CA2045919A1 - Method for forming artificially and rapidly patina on copper, products thereof and solutions therefor - Google Patents
Method for forming artificially and rapidly patina on copper, products thereof and solutions thereforInfo
- Publication number
- CA2045919A1 CA2045919A1 CA 2045919 CA2045919A CA2045919A1 CA 2045919 A1 CA2045919 A1 CA 2045919A1 CA 2045919 CA2045919 CA 2045919 CA 2045919 A CA2045919 A CA 2045919A CA 2045919 A1 CA2045919 A1 CA 2045919A1
- Authority
- CA
- Canada
- Prior art keywords
- copper
- grams
- ions
- substrate
- acetate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
- C23C22/52—Treatment of copper or alloys based thereon
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- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Treatment Of Metals (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
A method for artificially forming patina on copper comprising: a) removing any impurity present on the surface of copper substrate; b) polishing the copper substrate with an aqueous solution containing sodium ions, copper ions, acetate ions, chlorine ions, sulphate ions, H+ ions and an OH- ions until a brown colour is obtained; c) washing the polished copper substrate having brown colour of step (b), with water and drying; d) gently brushing the copper substrate having been dried according to step (c), washing and thoroughly drying; e) submitting the copper substrate after having been thoroughly dried according to step (d), to a filtered aqueous solution containing copper carbonate, ammonium chloride, copper acetate, arsenic trioxide, copper nitrate and hydrochloric acid until the desired patinated copper substrate is obtained. The invention covers also the products resulting from the method, as well as specific solutions to carry steps (b) and (e).
A method for artificially forming patina on copper comprising: a) removing any impurity present on the surface of copper substrate; b) polishing the copper substrate with an aqueous solution containing sodium ions, copper ions, acetate ions, chlorine ions, sulphate ions, H+ ions and an OH- ions until a brown colour is obtained; c) washing the polished copper substrate having brown colour of step (b), with water and drying; d) gently brushing the copper substrate having been dried according to step (c), washing and thoroughly drying; e) submitting the copper substrate after having been thoroughly dried according to step (d), to a filtered aqueous solution containing copper carbonate, ammonium chloride, copper acetate, arsenic trioxide, copper nitrate and hydrochloric acid until the desired patinated copper substrate is obtained. The invention covers also the products resulting from the method, as well as specific solutions to carry steps (b) and (e).
Description
" 2~5~19 ~
TITLE OF THE INVENTION
~ethod for forminy artificially and rapidly patina on copper, produc-ts thereof and solutions therefor.
BACKGROUND OF Tl-IE INVENTION
Field of the invention This invention relates to a method for artificially and rapidly forming patina on copper substrates, to products therefrom, in particular to such copper subs-trates as roofing and outside covering, and to new solutions for rapidly forming patina on copper solution.
Description of related art Attempts have been made in order to obtain coloring of copper similar to patina on copper.
For instance in US patent no. 1,951,304, dated March 13, 1~34, as invented by FREEMAN et al., is disclosed a method producing on the surface of copper and alloys thereof, an adherent green coloration patina by treating the copper or copper alloy with a solution of ammonium sulphate and therea~ter exposing to oxygen. In some cases a color is developed which is darker green than that which de~elops by natural weathering.
In US patent no. 2,587,216, dated February 26, 1952, as invented by QUADRIO, is disclosed a method involving the following steps: dipping an objec-t in a bath containing a solution oE potassium sulfide, then a second bath o~
sulphuric acid, drying, then dipping in a third bath "
TITLE OF THE INVENTION
~ethod for forminy artificially and rapidly patina on copper, produc-ts thereof and solutions therefor.
BACKGROUND OF Tl-IE INVENTION
Field of the invention This invention relates to a method for artificially and rapidly forming patina on copper substrates, to products therefrom, in particular to such copper subs-trates as roofing and outside covering, and to new solutions for rapidly forming patina on copper solution.
Description of related art Attempts have been made in order to obtain coloring of copper similar to patina on copper.
For instance in US patent no. 1,951,304, dated March 13, 1~34, as invented by FREEMAN et al., is disclosed a method producing on the surface of copper and alloys thereof, an adherent green coloration patina by treating the copper or copper alloy with a solution of ammonium sulphate and therea~ter exposing to oxygen. In some cases a color is developed which is darker green than that which de~elops by natural weathering.
In US patent no. 2,587,216, dated February 26, 1952, as invented by QUADRIO, is disclosed a method involving the following steps: dipping an objec-t in a bath containing a solution oE potassium sulfide, then a second bath o~
sulphuric acid, drying, then dipping in a third bath "
2 ~ g containing salt ammoniac, and -then coating with shellac and a protective coating.
In US patent no. 3,152,927, dated October 13, 1964, as inven-ted by MATTSON et al., is disclosed an agent for the arti.ficial green patination oE object comprising an aqueous sludge obtained by admixing an aqueous solution containing copper nitrate, iron sulphate and sodium hydroxide.
In US patent no. 3,434,890, dated March 25, 1969, as invented by ARONBERG, is disclosed a process for forming patina involving wetting a copper base alloy with a solution volatile water soluble organic solvent such as alcohol and salts of inorganic acids and primary amines.
In US patent no. 3,473,970, dated October 21, 1969, as invented by ROBEY, is disclosed a composition ~or imparting patina comprising copper sulphate, ammonium sulphate lithium chloride, sodium dicromate, hydrochloric acid, magnesium montmorillonite and water.
In US patent no. 3,497,~01, dated February 24, 1970, as invented by HANSON et al~, is disclosed a me-thod for producing synthetic patina by immersion in an aqueous acidic solution with potassium chlorate and copper sulphate.
In US patent no. 3,725,138, dated April 3, 1973, as invented by JONES, is disclosed a patina produced on a copper surface by applying an aqueous acidic solution of ammonium sulphate, sulphamic acid and iron sulphate, drying the solution to form a film on the copper surface. The film is then reacted with the copper surface in a humid atmosphere at a tempera-ture oE a-t least 30C for a period of -time to form an adhered corrosion product of which a major portion is 2~59~
insolubilized. The soluble par-ts are then dissolved, thereby developing in the reaction produc-t the color of natural pa-tina.
In US patent no. 4,416,940, dated November 22, 1983, as invented by LOYE et al., is disclosed a two step process comprising first applying an opaque pigmented base coat containing a patina color producing colorant to a primed or unprimed substrate, curing the base coat, applying to the cure base coat a non-opaque top coat containing one or rnore copper color producing additives.
SUMMARY OF THE INVENTION
Broadly stated, the invention is directed to a rapid me-thod for artificially forming patina on copper comprising:
a) removing any impurity present on the surface of a copper substrate, b) coating said copper substrate with an aqueous solution containing sodium ions, cupper ions, acetate ions, chlorine ions, sulphate ions, H~ ions and an OH- ions;
c) washing the copper substrate coated as in step (b) with water and drying;
d) gently brushing the copper substrate having been dried according to step (c), washing and drying;
e) coating said copper substrate after having been dried according to step (d), with a aqueous solution containing copper carbonate, ammonium chloride, copper acetate, arsenic trioxide, copper nitrate and hydrochloric acid.
The invention is also direc-ted -to new products obtained by -the method as deEined above and to produc-ts for forming patina on copper.
7, ~
DESCRIPTION OF A PREFERRED EMBODIMENT
The first step of the method involves cleaning of the surface i.n order to remove any impurity present on the surface of the copper substrate such as varnish, grease, copper oxide, e-tc. This cleaning is easily conduc-ted by brushing. In a preferred embodimen-t, cold brushing is conducted with nylon brushes having abrasive particles embedded in cured binders such as cured phenolformaldehyde resins, polyurethane resins and epoxy resins, These brushes may for instance be mechanically mounted on a driven roller bearing in mind tha-t the copper metal must touch sideways in order to obtain good patina Eixation and polishing could also be conducted if desired. Scoth Brite R brown pads may be used.
After removing any impurity present on the surface of the copper substrate, it should be borne in mind that the substra-te must be manipulated with dirt free and grease free intermediates and never with hands; one may use metallic instruments or cotton gloves for instance.
After removal of -the impurities, it is important to polish as quickly as possible the copper substrate with an aqueous solution containing sodium ions, copper ions~ acetate ions, chloride ions, sulphate ions, hydrogen ions and hydroxy ions. This aqueous solu-tion is preferably obtained by mixing from 100 to 150 ml of concentrated acetic acid, 500 to 600 grams of copper sulphate, 80 to 120 grams of sodium chloride, 11 -to 13 grams oE hydroxide and 11 to 15 grams of copper acetate in 4 liters of distilled water. More preferably, the solu-tion contains 4 liters of distilled water, 135 ml of concentra-ted acetic acid, 563 grams of copper sulphate, 100 grarns of sodium chloride, 12 grams of sodium hydroxide and 12 grams of copper aceta-te. The solution is applied in large quantity whether by jet, hand, mechanically or manually brushed until a brownish color is obtained. Thereafter, any excess of reactant is removed with thorough water washing. Drying is then conducted under air pressure over all coated surfaces and -then the copper substrate is cured for at least 12 hours, preferably in a room having a light used for growing plants such as Gro-Lux R Sylvania, simulating the solar light. Preferably, the sides of the room are reflecting light with surfaces such as mirror polished aluminum and the like. The room temperature is about 20 à 35C and preferably 25C with a relative humidity oE between 35 to 80% and preferably 50%.
After the drying step, the copper substrate is thoroughly washed and lightly brushed, whether manually or mechanically, in order to remove brownish color which is not sufficiently adhering to the substrate. The substrate is then pressure air dried. Thereafter, the copper substrate is submitted to a filtered aqueous solution containing copper carbonate, ammonium chloride, copper acetate, arsenic trioxide, copper nitrate and hydrochloric acid until the desired patinated copper substrate is obtained. This last step may be repeated if desired. This solution may be applied with a brush or a gun as desired.
Preferably, this lost solution is obtained by mixing in 6 liters of distilled water, from 300 to 360 ml of concentrated hydrochloric acid, 100 to 160 grams of copper carbonate, 350 to 420 grams of ammonium chloride, 375 to 450 grams of copper acetate, 20 to 75 grams of arsenic trioxide, and 10 to 25 grams of copper nitrate. More preferably, the solution is prepared by mixing in 6 liters of distilled water, 330 ml of concentrated hydrochloric acid, 130 grams of copper carbonate, 400 grams of ammonium chloride, 400 grams of copper acetate, 65 grams of arsenic trioxide and 15 grams of copper nitrateO Then, the solu-tion is left standing to reach equilibrium and filteredO As a prac-tical method, a standing period of one day to ensure equilibrium is generally considered safe before filtration.
Thereafter, the copper substrate may be allowed to dry in the room as defined abGve for a period of 2 to 4 hours.
It is important to never handle the copper substrate with the hands during this process.
It should be noted that these drying stages may, if desired, be referred to as curing. ~;
The day af-ter, the patinate copper substrate is obtaine. It may be placed in a wharehouse protected with a paper in between.
Al-though the present invention has been explained hereinabove by way of preferred embodiments thereof, it should be pointed out that any modifications to these preferred embodiments, within the scope of the appended claims, is not deemed to change or alter the nature and scope of the invention.
'~
In US patent no. 3,152,927, dated October 13, 1964, as inven-ted by MATTSON et al., is disclosed an agent for the arti.ficial green patination oE object comprising an aqueous sludge obtained by admixing an aqueous solution containing copper nitrate, iron sulphate and sodium hydroxide.
In US patent no. 3,434,890, dated March 25, 1969, as invented by ARONBERG, is disclosed a process for forming patina involving wetting a copper base alloy with a solution volatile water soluble organic solvent such as alcohol and salts of inorganic acids and primary amines.
In US patent no. 3,473,970, dated October 21, 1969, as invented by ROBEY, is disclosed a composition ~or imparting patina comprising copper sulphate, ammonium sulphate lithium chloride, sodium dicromate, hydrochloric acid, magnesium montmorillonite and water.
In US patent no. 3,497,~01, dated February 24, 1970, as invented by HANSON et al~, is disclosed a me-thod for producing synthetic patina by immersion in an aqueous acidic solution with potassium chlorate and copper sulphate.
In US patent no. 3,725,138, dated April 3, 1973, as invented by JONES, is disclosed a patina produced on a copper surface by applying an aqueous acidic solution of ammonium sulphate, sulphamic acid and iron sulphate, drying the solution to form a film on the copper surface. The film is then reacted with the copper surface in a humid atmosphere at a tempera-ture oE a-t least 30C for a period of -time to form an adhered corrosion product of which a major portion is 2~59~
insolubilized. The soluble par-ts are then dissolved, thereby developing in the reaction produc-t the color of natural pa-tina.
In US patent no. 4,416,940, dated November 22, 1983, as invented by LOYE et al., is disclosed a two step process comprising first applying an opaque pigmented base coat containing a patina color producing colorant to a primed or unprimed substrate, curing the base coat, applying to the cure base coat a non-opaque top coat containing one or rnore copper color producing additives.
SUMMARY OF THE INVENTION
Broadly stated, the invention is directed to a rapid me-thod for artificially forming patina on copper comprising:
a) removing any impurity present on the surface of a copper substrate, b) coating said copper substrate with an aqueous solution containing sodium ions, cupper ions, acetate ions, chlorine ions, sulphate ions, H~ ions and an OH- ions;
c) washing the copper substrate coated as in step (b) with water and drying;
d) gently brushing the copper substrate having been dried according to step (c), washing and drying;
e) coating said copper substrate after having been dried according to step (d), with a aqueous solution containing copper carbonate, ammonium chloride, copper acetate, arsenic trioxide, copper nitrate and hydrochloric acid.
The invention is also direc-ted -to new products obtained by -the method as deEined above and to produc-ts for forming patina on copper.
7, ~
DESCRIPTION OF A PREFERRED EMBODIMENT
The first step of the method involves cleaning of the surface i.n order to remove any impurity present on the surface of the copper substrate such as varnish, grease, copper oxide, e-tc. This cleaning is easily conduc-ted by brushing. In a preferred embodimen-t, cold brushing is conducted with nylon brushes having abrasive particles embedded in cured binders such as cured phenolformaldehyde resins, polyurethane resins and epoxy resins, These brushes may for instance be mechanically mounted on a driven roller bearing in mind tha-t the copper metal must touch sideways in order to obtain good patina Eixation and polishing could also be conducted if desired. Scoth Brite R brown pads may be used.
After removing any impurity present on the surface of the copper substrate, it should be borne in mind that the substra-te must be manipulated with dirt free and grease free intermediates and never with hands; one may use metallic instruments or cotton gloves for instance.
After removal of -the impurities, it is important to polish as quickly as possible the copper substrate with an aqueous solution containing sodium ions, copper ions~ acetate ions, chloride ions, sulphate ions, hydrogen ions and hydroxy ions. This aqueous solu-tion is preferably obtained by mixing from 100 to 150 ml of concentrated acetic acid, 500 to 600 grams of copper sulphate, 80 to 120 grams of sodium chloride, 11 -to 13 grams oE hydroxide and 11 to 15 grams of copper acetate in 4 liters of distilled water. More preferably, the solu-tion contains 4 liters of distilled water, 135 ml of concentra-ted acetic acid, 563 grams of copper sulphate, 100 grarns of sodium chloride, 12 grams of sodium hydroxide and 12 grams of copper aceta-te. The solution is applied in large quantity whether by jet, hand, mechanically or manually brushed until a brownish color is obtained. Thereafter, any excess of reactant is removed with thorough water washing. Drying is then conducted under air pressure over all coated surfaces and -then the copper substrate is cured for at least 12 hours, preferably in a room having a light used for growing plants such as Gro-Lux R Sylvania, simulating the solar light. Preferably, the sides of the room are reflecting light with surfaces such as mirror polished aluminum and the like. The room temperature is about 20 à 35C and preferably 25C with a relative humidity oE between 35 to 80% and preferably 50%.
After the drying step, the copper substrate is thoroughly washed and lightly brushed, whether manually or mechanically, in order to remove brownish color which is not sufficiently adhering to the substrate. The substrate is then pressure air dried. Thereafter, the copper substrate is submitted to a filtered aqueous solution containing copper carbonate, ammonium chloride, copper acetate, arsenic trioxide, copper nitrate and hydrochloric acid until the desired patinated copper substrate is obtained. This last step may be repeated if desired. This solution may be applied with a brush or a gun as desired.
Preferably, this lost solution is obtained by mixing in 6 liters of distilled water, from 300 to 360 ml of concentrated hydrochloric acid, 100 to 160 grams of copper carbonate, 350 to 420 grams of ammonium chloride, 375 to 450 grams of copper acetate, 20 to 75 grams of arsenic trioxide, and 10 to 25 grams of copper nitrate. More preferably, the solution is prepared by mixing in 6 liters of distilled water, 330 ml of concentrated hydrochloric acid, 130 grams of copper carbonate, 400 grams of ammonium chloride, 400 grams of copper acetate, 65 grams of arsenic trioxide and 15 grams of copper nitrateO Then, the solu-tion is left standing to reach equilibrium and filteredO As a prac-tical method, a standing period of one day to ensure equilibrium is generally considered safe before filtration.
Thereafter, the copper substrate may be allowed to dry in the room as defined abGve for a period of 2 to 4 hours.
It is important to never handle the copper substrate with the hands during this process.
It should be noted that these drying stages may, if desired, be referred to as curing. ~;
The day af-ter, the patinate copper substrate is obtaine. It may be placed in a wharehouse protected with a paper in between.
Al-though the present invention has been explained hereinabove by way of preferred embodiments thereof, it should be pointed out that any modifications to these preferred embodiments, within the scope of the appended claims, is not deemed to change or alter the nature and scope of the invention.
'~
Claims (14)
- The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:
l. A method for artificially forming patina on copper comprising:
a) removing any impurity present on the surface of copper substrate;
b) polishing said copper substrate with an aqueous solution containing sodium ions, copper ions, acetate ions, chlorine ions, sulphate ions, H+ ions and an OH- ions until a brown colour is obtained;
c) washing the polished copper substrate having brown colour of step b), with water and drying;
d) gently brushing the copper substrate having been dried according to step c), washing and thoroughly drying;
e) submitting said copper substrate after having been thoroughly dried according to step d), to a filtered aqueous solution containing copper carbonate, ammonium chloride, copper acetate, arsenic trioxide, copper nitrate and hydrochloric acid until the desired patinated copper substrate is obtained. - 2. A method according to claim 1, wherein said solution for step b) is obtained by mixing from 100 to 150 ml of concentrated acetic acid, 500 to 600 grams of copper sulfate, 80 to 120 grams of sodium chloride, 11 to 13 grams of sodium hydroxide and 11 to 15 grams of copper acetate in 4 liters of distilled water, and the aqueous solution for conducting the step e) is obtained by mixing in 6 liters of distilled water, from 300 to 360 ml of concentrated hydrochloric acid, 100 to 160 grams of copper carbonate, 350 to 420 grams of ammonium chloride, 375 to 450 grams of copper acetate 20 to 75 grams of arsenic trioxide, and 10 to 25 grams of copper nitrate.
- 3. The method as defined in claim 1, wherein said step (a) consists in dry brushing the surface of said substrate.
- 4. The method as defined in claim 1, wherein said step (a) consists in brushings said copper substrate sideways with a brush of nylon fibers having abrasive parts bonded thereto with cure resinous binder.
- 5. The method as defined in claim 1, wherein said drying as defined under step (c) is conducted during a period of about half a day.
- 6. The method as defined in claim 1, wherein said step (e) is repeated.
- 7. The method as defined in claim 1, wherein said coating in step (b) is applied with an air jet.
- 8. The method as defined in claim 3, wherein said brushing in step (d) is mechanically conducted.
- 9. The method as defined in claim 1, wherein step (c), said drying is conducted with pressurized air after said washing, and then said substrate is placed for 12 hours at about room temperature under the presence of a light source.
- 10. The method as defined in claim 9, wherein said light source is a light used for growing plants.
- 11. The method as defined in claim 1, wherein step (b) is immediately conducted after step (a).
- 12. The product obtained by the method as defined in claim 1.
- 13. The product obtained by the method as defined in claim 2.
- 14. A pair of solutions forming patina on copper comprising a first solution obtained by mixing from 100 to 150 ml of concentrated acetic acid, 500 to 600 grams of copper sulphate, 80 to 120 grams of sodium chloride, 11 to 13 grams of sodium hydroxide and 11 to 15 grams of copper acetate in 4 liters of distilled water, and a second solution obtained by mixing in 6 liters of distilled water from 300 to 360 ml of concentrated hydrochloric acid, 100 to 160 grams of copper carbonate, 350 to 420 grams of ammonium chloride, 375 to 450 grams of copper acetate, 20 to 75 grams of arsenic trioxide, and 10 to 25 grams of copper nitrate and then filtering said second solution.
R O B I C .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA 2045919 CA2045919A1 (en) | 1991-06-28 | 1991-06-28 | Method for forming artificially and rapidly patina on copper, products thereof and solutions therefor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA 2045919 CA2045919A1 (en) | 1991-06-28 | 1991-06-28 | Method for forming artificially and rapidly patina on copper, products thereof and solutions therefor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2045919A1 true CA2045919A1 (en) | 1992-12-29 |
Family
ID=4147931
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2045919 Abandoned CA2045919A1 (en) | 1991-06-28 | 1991-06-28 | Method for forming artificially and rapidly patina on copper, products thereof and solutions therefor |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA2045919A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10119038B2 (en) | 2015-05-08 | 2018-11-06 | PatinaNow, LLC | Patina solution, method for producing patina on object, and patina kit |
-
1991
- 1991-06-28 CA CA 2045919 patent/CA2045919A1/en not_active Abandoned
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10119038B2 (en) | 2015-05-08 | 2018-11-06 | PatinaNow, LLC | Patina solution, method for producing patina on object, and patina kit |
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