All venous blood from the intestines, for

From the book Anesthesiology and Resuscitation: Lecture Notes author Marina Aleksandrovna Kolesnikova

7. Poisoning with concentrated acids (nitric, acetic, sulfuric) Clinic When inhaling vapors, irritation of the eyes and upper respiratory tract occurs (lacrimation, runny nose, cough, difficulty breathing). Reflexive cessation of breathing is possible. After the hidden period

From the book Children's Diseases. Complete guide author Author unknown

LIVER The liver of a newborn is the largest organ, occupying 1/3 of the volume of the abdominal cavity. At 11 months its mass doubles, by 2–3 years it triples, by 8 years it increases 5 times, by 16–17 years the weight of the liver increases 10 times. The liver performs the following

From the book Disease as a Path. The meaning and purpose of diseases by Rudiger Dahlke

Liver Talking about the liver is quite difficult due to the huge number of its functions. This is one of the largest human organs, the basis for intermediate metabolism or, figuratively speaking, the laboratory of the human body. Let me tell you briefly about the most

From the book Practical Homeopathy author Victor Iosifovich Varshavsky

ACIDUM SULFURICUM, ACIDUM SULFURICUM - SULFURIC ACID Specific action. On the central nervous system, mucous membranes (mainly the gastrointestinal tract), hematopoietic system. Main symptoms. Severe intoxication with adynamia. Functional

From the book Homeopathy Classic Encyclopedia of Home Medicine by J Laurie

HEPAR SULFUR. HEPAR SULFURIS - SULFUR LIVER Specific action. On mucous membranes, lymph nodes, skin and subcutaneous tissue. Has no natural analogue. Obtained by calcining finely crushed oyster shells with a sulfur color. Symptoms. Inflammation with

From the book Homeopathy for General Practitioners author A. A. Krylov

SULFUR, SULFUR - SULFUR COLOR Specific action. Affects the processes that cause autointoxication, the development of allergic reactions, chronicity of pathological conditions. It has an effect on all organs and systems, mainly on the digestive organs, skin,

From the book Paramedic's Handbook author Galina Yurievna Lazareva

SULFUR (SULFUR) Related drugs. Nerag, Ledum. Specific action. On the skin and mucous membrane, especially the eyes, bronchi and rectum; also given to eliminate predisposition to diseases, hereditary or acquired, and to induce susceptibility to

From the book Exercises for internal organs for various diseases author Oleg Igorevich Astashenko

SULFURIC ACID (ACIDUM SULFURICUM) Related drugs. Acidum nitricum, Acidum muriaticum, Gelseminum, Sanguinaria, Baptisia, Cimicifuga. Specific action. On the mucous membrane, skin and blood. Application. Nausea in the morning; nervous fever; chills; insomnia; indigestion; chronic diarrhea;

From the book Alcoholism author Alexander Vitalievich Melnikov

Hepar sulfuris Sulfur liver A distinctive feature is a tendency to inflammatory and suppurative processes in the skin, subcutaneous tissue, mucous membranes, in any organs and tissues. The type of sulfur liver is irritable, anxious, with a constantly depressed mood, but has

From the book How not to turn into Baba Yaga by Doctor Nonna

Sulfur Sulfur It is difficult to determine the constitutional type of sulfur: it can be either full blooming hypersthenics or pronounced asthenics. The most characteristic constitutional sign is skin manifestations with severe burning and itching, relieved by coolness.

From the book The Secret Wisdom of the Human Body author Alexander Solomonovich Zalmanov

Sulfur plug It occurs as a result of increased function of the glands located in the membranous-cartilaginous part of the external auditory canal. Sulfur plug is a conglomerate of dried secretion from the skin of the ear canal. Under normal conditions, sulfur, when dried, is removed from

From the author's book

Liver Therapeutic movements for liver diseases In various liver diseases (cholelithiasis, chronic forms of cholecystitis and biliary dyskinesias), one of the main problems is insufficient emptying of the gallbladder. Stagnation of bile in

From the author's book

Liver Who hasn't heard that alcohol abuse leads to liver damage? A terrible diagnosis immediately comes to mind - cirrhosis. This is partly fair. Indeed, alcoholism is considered one of the main causes of liver cirrhosis. However, cirrhosis develops only in

From the author's book

The liver is, without exaggeration, a unique organ. The liver not only removes toxins and other harmful substances (generally called xenobiotics), but rather converts them into harmless, or less toxic, or easier to remove compounds from the body. She's in charge

From the author's book

Liver The liver produces from 1 to 1.5 liters of bile in 24 hours; one part of it goes to the intestines, the other to the gall bladder, which serves as a warehouse, a reservoir. Bile converts the fats contained in food into a substance that is then broken down into more complex forms in the small intestine.

Patination and oxidation of metals

OXIDATION OF THE SURFACE OF METAL ELEMENTS
AGING OF COPPER, SILVER, BRONZE OR BRASS WITH AN AQUEOUS SOLUTION
LIVER SULFUR

Sulfur liver (Liver of sulfur / Liver of sulfur) - potassium polysulfide or sodium polysulfide.

Copper and silver are well patinated with an aqueous solution of liver sulfur, gradually acquiring a thick black color, while bronze and brass have faint shades.

Sintering of the patinated composition over a fire gave it the name “liver” in the old days - from the word “furnace”, “to sinter”.

Patina- film (plaque).
Patina comes in two types: natural and artificial.

Natural patinaA- this is a thin, but quite dense and durable oxide film that forms on the surface of decorative elements under natural conditions (under the influence of the environment).

Natural patina is often considered noble and, as a rule, they try to protect it.

Artificial patina- a coating formed on the surface of decorative elements after applying various mastics, solutions and other compositions intended for this purpose to their surface.

Oxidation- creation of an oxide film on the surface of a decorative element as a result of an oxidation-reduction reaction. Oxidation is used, among other things, to obtain a beautiful decorative coating.

To oxidize copper, silver, bronze or brass you will need:
- the object itself, the surface of which will be treated with a solution of sulfur liver (here, for example, a copper-plated sheet);
- a pinch of liver sulfur;
- glass or plastic container;
- brush.

Dissolve the powder in water.
The presence of sediment at the bottom is quite acceptable and does not affect the result of oxidation.

Apply the compound to the copper piece with a brush.

Do not allow the blackening compound to come into contact with the surface of natural stones and pearls.
This can lead to changes in the structure of the stone.

In no more than a minute, copper and silver are covered with a brownish-violet oxide film.
When the composition is reapplied, the copper surface darkens, even black.

Let's take a break from the process :)
This is how the oxide film turns out if the liver sulfur solution was too weak:

Let's continue... :)
Sand the part in places where the artistic intent requires it.

The scroll on the right is oxidized with sulfur liver and sanded with a Dremel.

Features of storage of the composition:

Composition in granules
Storage conditions: dry and protected from direct sunlight
in a tightly closed container at a temperature not exceeding 25 degrees. WITH.
Shelf life and use: more than 1 year.

Ready aqueous solution
Storage conditions: in a tightly closed container in a cool place (for example, in the refrigerator).
Shelf life and use: no more than 1-2 days.

Natural method

1. Boil 2-4 eggs in boiling water for 15 minutes.

2. Remove the boiled eggs from the water and place on a cutting board. Using a spoon, mash the eggs and shells together.

3. Place the crushed eggs in a plastic zip-top bag. The bag must be large enough to contain the product. Alternatively, use a large, airtight container.

4. Place the copper item in a plastic bag and seal it. If you place more than one item in a bag, make sure they are not touching each other so that they oxidize on all sides. Egg yolks are a must because they contain large amounts of sulfur, which oxidizes copper.

5. 20 minutes later, remove the copper item from the bag using metal tongs. You will notice that the surface of the copper has darkened. If you want a darker patina, leave the piece in the bag overnight.

6. Remove the item from the bag and rinse with slightly warm water to remove the egg.

PATINATION and OXIDATION of copper

To change the color of a reddish metal, they most often use PATINATED liver sulfur and ammonium sulphide or BY OXIDATION nitric acid.

PATINATION sulfur liver

The composition of sulfur liver includes potash and sulfur. Sulfur is flammable and therefore requires careful handling. Its vapors with air form explosive mixtures. Sulfur should be stored in a dry place, isolated from oxidizing agents (sulfuric acid, potassium permanganate, berthollet salt). Doses of potash and sulfur may vary. Most often, 1 part sulfur is mixed with 2 parts potash. Poured together, both powdered substances are thoroughly mixed, placed in a metal vessel with a handle and set to heat. It is recommended to stir the contents of the vessel. Fusion of the reagents occurs within 15-25 minutes. The reaction produces a dark mass of liver sulfur. High temperatures cause sulfur to smolder with a blue-green fire. This shouldn't be a cause for concern since patination the properties of sulfur liver will be preserved. The finished hot mass is poured with water, in which the resulting melt dissolves. The water takes on an intense black color.

Pre-treated copper products are dipped into a hot aqueous solution of liver sulfur. If the leaf is large and does not fit into the vessel, it is watered on top with a solution or lubricated with a soft brush.

Copper turns black very quickly. From the interaction of sulfur ions with metal, copper sulfide is formed. This salt is black in color and insoluble in water and dilute acids.

The reaction is faster and PATINATION It will be of better quality if the plate is preheated. In this case, you should not use an open fire, but an electric stove. Then the plate is washed in warm running water and the convex areas are lightly wiped with pumice powder. The color is black in recesses, greyish on inclined surfaces, and shiny red copper on protrusions. An antique imitation is created.

An aqueous solution of liver sulfur can also affect items made of silver or galvanically plated with silver. They are also covered with a black coating.

Oxidation and patination of copper, brass and bronze.

Some chemical reactions lead to the formation of oxides and oxides, i.e., oxygen compounds, on the surface of metals. This process is called oxidation.

Often, chemical elements, interacting with a metal or alloy, contribute to the appearance of sulfur or chloride compounds. The process of forming such compounds is called patination.

If you dip a metal product into the prepared solution, it literally changes color before your eyes. A sparkling metal product takes on the appearance of an antique product in a few seconds.

Most chemical compounds that are used for patination and oxidation of metals are toxic and dangerous to humans. Therefore, they need to be stored in vessels with ground-in stoppers, and all work involving the release of toxic and flammable vapors and gases should be carried out in a fume hood. The cabinet doors should be slightly open.

Before changing the color of the metal, it is necessary to carry out some preparatory operations. The item is cleaned and degreased, washed well and dried in sawdust. Metal art objects and coins should never be wiped with a towel. A towel erases fragile patina films that are not secured with varnish, moisture remains in the deep reliefs, the fabric gets caught on high protrusions and can bend them. Sawdust quickly and evenly draws water away from the metal surface.

Patina from gray to black

Preparation of sulfur liver:
To prepare sulfur liver, you need to mix one part of powdered sulfur with two parts of potash in a tin can and put on fire. After a few minutes, the powder will melt, darken and begin to sinter, gradually acquiring a dark brown color. (By the way, the sintering of the patination mass gave the name “liver” in the old days - from the words “oven”, “sinter”.)
During sintering, sulfur vapor may ignite with a weak blue-green flame. Do not knock down the flame - it will not deteriorate the quality of the sulfur liver. After about 15 minutes, stop sintering. For long-term storage, crush the sulfur liver into powder and place it in a glass jar with a tight lid.

Method No. 1
Applies to:
Copper, sterling silver, and bronze or brass (light shade). Does not work on nickel silver.
Colors:
On copper and silver there is a range of shades from purple/blue (difficult to obtain) to brown-gray, gray, black. On brass and bronze - only soft golden.

A durable and beautiful patina forms on the surface of copper treated in an aqueous solution of liver sulfur.

When making a solution in 1 liter of water, add 10-20 g of liver sulfur powder. The patina obtained on metal with a solution of sulfur liver is durable and beautiful, deep black in color. But such intense coloring is not always necessary. Sometimes, to give an antique look to a copper product, it is enough to apply a light gray patina. Pour 2-3 g of table salt and 2-3 g of sulfur liver into a liter of water. Dip a copper plate into the solution. After the required gray color appears, rinse the plate with clean water and dry.

Method No. 2
To blacken a copper item, prepare a saturated solution of copper sulfate, add ammonia to it until the mixture takes on a bright transparent blue color. The copper item being processed is dipped into this solution for a few minutes, then removed and slightly heated until it turns black.

Method No. 3
The copper item to be blackened is first cleaned with fine sandpaper, after which try not to touch its cleaned surface with your fingers. It is then either immersed in a liquid solution of platinum chloride or moistened with it using a brush. This solution, if it does not have an acidic reaction, is slightly acidified with hydrochloric acid.

Method No. 4
A very durable blackening of copper products is obtained by immersing them in a saturated solution of copper metal in nitric acid and then heating it slightly.

Patina red-brown

An aqueous solution of zinc chloride and copper sulfate colors copper red-brown. Mix one part copper sulfate with one part zinc chloride and dilute in two parts water. A few minutes are enough for the copper to acquire a red-brown color. After washing and drying, wipe the metal surface with oil.

Patina from light brown to black

Blackening of the metal is observed when copper is patinated with ammonium sulfide.
20 g of ammonium sulfide is diluted in a liter of water. The product is dipped into the resulting solution or poured on top and wiped with a brush. The work is carried out in a fume hood. Sulfur ions present in an aqueous solution of ammonium sulfide interact with copper ions. Black copper sulfide is formed.
The intensity of the patina on the metal can be of different shades, from light brown to black. The color is adjusted by changing the heating temperature of the plate before patination.

Patina light brown

Gram per liter:
sodium dichromate - 124
nitric acid (density 1.40 gcm3) - 15.5
hydrochloric acid (1.192) - 4.65
Ammonium sulfide 18% solution - 3-5
Apply with a brush immediately after preparation, rinse off after 4-5 hours and repeat after drying 2 times, polish with a dry cloth.

Dark brown to warm black patina

Gram per liter:
ammonium persulfate - 9.35
caustic soda - 50.0
for 5-25 minutes in a bath with a solution heated to 90 -95 degrees. rinse, dry, repeat 2-3 times

Olive to brown patina

Gram per liter:
Berthollet salt - 50*70
copper nitrate - 40*50
Ammonium chloride - 80*100
for 10-15 minutes in a bath with a heated solution to 60-70 degrees.
the resulting films have mechanical strength and corrosion resistance

Patina brown-black

Gram per liter:
Ammonium molybdate - 10
ammonia 25% aqueous solution - 7
the solution should be heated to 60 - 70 degrees

Golden patina

Gram per liter:
copper sulfide - 0.6
caustic soda - 180
milk sugar - 180

A solution of alkali and lactose is prepared separately and only then poured together, boiled for 15 minutes and copper sulfide added.
place the product in a heated to 90 gr. solution for 15 minutes.

Patina golden brown with crimson tarnish and moderate shine

After cleaning copper coins, you can create an artificial patina on them by placing 50 g of copper sulfate and 5 g of potassium permanganate per 1 liter of water in a solution, heating it to a temperature of 70-80C and holding it there until the desired color is obtained.

Green patina

The surface of copper, brass or bronze products can be painted green in various ways.

Method No. 1
Using a sponge, the surface of things is first lubricated with a highly diluted solution of copper nitrate with the addition of a small amount of table salt. Then, when the item dries, it is lubricated in exactly the same way with a solution of 1 part potassium oxalate and 5 parts ammonia in 94 parts weak vinegar. Let it dry again and again lubricate with the first solution; then, after drying, again with a second solution, etc. alternately until the coloring acquires the proper strength.
Before lubricating, the sponge soaked in the solution should be squeezed out firmly so that it is damp, but not wet. After painting the surface, rub the items thoroughly with hard hair brushes, especially in the recesses and crevices. After 8-14 days of work, a brownish-greenish color is obtained.

Method No. 2
Things are rubbed in several stages with cloth soaked in crude oleic acid (a product obtained in stearin factories). On the surface of things, a dark green layer of copper oleic acid is first formed, which, under the influence of oxygen and air moisture, gradually turns into lighter green copper carbonate.
The process is significantly accelerated if oleic acid is first infused on copper shavings for quite a long time, and after each lubrication with such acid, after the lubricant has dried, the items are lightly sprayed (no more than a few drops!) with an aqueous solution of ammonium carbonate.

Patination is the artificial aging of materials to give them an exquisite decorative and antique look. We would like to offer you a recipe for liver sulfur solution for patination of products.

You will need:

feed sulfur
baking soda
heating container
spoon
dark glass container

Sulfur can be bought at any pet store, it costs about 30 rubles. Use an iron mug for heating and an aluminum spoon for stirring. You will also need a dark glass container for the finished solution (preferably with a large neck, so that some products can be immersed immediately). Prepare in a well-ventilated area with an exhaust hood. Remember that the rate of oxidation of the product depends on the concentration, temperature and time of exposure of the product in the solution. Some stones are sensitive to sulfur liver (malachite, turquoise, etc.), in such cases the solution must be carefully applied with a brush to a heated product. The prepared solution can be stored in the refrigerator for more than a month. Don't forget to sign!

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So, let's start preparing sulfur liver. Pour 1 part sulfur and 1 part baking soda into a cooking container. Mix thoroughly and get rid of lumps. Then heat the mixture over low heat, stirring it with a spoon ( If heated quickly, the sulfur may ignite!). Bring to a bright yellow, slightly brownish color. Add warm water and stir. Carefully pour the solution into a dark glass container.

To reuse the solution, heat it in a water bath. Place the product in the container and wait for the color you want. Then rinse under running water, wipe with a cloth and polish with a metal sponge.

The finished embossed composition can be left in the natural metallic color of the original plaque, but it can also be “aged”, darkened, chemically treated, followed by grinding, polishing, and, if necessary, varnishing.

Before patination, the product can be treated not with acid, but by thoroughly brushing (cleaning) the relief with a metal brush made of steel wire.

Chemical processing of copper

To change the color of this reddish metal, patination with sulfur liver and ammonium sulfide or oxidation with nitric acid is most often used.

Patination with sulfur liver

The composition of sulfur liver includes potash and sulfur. Sulfur is flammable, so it requires careful handling. Its vapors with air form explosive mixtures. Sulfur should be stored in a dry place, isolated from oxidizing agents (sulfuric acid, potassium permanganate, berthollet salt). Doses of potash and sulfur may vary. Most often, 1 part sulfur is mixed with 2 parts potash. Poured together, both powdered substances are thoroughly mixed, placed in a metal vessel with a handle and set to heat. It is recommended to stir the contents of the vessel. Fusion of the reagents occurs within 15-25 minutes. The reaction produces a dark mass of liver sulfur. High temperatures cause sulfur to smolder with a blue-green fire. This should not be a cause for concern, as the patination properties of the liver of sulfur will remain. The finished hot mass is poured with water, in which the resulting melt dissolves. The water takes on an intense black color.

Copper turns black very quickly. From the interaction of sulfur ions with metal, copper sulfide is formed. It is a black salt, insoluble in water and dilute acids.

The reaction goes faster and the patination will be better if the plate is preheated. (You should use an electric stove rather than an open fire.) Then the plate is washed in warm running water and the convex areas are lightly wiped with pumice powder. The color is black in recesses, greyish on inclined surfaces, and shiny red copper on protrusions. An antique imitation is created. Pumice powder can be replaced with powders used for cleaning dishes (Pemoxol, Chistol, etc.). You can also use abrasive powder from an emery wheel. You need to drop a drop of oil (machine, household, vegetable, etc.) onto a cloth, dip it into the powder and wipe the protuberances of the embossing. It is convenient to use a large eraser - wrap it in a cloth and apply oil to a wide surface so that the powder sticks. In this case, when wiping the relief, only the raised areas are highlighted, since the eraser does not touch the background recesses.

An aqueous solution of liver sulfur can affect both silver products and products silver-plated by galvanic means. They are also covered with a black coating.

It is recommended to use liver sulfur solution within 24 hours. Sulfur liver can be prepared for future use and consumed in small doses. The melt of sulfur and potash is poured onto a non-hot surface, cooled, and then broken into pieces and stored in a vessel with a ground stopper. Prepare a liver solution at the rate of 5-20 g of powder per liter of water.

Patination with ammonium sulphide

Blackening of the metal is observed when copper is patinated with ammonium sulfide. 20 g of ammonium sulfide is diluted in a liter of water. The product is dipped into the resulting solution or poured on top and wiped with a brush. The work is carried out in a fume hood. Sulfur ions present in an aqueous solution of ammonium sulfide interact with copper ions. Black copper sulfide is formed.

The intensity of the patina on the metal can be of different shades - from light brown to black. Adjust the color by changing the heating temperature of the plate before patination. If you need to clean the product to the natural color of the metal, do this: dip it in a mixture of nitric and sulfuric (10-15%) acids. Sulfuric acid is added to nitric acid to increase the concentration, since it has the property of attracting moisture. When concentrated sulfuric and nitric acids are mixed, a reaction occurs that releases a large amount of heat, and thick-walled vessels may burst, so you should use only thin-walled chemical containers. When a copper plate is dipped into a mixture of acids, the patina film instantly falls off and the black color disappears. The following precautions should be observed when working with concentrated acids:

a) pour them through a funnel under the draft;

b) when diluting concentrated acids, pour the acid in portions into water and mix lightly.

Nitric and sulfuric acids are particularly dangerous substances. They cause severe burns. It is recommended to store acids in glass containers away from flammable materials. Children are allowed to work with them only under supervision. If safety regulations are followed, working with chemicals does not pose a threat. Injury cases mostly involve violations of these rules.

If drops of concentrated acid do get on exposed areas of the body, you need to quickly wash the burned area with plenty of water (put it under the tap), and then wipe it with a 3% solution of soda or a 5% solution of sodium bicarbonate, or baking soda.

Oxidation of copper with nitric acid

This method is simple and reliable, but requires caution, since the work is carried out with concentrated acid. Using a piece of cotton wool tied to a wooden stick or clamped with tweezers, a layer of concentrated nitric acid is applied to the surface and the plate is heated. As the temperature rises, the color of the surface changes from greenish-blue to black. The metal relief is covered with a uniform blackness. The cooled product is washed under the tap, and then the convex elements of the composition are highlighted for greater expressiveness. To do this, a piece of felt or thick wool is moistened in gasoline, rubbed with GOI paste and pressed several times along the front side of the metal product. Then wipe dry with cloth. It should be remembered that copper salts are poisonous even if the dust is inhaled. Therefore, after work, you need to wash your hands thoroughly.

Patination and oxidation of brass

Brass has a very wide range of shades obtained by chemical processing: yellow, orange, red, blue, violet, indigo, black. Moreover, a variety of colors can be achieved on the surface of one plaque.

In addition to intense, bright, chromatic brass can be patinated in achromatic, light or dark gray and black tones.

Patination with sodium trisulfate and nitric acid

0.5 liters of hot water is poured into an enamel, plastic or nylon bowl and 20-30 g of sodium trisulfate, better known as hyposulfite (fixer for photographic film), is poured into it. If you add a little (about two thimbles) of some acid, such as nitric acid, to this solution, the smell of sulfur dioxide appears and after a while the clear liquid becomes cloudy yellow with a slight green tint from the sulfur released. The duration of the patination solution is very short, only 15 minutes. Brass is dipped into the solution and the surface is observed to darken. A plate preheated in a stream of hot water and dipped into the solution quickly darkens, acquiring grayish-blue or brownish-violet shades, replacing one another.

The patinated plate is removed with tweezers or hands wearing rubber gloves, and, after washing in hot water, the entire plane of the metal is wiped with a brush and sand, as if applying a chemical primer to the background. The plate is then dipped back into the solution to obtain the final color. Observe changes in the color of the plate by slightly tilting the vessel so that metal can be seen from time to time from the opaque solution.

When the desired color is achieved, the product is removed, washed in hot water and, taking pumice powder on wet fingers, very carefully (the film is very fragile) wipe the convex places, exposing clean metal. Pumice easily removes patina from a wet plate. Wash off the pumice powder with water.
After drying in sawdust, the product seems to be dusted with a cloudy coating. To return the metallic shine to the coinage, it is wiped with sewing oil or coated with colorless varnish. You shouldn't get carried away with varnish. It is not applied to add shine to the embossed relief, but only to lightly fix weak patina coatings.

Patination with a mixture of solutions of sodium triosulfate and lead acetate or lead nitrate
This patination method allows you to get all the rainbow shades on the surface of a brass product: yellow, orange, crimson, purple, blue.

Patination proceeds as follows. 130-150 g of sodium trisulfate are dissolved in one liter of hot water. In another vessel, 35-40 g of lead acetate or lead nitrate are dissolved in the same amount of water. Both solutions are poured into one container. The solution is heated to 80-90°C and a bleached, etched in nitric acid and well washed brass plate is lowered into it. On the surface of the metal, shades quickly change: yellow turns into orange, which in turn gives way to red-crimson, then purple. Then the plate gradually turns blue, twitches with a grayish coating, turns black, and the reaction stops. All of the colors listed appear continuously. The lifetime of each of them is short. Therefore, as soon as the desired color appears on the plate, it should be immediately removed, washed and dried.

If the product is removed from the solution, washed, and then dipped into the solution again, then removed again, washed, and dipped again in the patination mixture, you will get interesting rainbow colors with relatively sharp transition lines. If the product is gradually removed from the solution, the colors will gently transition into each other. You need to know these methods in order to achieve the intended effect.

Change in color of brass under the influence of antimony chloride

Not everyone likes bright colors on metal, and they are not always appropriate. Sometimes the metal just needs to be blackened. For this purpose, minting masters quite widely use antimony chloride. It is applied with a brush to the finished plate and rubbed with a brush or stiff brush. Work with rubber gloves. The plate is painted in a black velvety color. Depending on the concentration of the solution and the duration of treatment, colors from light gray to velvety black are obtained. When the desired color is obtained, the plate is washed well and dried. The film should not be sealed with varnish.

Oxidation with nitric acid

Coated with a layer of acid, the brass plate turns bluish-green as it heats up, as copper nitrate is formed. With a further increase in temperature, copper nitrate decomposes. A black coating appears on the coinage. The product is cooled, thoroughly washed and dried. The oxide film is firmly and securely bonded to the metal.

Depending on the design, the creator of the coinage can stop the reaction at any stage. To maintain the desired shade, it is enough to interrupt the heating and quickly and thoroughly rinse and dry the plate.

Highlight the convex areas in the same way as on copper, i.e. rub them with GOI paste, after moistening a piece of felt with gasoline. The safety rules are the same.

An interesting and practically easy to perform method is the long-known method of silvering copper and its alloys (including brass) with a used fixer, but with a subsequent change in the silver color with a solution of sulfur liver. The tinting process in this way is carried out as follows:

the finished brass coinage is clarified in the usual way (in a weak solution of sulfuric acid) and washed in running water;

a paste is made from chalk, ground into powder, and used photographic fixative; add a few drops of ammonia to it;

Using a bristle brush (if the relief is high with deep and narrow areas of the background) or a clean cloth, thoroughly rub the surface of the embossing with the paste; the product acquires a silver color;

under running water, wash off the remaining chalk from the coinage and immerse it in a solution of sulfur liver; the product darkens (with slight color tints), taking on the appearance of old silver;

After washing and drying, the patination operations are completed.