Brazing sheet product and method of its manufacture
Disclosed is a brazing sheet product including a core metal sheet ( 1 ), on at least one side of the core metal sheet ( 1 ) a clad layer ( 2 ) made of an aluminium brazing alloy comprising silicon in an amount in the range of 4 to 14% by weight, and on at least one outersurface of the clad layer ( 2 ) a layer comprising iron or iron alloy ( 4 ), and on the outersurface of the layer comprising iron or iron alloy ( 4 ) a further layer ( 3 ) including a metal X, whereby X is selected from the group consisting of tin, zinc, bismuth, indium, antimony, strontium, titanium, manganese, copper, or combinations of two or more thereof. Also, disclosed is a method of manufacturing such a brazing product, and a brazed assembly including at least one component made of this brazing product.
1. A brazing sheet product comprising a core metal sheet ( 1 ), on at least one side of said core metal sheet ( 1 ) a clad layer ( 2 ) made of an aluminium brazing alloy comprising silicon in an amount in the range of 4 to 14% by weight, and on at least one outersurface of said clad layer ( 2 ) a layer comprising iron or iron alloy ( 4 ), and on the outersurface of said layer comprising iron or iron alloy ( 4 ) a further layer ( 3 ) comprising a metal X, whereby X is selected from the group consisting of tin, zinc, bismuth, indium, antimony, strontium, titanium, manganese, copper, or combinations of two or more thereof.
2. A brazing sheet product according to claim 1 , wherein the further layer comprises an iron-X alloy, wherein X is selected from the group consisting of tin, zinc, bismuth, indium, antimony, strontium, titanium, copper, or combinations of two or more thereof.
3. A brazing sheet product according to claim 2 , wherein the layer comprising iron-X alloy is formed by a plating method.
4. A brazing sheet product according to claim 2 , wherein the layer comprising iron-X alloy is formed by an electrolytic plating method.
5. A brazing sheet product according to claim 2 , wherein the layer comprising iron-X alloy is a diffusion layer.
6. A brazing sheet product according to claim 5 , wherein the iron-X alloy diffusion layer has a thickness in the range of about 0.1 to 0.8 μm.
7. A brazing sheet product according to claim 1 , wherein there is a bonding layer between said outer surface of said clad layer and said layer comprising iron or iron alloy.
8. A brazing sheet product according to claim 1 , wherein there is a layer comprising zinc or tin as a bonding layer between said outer surface of said clad layer and said layer comprising iron or iron alloy.
9. A brazing sheet product according to claim 7 , wherein said bonding layer has a thickness of at most 0.5 micron.
10. A brazing sheet product according to claim 7 , wherein said bonding layer has a thickness of at most 0.3 μm.
11. A brazing sheet product according to claim 7 , wherein said bonding layer has a thickness in the range of 0.01 to 0.15 μm.
12. A brazing sheet product according to claim 1 , wherein the clad layer and all layers exterior thereto form a metal filler for a brazing operation and have a composition with the proviso that the mol-ratio of Fe:sum of X is in the range of 10:(0.3 to 6).
13. A brazing sheet product according to claim 1 , wherein the mol-ratio of Fe:sum of X is in the range of 10:(0.5 to <5).
14. A brazing sheet product according to claim 1 , wherein the core metal sheet comprises a member of the group consisting of aluminium alloy, steel, aluminised steel, stainless steel, plated or coated stainless steel, bronze, brass, nickel, nickel alloy, titanium, and plated or coated titanium.
15. A brazing sheet product according to claim 1 , wherein the core metal sheet comprises aluminium alloy.
16. A brazing sheet product according to claim 1 , wherein the core metal sheet comprises an aluminium alloy selected from the group consisting of AA3xxx, AA5xxx, and AA6xxx-series aluminium alloy.
17. A brazing sheet product according to claim 1 , wherein the metal X layer is substantially lead-free.
18. A brazing sheet product according to claim 1 , wherein the layer comprising iron or iron alloy comprises at least 80 weight percent iron.
19. A brazing sheet product according to claim 1 , wherein the layer comprising iron or iron alloy comprises at least 85 weight percent iron.
20. A brazing sheet product according to claim 1 , wherein the layer comprising iron or iron alloy comprises at least 90 weight percent iron.
21. A brazing sheet product according to claim 1 , wherein the layer comprising iron or iron alloy comprises at least 96 weight percent iron.
22. A brazing sheet product according to claim 1 , wherein the layer comprising iron or iron alloy comprises at least 98 weight percent iron.
23. A brazing sheet product according to claim 1 , wherein the layer comprising iron or iron alloy has a thickness of at most 2.0 μm.
24. A brazing sheet product according to claim 1 , wherein the layer comprising iron or iron alloy has a thickness of at most 1.0 μm.
25. A brazing sheet product according to claim 1 , wherein the layer comprising iron or iron alloy has a thickness in the range of 0.05 to 0.5 μm.
26. An assembly of components joined by brazing, at least one said components being a brazing sheet product according to claim 1 .
27. An assembly according to claim 26 , wherein the assembly is brazed under a vacuum or in an inert atmosphere in the absence of a brazing-flux material.
28. An assembly according to claim 26 , wherein the assembly is a heat exchanger.
29. An assembly according to claim 26 , wherein the assembly is a fuel cell.
30. An assembly according to claim 26 , wherein the assembly is an electrochemical fuel cell.
31. A method of manufacturing a brazing product according to claim 1 , comprising the steps of: (a) providing a core metal sheet having on at least one side of said core metal sheet a clad layer made of an aluminium alloy containing silicon in an amount in the range of 4 to 14% by weight, (b) applying a metal layer comprising iron or iron-alloy onto at least one outersurface of said aluminium substrate, (c) applying a metal layer comprising X onto the outersurface of layer comprising iron or iron-alloy and wherein X is selected from the group consisting of tin, zinc, bismuth, antimony, strontium, indium, titanium, manganese, copper, or combinations of two or more thereof, and (d) subjecting the coated brazing product to a diffusion annealing treatment to form on the outer surface of said aluminium base substrate and onto the iron or iron-alloy layer a diffusion layer comprising iron-X alloy.
32. A method according to claim 31 , wherein the diffusion annealing treatment comprises holding the coated brazing product at a temperature in the range of 100 to 500° C. for a period of up to 300 minutes.
33. A method according to claim 31 , wherein the diffusion annealing treatment comprises holding the coated brazing product at a temperature in the range of 100 to 500° C. for a period of 1 sec. to 300 minutes.
34. A method according to claim 31 , wherein the metal X is tin or tin alloy and the diffusion annealing treatment is carried out below the melting temperature of tin.
35. A method according to claim 31 , wherein the metal X is tin or tin alloy and the diffusion annealing treatment is carried out above the melting temperature of tin.
36. A method according to claim 31 , wherein the metal X is tin or tin alloy and the diffusion annealing treatment is carried out at about 250° C. or about 300° C., whereby the tin diffuses into the solid iron or iron-alloy layer.
37. A method according to claim 31 , wherein the diffusion annealing treatment is at a temperature in a range of 230 to 350° C. for a soaking time of 1 sec. to 600 sec.
38. A method according to claim 31 , wherein the diffusion annealing treatment is at a temperature in a range of 230 to 350° C. for a soaking time of 1 sec. to 300 sec.
39. A method according to claim 31 , wherein the layer comprising iron or iron-alloy is applied using a plating method.
40. A method according to claim 31 , wherein the layer comprising iron or iron-alloy is applied using an electrolytic plating method.
41. A method according to claim 31 , wherein the metal layer comprising X is applied using a plating method.
42. A method according to claim 31 , wherein the metal layer comprising X is applied using an electrolytic plating method.
43. A method according to claim 31 , wherein the metal layer comprising iron or iron alloy is applied using a PVD method.
44. A method according to claim 31 , wherein the metal layer comprising X is applied using a PVD method.
45. A method according to claim 31 , wherein the metal layer comprising iron or iron alloy is applied using thermal spraying.
46. A method according to claim 31 , wherein the metal layer comprising X is applied using thermal spraying.
47. A method according to claim 31 , wherein the diffusion annealing treatment is carried out in a protective atmosphere.
48. A method according to claim 31 , wherein the core metal sheet comprises a member of the group consisting of aluminium alloy, steel, aluminised steel, stainless steel, plated or coated stainless steel, bronze, brass, nickel, nickel alloy, titanium, and plated or coated titanium.
49. A method according to claim 31 , wherein the core metal sheet comprises aluminium alloy.
50. A method according to claim 31 , wherein the core metal sheet comprises an aluminium alloy selected from the group consisting of AA3xxx, AA5xxx, and AA6xxx-series aluminium alloy.
51. A method according to claim 31 , wherein taken together the clad layer comprising silicon in an amount in the range of 4 to 14% by weight and all layers exterior thereto form a filler metal for a brazing operation and having a composition comprising at least, by weight percent:
Si in the range of 5 to 14%,
Fe in the range of 0.15 to 8%,
X in the range of 0.01 to 7%, and wherein X is selected from the group consisting of Sn, Zn, Bi, In, Sb, Sr, Mn, Ti, and Cu or combinations of two or more thereof,
Sn in the range of 0.0 to 0.3% if not present as X,
Bi in the range of 0.0 to 0.3% if not present as X,
Sb in the range of 0.0 to 0.3% if not present as X,
In in the range of 0.0 to 0.3% if not present as X,
Zn in the range of 0.0 to 0.3% if not present as X,
Sr in the range of 0.0 to 0.1% if not present as X,
Mn in the range of 0.0 to 0.3% if not present as X,
Ti in the range of 0.0 to 0.1% if not present as X,
Cu in the range of 0.0 to 0.3% if not present as X,
Mg in the range of 0.0 to 5%,
balance aluminium and inevitable impurities.
52. A method according to claim 51 , wherein the mol-ratio of Fe:sum of X is in the range of 10:(0.3 to 6).
53. A method according to claim 51 , wherein the mol-ratio of Fe: sum of X is in the range of 10:(0.5 to <5).
54. A method according to claim 31 , wherein prior to applying a coating according to step (b), there is deposited onto the outer surface of the clad layer a bonding layer having a thickness of not more than 0.5 micron.
55. A method according to claim 31 , wherein prior to applying a coating according to step (b), there is deposited onto the outer surface of the clad layer a bonding layer comprising zinc or tin, said bonding layer having a thickness of at most 0.5 micron.
56. A method according to claim 55 , wherein said bonding layer has a thickness of at most 0.3 μm.
57. A method according to claim 55 , wherein said bonding layer has a thickness in the range of 0.01 to 0.15 μm.
58. A method according to claim 31 , wherein the metal X layer is substantially lead-free.
59. A method according to claim 31 , wherein the layer comprising iron or iron alloy comprises at least 80 weight percent iron.
60. A method according to claim 31 , wherein the layer comprising iron or iron alloy comprises at least 85 weight percent iron.
61. A method according to claim 31 , wherein the layer comprising iron or iron alloy comprises at least 90 weight percent iron.
62. A method according to claim 31 , wherein the layer comprising iron or iron alloy comprises at least 96 weight percent iron.
63. A method according to claim 31 , wherein the layer comprising iron or iron alloy comprises at least 98 weight percent iron.
64. A method according to claim 31 , wherein the layer comprising iron or iron alloy has a thickness of at most 2.0 μm.
65. A method according to claim 31 , wherein the layer comprising iron or iron alloy has a thickness of at most 1.0 μm.
66. A method according to claim 31 , wherein the layer comprising iron or iron alloy has a thickness in the range of 0.05 to 0.5 μm.
67. A method according to claim 31 , wherein X in the range of 0.35 to 2%.
68. A method according to claim 31 , wherein Fe in the range of 0.9 to 5%.
69. A method according to claim 31 , wherein the iron-X alloy diffusion layer has a thickness in the range of about 0.1 to 0.8 μm.
70. An assembly of components joined by brazing, at least one said components being a product obtained by the method according to claim 31 .
71. An assembly according to claim 70 , wherein the assembly is brazed under a vacuum or in an inert atmosphere in the absence of a brazing-flux material.