WO2010006562A1 - Method of protection of silver and copper surfaces against corrosion - Google Patents

Method of protection of silver and copper surfaces against corrosion Download PDF

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Publication number
WO2010006562A1
WO2010006562A1 PCT/CZ2009/000087 CZ2009000087W WO2010006562A1 WO 2010006562 A1 WO2010006562 A1 WO 2010006562A1 CZ 2009000087 W CZ2009000087 W CZ 2009000087W WO 2010006562 A1 WO2010006562 A1 WO 2010006562A1
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Prior art keywords
silver
protection
copper
boron
against corrosion
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PCT/CZ2009/000087
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French (fr)
Inventor
Tomas Base
Michael Geoffres Stephen Londesborough
Jonathan Bould
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Institute Of Inorganic Chemistry As Cr, V.V.I.
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Application filed by Institute Of Inorganic Chemistry As Cr, V.V.I. filed Critical Institute Of Inorganic Chemistry As Cr, V.V.I.
Priority to EP09775811A priority Critical patent/EP2313539A1/en
Publication of WO2010006562A1 publication Critical patent/WO2010006562A1/en

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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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/0021—Reactive sputtering or evaporation
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/24—Vacuum evaporation
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/58—After-treatment
    • C23C14/584—Non-reactive treatment
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/58—After-treatment
    • C23C14/5873—Removal of material
    • 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
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/18—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using inorganic inhibitors
    • C23F11/182—Sulfur, boron or silicon containing compounds

Definitions

  • This invention deals with the protection of metals, namely silver and copper, against corrosion.
  • dielectric layers Surfaces of silver telescope mirrors are protected with dielectric layers.
  • a common procedure is the deposition of a thin layer of silicon (Si) by sputtering followed by oxidation to yield a thin surface layer of SiO 2 .
  • Other materials commonly used for the protection of silver are for example HfO 2 and Si 3 N 4 . Layers of these materials prevent the direct exposure of the silver surface to corrosives from the atmosphere.
  • silver surfaces can be protected by a deposition of polymeric layers. The choice of which dielectric layer depends on the required final properties of the protected surfaces. For example, in the case of telescope mirrors, it is the absorption properties of the deposited protective layers that are of prime concern.
  • boron cluster hydrides compounds that consist of boron and hydrogen atoms. These are inorganic cluster species with geometries derived from a regular icosahedron, and can have various heteroatoms (elements other than boron) in the cluster framework. Common heteroatoms include most elements from the carbon (C) and nitrogen (N) groups of the periodic table, and ⁇ ?-block transition metal elements. Especially important is a class of boron cluster hydrides called carboranes that have in their molecules, aside to the atoms of boron (B) and hydrogen (H), at least one atom of carbon.
  • the most studied derivatives from this group of compounds are the positional isomers C 2 B 10 H 12 : ortho-, meta- a para-.
  • the first two have a dipole moment because of the presence and positioning of the two carbon atoms in the boron cluster skeleton.
  • Thiol (-SH) derivatives of these carborane cluster compounds react with metals to form a bond through the sulphur atom.
  • a mono-molecular layer of carborane clusters can be immobilized.
  • a thiol derivative of boron cluster hydrides is 9,12-(HS) 2 -I ⁇ -C 2 B 10 H 1O with the following schematic representation:
  • Carboranethiols can be immobilised onto a silver or copper surfaces by either (a) immersion of these metals into their solutions or (b) by exposure to their vapours. Both methods require the washing of excess material away from the surface with clean solvent.
  • appropriate solvents are ethanol, methanol, isopropanol, chloroform, hexane, heptane, toluene, benzene, acetone, dichlormethane, acetonitril, or diethylether.
  • Silver and copper surfaces react with thiolated boron hydride cluster species to yield a monomolecular coverege of these surfaces.
  • metal atoms from the surface form bonds with sulphur atoms attached to the boron hydride cluster via either cluster boron or carbon atoms.
  • boron cluster hydrides that make a bond to a silver or copper surface through atoms of sulphur attached to boron atoms (Ag(Cu)- S - B) offer particularly desirable characteristics.
  • a surface treated by these cluster compounds is, when exposed to an aggresive corrosive environment such as an atmosphere of H 2 S, significantly more durable and corrosion-resistant than an untreated surface.
  • Fig. 1 A schematic representation of the boron cluster hydride 9,12-(HS) 2 -l,2-C 2 B 10 H 10 with carbon atoms in positions 1 and 2. The atoms of hydrogen in the vertices are omitted for the reason of clarity.
  • a freshly deposited 200 nm silver film on a glass plate is immersed in 2 ml of a chloroform solution of 9, 12-(HS) 2 - 1,2-C 2 B J 0 HiO for one hour.
  • the plate with a silver film is removed from the solution, washed with clean and dry chloroform solvent, and left to dry in air.
  • Such a modified surface exhibits much better durability against blackening in the atmosphere of sulphane (H 2 S) than a bare silver film.
  • the modified silver film is placed in a closed container (for example a dessicator) above an aqueous solution OfNa 2 S for one month.
  • the silver film modified with 9,12-(HS) 2 -I ⁇ -C 2 B 1O H 10 remains silvery in comparison with a non-modified silver surface which blackens due to the formation of a layer of silver sulphide.
  • a freshly deposited 200 nm silver film on a glass plate is exposed to the vapours of sublimating 9,12-(HS) 2 -l,2-C 2 B 10 H 10 overnight. Subsequently the film is washed with an excess of clean and dry chloroform solvent, and dried in air.
  • Such a modified surface exhibits much better durability against blackening in the atmosphere of sulphane (H 2 S) than a bare silver film.
  • the modified silver film is placed in a closed container (for example a dessicator) above an aqueous solution of Na 2 S for one month. After this period the film modifed with 9,12-(HS) 2 -I ⁇ -C 2 B 1O H 10 still remains silvery in comparison with a non-modified silver surface which blackens due to the formation of a layer of silver sulphide.
  • a freshly deposited 200 nm silver film on a glass plate is exposed to an aqueous solution (2 ml) of sodium carboranethiolate 9, 12-(NaS) 2 -1, 2-C 2 Bi 0 H 10 (100 mg) for one hour. Additionally the silver surface is washed by rinsing in an excess of distilled water, and is dried in air. Such a modified surface exhibits much better durability against blackening in the atmosphere of sulphane (H 2 S) than a bare silver film.
  • the modified silver film is placed in a closed container (for example a dessicator) above an aqueous solution OfNa 2 S for one month.
  • the film modified with sodium carboranethiolate, 9,12-(NaS) 2 -I ⁇ -C 2 B 1O H 1O still remains silvery in comparison with a non-modified silver surface which blackens due to the formation of a layer of silver sulphide.

Abstract

Protection of silver and copper surfaces using a monomolecular layer of boron cluster hydrides that have attached to their boron atoms at least one functional group with at least one atom of sulphur. Such a modified surface of silver or copper is stable against harsh corrosive environments.

Description

Method of protection of silver and copper surfaces against corrosion
Technical field
This invention deals with the protection of metals, namely silver and copper, against corrosion.
State of the art
The corrosion of silver and copper is an important problem because of the many technical applications of both of these metals. In the case of silver, corrosion usually results in its blackening as a consequence of its reaction with hydrogen sulfide (H2S) from air and the formation of a surface layer of silver sulfide. With copper objects, a bigger problem is surface oxidation that engenders a layer of copper oxides. Both metals are used for decorative purposes, conductive leads, etc., and silver is particularly important in the fabrication of highly reflective surfaces. Both silver and copper are, for historical reasons, labeled as coinage metals and have always enjoyed a high associated value. Concordantly, the protection of silver and copper surfaces has a special importance with objects of historical value. Surfaces of silver telescope mirrors are protected with dielectric layers. A common procedure is the deposition of a thin layer of silicon (Si) by sputtering followed by oxidation to yield a thin surface layer of SiO2. Other materials commonly used for the protection of silver are for example HfO2 and Si3N4. Layers of these materials prevent the direct exposure of the silver surface to corrosives from the atmosphere. Alternatively, silver surfaces can be protected by a deposition of polymeric layers. The choice of which dielectric layer depends on the required final properties of the protected surfaces. For example, in the case of telescope mirrors, it is the absorption properties of the deposited protective layers that are of prime concern.
Disclosure of the invention
Protection of silver and copper against corrosion (especially against blackening of silver) can be achieved with the use of boron cluster hydrides, compounds that consist of boron and hydrogen atoms. These are inorganic cluster species with geometries derived from a regular icosahedron, and can have various heteroatoms (elements other than boron) in the cluster framework. Common heteroatoms include most elements from the carbon (C) and nitrogen (N) groups of the periodic table, and β?-block transition metal elements. Especially important is a class of boron cluster hydrides called carboranes that have in their molecules, aside to the atoms of boron (B) and hydrogen (H), at least one atom of carbon. The most studied derivatives from this group of compounds are the positional isomers C2B10H12: ortho-, meta- a para-. The first two have a dipole moment because of the presence and positioning of the two carbon atoms in the boron cluster skeleton. Thiol (-SH) derivatives of these carborane cluster compounds react with metals to form a bond through the sulphur atom. Thus, on silver or copper surfaces, a mono-molecular layer of carborane clusters can be immobilized. One example of a thiol derivative of boron cluster hydrides is 9,12-(HS)2-I^-C2B10H1O with the following schematic representation:
Figure imgf000004_0001
Carboranethiols can be immobilised onto a silver or copper surfaces by either (a) immersion of these metals into their solutions or (b) by exposure to their vapours. Both methods require the washing of excess material away from the surface with clean solvent. With regards to method (a), appropriate solvents are ethanol, methanol, isopropanol, chloroform, hexane, heptane, toluene, benzene, acetone, dichlormethane, acetonitril, or diethylether. Concerning the modification of silver or copper surface from an aqueous solution, it is appropriate to use a sodium, 9,12-(NaS)2-I^-C2B10H10, potasium, 9,12-(KS)2-1, 2-C2B10H10, or other salt of 9,12-(HS)2-l,2-C2B10H10 that is soluble in water or a mixture of alcohol and water. It is noteworthy that the modification of copper and silver surfaces using method (b) is, in many circumstances, advantageous because it avoids the use of solvent, a potential source of impurities of organic character.
Silver and copper surfaces react with thiolated boron hydride cluster species to yield a monomolecular coverege of these surfaces. In such a system, metal atoms from the surface form bonds with sulphur atoms attached to the boron hydride cluster via either cluster boron or carbon atoms. We have found that boron cluster hydrides that make a bond to a silver or copper surface through atoms of sulphur attached to boron atoms (Ag(Cu)- S - B) offer particularly desirable characteristics. A surface treated by these cluster compounds is, when exposed to an aggresive corrosive environment such as an atmosphere of H2S, significantly more durable and corrosion-resistant than an untreated surface. If the sulphur atom is attached at a carbon atom, a heteroatom in the cluster, the protection is less effective. This has been demonstrated by comparing 9,12-(HS)2-1, 2-C2B10H10 with the derivative l,2-(HS)2-l,2-C2B10H10 and with organic thiols. One of the reasons of this observance might be the lower stability of Ag(Cu)- S - C bonds compared to Ag(Cu)- S - B bonds.
A key advanatageous property obtained by using boron hydride species (BxHy)3 and their various derivatives, is their durability against high temperature and various types of radiation. This aspect makes these compounds suitable candidates for the protection of temperature and radiation stressed components of various devices. Examples are silver or copper electrical connections, contacts, and other parts of electrical circuits. Additionally, we can mention the protection of surfaces of silver telescopic mirrors, or the use of boron cluster hydrides for the protection of silver or copper components of devices designed for the study or analysis of samples in harsh environments where their protection can significantly enhance the life-time of these components or devices.
The discussed protection of silver surfaces against corrosion (blackening) can be potentially used to protect silver objects of historcial value, such as silver coins, dishes, jewellery, etc. The jewellery-making industry is an area of great potential because of its wide spread. The use of boron cluster hydrides for the purposes of protection of silver and copper surfaces has not been described before, and their use in a procedure described later in this text leads to a formation of mono-molecular layers on a silver or copper surface: An extremely thin layer of about 1 nm. A further advantage of this surface protection system is that by the nature of it being a monomolecular layer protection there is almost zero light absorption by the protective layer and is therefore highly suitable for applications where reflectivity and absorption is vital. The deposition of these derivatives does not require any sophisticated device or assembly for its application. Description of Figures
Fig. 1: A schematic representation of the boron cluster hydride 9,12-(HS)2-l,2-C2B10H10 with carbon atoms in positions 1 and 2. The atoms of hydrogen in the vertices are omitted for the reason of clarity.
Examples of preparation
Example 1
A freshly deposited 200 nm silver film on a glass plate is immersed in 2 ml of a chloroform solution of 9, 12-(HS)2- 1,2-C2B J0HiO for one hour. The plate with a silver film is removed from the solution, washed with clean and dry chloroform solvent, and left to dry in air. Such a modified surface exhibits much better durability against blackening in the atmosphere of sulphane (H2S) than a bare silver film. The modified silver film is placed in a closed container (for example a dessicator) above an aqueous solution OfNa2S for one month. The silver film modified with 9,12-(HS)2-I^-C2B1OH10 remains silvery in comparison with a non-modified silver surface which blackens due to the formation of a layer of silver sulphide.
Example 2
A freshly deposited 200 nm silver film on a glass plate is exposed to the vapours of sublimating 9,12-(HS)2-l,2-C2B10H10 overnight. Subsequently the film is washed with an excess of clean and dry chloroform solvent, and dried in air. Such a modified surface exhibits much better durability against blackening in the atmosphere of sulphane (H2S) than a bare silver film. The modified silver film is placed in a closed container (for example a dessicator) above an aqueous solution of Na2S for one month. After this period the film modifed with 9,12-(HS)2-I^-C2B1OH10 still remains silvery in comparison with a non-modified silver surface which blackens due to the formation of a layer of silver sulphide.
Example 3
A freshly deposited 200 nm silver film on a glass plate is exposed to an aqueous solution (2 ml) of sodium carboranethiolate 9, 12-(NaS)2-1, 2-C2Bi0H10 (100 mg) for one hour. Additionally the silver surface is washed by rinsing in an excess of distilled water, and is dried in air. Such a modified surface exhibits much better durability against blackening in the atmosphere of sulphane (H2S) than a bare silver film. The modified silver film is placed in a closed container (for example a dessicator) above an aqueous solution OfNa2S for one month. After this period the film modified with sodium carboranethiolate, 9,12-(NaS)2-I^-C2B1OH1O, still remains silvery in comparison with a non-modified silver surface which blackens due to the formation of a layer of silver sulphide.
Industrial applicability
For silver components and devices in astronomy, electronics, or space industry. Furthermore, for jewellery-making industry, and for the protection of objects of historical value.

Claims

1. The method of protection of silver and copper surfaces against corrosion characterized in that these surfaces are modified by the vapours or solutions of boron cluster hydrides that have attached to their boron atoms at least one functional group with at least one atom of sulphur.
2. The method of protection of silver and copper surfaces against corrosion according to claim 1 characterized in that the boron cluster hydride is 9,12-(HS)2-l,2-C2B10H10.
3. The method of protection of silver and copper surfaces against corrosion according to the claim 1 characterized in that as solvent is used chloroform, or dichlormethane, or hexane, or heptane, or toluene, or benzene, or acetone, or acetonitrile, or diethylether, or tetrahydrofurane, or methanol, or ethanol, or isopropanol, or water, or their mixtures.
PCT/CZ2009/000087 2008-06-23 2009-06-23 Method of protection of silver and copper surfaces against corrosion WO2010006562A1 (en)

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