Enhanced techniques for production of golden bronze by inter-diffusion of tin and copper under contr

专利摘要:
Golden bronze appearance article, multiple-layer substrate, related methods and uses thereof, particularly for coinage blanks. Methods of producing an article having a golden bronze appearance include annealing a multiple-layer substrate at an annealing temperature for an annealing residence time. The multiple-layer substrate includes a 10 core, contiguous to a copper layer and subsequent tin layer. The annealing temperature and annealing residence time are controlled in accordance with each other for allowing diffusion of the tin layer into the copper layer and producing an annealed substrate comprising an inter-diffused outer bronze layer having a golden appearance. The tin layer thickness is in accordance to the copper layer thickness such that the inter-diffused outer bronze layer has a tin content between about 8%wt. and about 15.8%wt. The core has a sufficiently low content of nickel to reduce or prevent formation of intermetallic compound comprising tin and nickel proximate to the core during annealing.
公开号:ES2544495A2
申请号:ES201590044
申请日:2012-11-08
公开日:2015-08-31
发明作者:Taixiang Jiang；Sridhar Bushigampala；Xianyao Li
申请人:MONNAIE ROYALE CANADIENNE / ROYAL CANADIAN MINT；MONNAIE ROYALE CANADIENNE ROYAL CANADIAN MINT；
IPC主号:

专利说明:

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P201590044 05-08-2015
core and that has a copper layer thickness; Y
a layer of tin applied as a coating on the copper layer;
5 in which the core contact area has a nickel content sufficiently low to reduce or prevent the formation of intermetallic compounds comprising tin and nickel near the external contact area during annealing;
in which the annealing is carried out at an annealing temperature for a time of
10 annealing permanence, being controlled, the annealing temperature and the annealing residence time in correspondence with each other to allow diffusion of the tin layer in the copper layer and produce an annealed substrate comprising an inter external bronze layer -disseminated that looks golden; Y
15 in which the tin layer is applied as a coating in the form of a tin layer thickness in accordance with the thickness of the copper layer, so that the inter-diffused outer copper layer has a tin content approximately comprised between 8% by weight and 15.8% by weight.
In an optional aspect of the process, the thickness of the tin layer may be such that the interdiffused outer bronze layer has a tin content between about 10% by weight and 15% by weight.
In an optional aspect of the procedure, the procedure may include control of the
Annealing temperature, according to temperature levels to allow the multilayer substrate to remain at each temperature level for a period of time of annealing. The process may also include annealing temperature control to allow the multilayer substrate to remain at a constant temperature level during the time of annealing.
In an optional aspect of the process, the annealing temperature can be found between approximately 425 ° C and 815 ° C.
In an optional aspect of the process, the coating may include the passage of the substrate
35 multilayer through a series of heating zones operating at controlled annealing temperature to heat the multilayer substrate to the
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P201590044 05-08-2015
a copper layer applied as a coating on the external contact area of the core and having a copper layer thickness; Y
5 a layer of tin applied as a coating on the copper layer;
wherein the external contact area of the core has a sufficiently low nickel content to reduce or prevent the formation of intermetallic compounds comprising tin and nickel in the vicinity of the external contact area during a treatment of
10 annealed; Y
in which the tin layer has a thickness of the tin layer according to the thickness of the copper layer so that the tin layer and the copper layer interconnect in the annealing treatment forming a copper layer with a tin content
15 comprised approximately between 8% and 15.8% by weight.
In an optional aspect of the substrate, it may further comprise a top metal layer that includes copper and / or zinc applied as a coating on the tin layer.
20 In another aspect, the use of the process as defined above for the production of blank pieces for coin minting is envisaged.
In another aspect, the use of the article with the appearance of gilded bronze as defined above as pieces for coin minting is envisaged.
In another aspect, the use of a multilayer substrate as defined above is envisaged to produce an article with an appearance of gilt bronze by annealing.
In another aspect, a process for the production of an article having a golden bronze appearance is envisaged. The procedure includes annealing a multilayer substrate including:
a core that has an external contact area;
35 a copper layer applied as a coating on the external contact area of the core and having a copper layer thickness;
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P201590044 05-08-2015
one
Cutting of blanks for coins from metal coils 2
Beading of blanks 3
Pre-annealed, 750ºC to 900ºC in protective atmosphere 4
Chemical cleaning of blanks 5
Washing 6 Electro-washing of the blanks 7 Electrolytic coating with a metallic coining layer 8 Washing; electrochemical attack 9 Copper electrolytic coating 10 Wash 11 Acid attack 12 Tin electrolytic coating 13 Wash 14 Drying 15 Tin diffusion in copper to form bronze by low heat treatment
protective atmosphere 16 Burnishing of blank parts 17 Drying 18 Ready-to-use blank
Figure 2 1 Tin atomic percentage 2 Temperature ºC 3 Tin weight percentage
Figure 5 1 Tin weight percentage 2
Temperature ºC 3
Tin atomic percentage
Figure 7 1 BRONZE ALLOY WITH A GOLDEN BRONZE ZONE AND A PINK ZONE 2
RESIDUAL COPPER COAT 3
COUPLING COAT
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Cyanide electrolytic contain CN-cyanide anions that can be toxic under certain conditions. Additionally, the external contact area of the core of the substrate to be coated with copper may be made of steel, which is an alloy susceptible to corrosion under acidic conditions. In response to the risk of corrosion of the substrate, some coating procedures include coating a coining layer of a protective metal such as nickel on the steel substrate before carrying out copper acid coating. Alternatively, some implementations of the present process use non-acidic, non-cyanide electrolytic coating solutions for copper coating directly on the external contact area of the substrate core. Optionally, the copper electrolytic coating solution may be an alkaline copper electrolytic coating solution. Optionally, the present process may include coating a first copper layer on the substrate core using an alkaline electrolytic coating solution and effecting the coating of a second copper layer using an acid electrolytic coating solution for greater effectiveness and efficiency. Advantageously, the first copper layer can act as a protective coinage layer with respect to any risk of corrosion of the substrate core. The use of non-acidic cyanide copper electrolytic coating solutions makes it possible not to coat the core of the substrate with a metal coinage layer composed of a metal, such as nickel, which can be expensive and can interfere with the diffusion process from tin inside the copper to form a gilt bronze alloy.
More precisely, it has been discovered (see the examples below) that the diffusion between the copper layer and the tin layer is limited by the presence of nickel in the external contact area of the core that is adjacent to the layer of copper with coating. More precisely, in annealing intermetallic compounds including tin and nickel, in the form of dendrites, can be formed under certain annealing conditions within the internal copper-rich zone and near the external contact zone, especially when the layer Copper coating is not thick enough. These intermetallic dendritic phases are mainly composed of tin, copper and nickel indicating that a significant amount of tin can interdiffuse with nickel and copper during annealing by forming said intermetallic compounds instead of participating with copper in the formation of the bronze alloy in phase α. During the diffusion process and under certain annealing conditions, the activated and mobile tin layer atoms can diffuse within the copper layer and, simultaneously, some activated and mobile nickel atoms can diffuse into the layer of
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P201590044 05-08-2015
Approximately 0.2 µm to 0.8 µm being applied as a coating to reduce
or eliminate any residual accumulations of tin and achieve a uniform surface color in annealing obtaining a blank with multiple layers;
5
5) The multi-layer blank is annealed with a certain set of annealing conditions (550 ° C to 750 ° C for a time of 20 to 80 minutes in a reducing atmosphere in an annealing furnace) so that a ternary bronze of Sn , Zn and Cu;
10 6) The annealed blank is cooled appropriately; Y
7) The cooled blank is subjected to burnishing to produce a blank prepared for minting (RTS). fifteen
Embodiment 3
1) Complete cleaning, pickling and chemical attack cleaning of low carbon steel blanks; 2) Electrolytic coating by copper layer directly on the low carbon steel blanks using an alkaline copper solution;
3) Electrolytic coating on the blank previously provided with
25 alkaline copper coating. Tin thickness is in the approximate range of 1.0 µm to 5.0 µm depending on the thickness of the bronze layer required; you get a blank with multiple layers;
4) The multi-layer blank is annealed with a certain set of 30 annealing conditions (550 ° C to 750 ° C for a time of 20 to 80 minutes in a reducing atmosphere in an annealing oven);
5) The annealed blank is cooled properly; Y
35 6) The cooled blank is subjected to burnishing to produce a blank prepared for minting (RTS).
3. 4
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EXAMPLE 4
4.1 Experimental conditions
A coin-coated blank with a 5 µm nickel layer, a 20 µm alkaline copper layer, a 5.0 µm tin layer and a 0.3 µm top zinc layer was annealed at a constant annealing temperature of 650 ° C for an annealing time of 60 minutes in a reducing medium. It should be noted that these thicknesses have been measured at the center of the blank provided with a coating.
4.2 Results
The sectional view taken with back scattering electron microscopy of the center of the annealed blank shown in Figure 19 includes dendritic phases in a subregion of the blank. The SEM analysis shown in Figure 20 shows that these dendritic phases contain a significant amount of nickel, even at a distance of 10 to 14 µm from the nickel layer, in contrast to the surrounding copper-rich phases in which much is observed less nickel More precisely, the nickel content in these dendritic phases is high on the order of 20% by weight, while the nickel content in the surrounding area rich in copper is much less than 2% by weight. These results suggest that new phases containing tin, nickel and copper can be formed as a result of diffusion between these elements, that a considerable amount of nickel atoms can move upwards, and that a considerable amount of tin atoms can be consumed by formation of ternary intermetallic compounds of Ni-Cu-Sn. These results imply, therefore, that tin may participate insufficiently in the formation of the bronze layer.
As can be seen in Figure 21, when the intermediate copper layer is sufficiently thick before annealing, for example, at the edge of the blank, ternary intermetallic compounds containing nickel and tin are not observed after annealing. The EDS analysis of Figure 21 shows that the nickel has diffused within the copper layer but that the nickel content was lower than that found in the dendritic phases of Figure 19. In general, it may be difficult for copper diffuse in nickel, which has also been confirmed by the EDS analysis. This is one of the reasons.
41
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权利要求:
Claims (5)
[1]
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and the tin.
[41]
41. Article with the appearance of gilded bronze, according to any of claims 32 to
40, which is in the form of a coin, a disk, a flat object, or the like. 5
[42]
42. Substrate with multiple layers for use in the production of an article with the appearance of gilded bronze, the substrate comprising multiple layers:
a core that has an external contact area;
10 a copper layer applied as a coating on the external contact area of the core and having a copper layer thickness; Y
a layer of tin applied as a coating on the copper layer;
15 in which the external contact area of the core does not comprise nickel to prevent the formation of intermetallic compounds comprising tin and nickel in the vicinity of the external contact area during an annealing treatment; Y
20 in which the tin layer has a thickness of the tin layer according to the thickness of the copper layer so that the tin layer and the copper layer interlock in the annealing treatment forming a bronze layer that It has a tin content between 8% by weight and approximately 15.8% by weight.
43. Multi-layer substrate according to claim 42, further comprising:
a top metal layer comprising copper and / or zinc applied as a coating on the tin layer.
30 44. Use of the procedure defined in any one of claims 1 to 31 for the production of blanks for coin minting.
[45]
45. Use of the article with the appearance of gilded bronze, according to any of the
claims 32 to 42, as a material for coin minting. 35
[46]
46. Use of the multilayer substrate defined in claims 42 or 43 for
49
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PCT/CA2012/050795|WO2014071493A1|2012-11-08|2012-11-08|Enhanced techniques for production of golden bronze by inter-diffusion of tin and copper under controlled conditions|

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