Articles comprising thermally stable, grain-refined alloys
Articles including electrodeposited layers of fine-grained alloys of Ni, Cu, Co, Fe and Zn with minor additions of B, O, P and S that provide high strength, ductility and thermal stability, are disclosed. The disclosure further relates to a process for fabricating the articles. Non-metallic additions of ≤2% are required to significantly increase the maximum temperature at which softening and grain-growth occurs. The grain-refined metallic layers or coatings are particularly suited for use in strong and lightweight parts required in aerospace, automotive and industrial applications subject to at least, at times, higher than ambient operating temperatures.
1 . An electrodeposited metallic material comprising:
(i) a microcrystalline grain structure with an average grain-size in the range of 2 to 1,000 nm;
(ii) at least two metallic elements selected from the group consisting of Co, Cu, Fe, Ni and Zn;
iii) each of said metallic element present comprising at least 5% per weight of the metallic material;
(iv) at least one non-metallic element selected from the group consisting of B, O, P and S;
(v) said non-metallic elements in total comprising between 50 ppm and 10,000 ppm per weight of the metallic material;
(vi) wherein the hardness of said electrodeposited metallic material after heat-treatment for 12 hours at a temperature of 100° C. in an inert atmosphere retains at least 90% of the as-deposited hardness,
(vii) wherein the metallic elements comprise Co and Ni, the non-metallic elements include P and O, the metallic alloy composition includes [PO 3 ] 3− , and said electrodeposited metallic alloy contains less than 75 ppm [PO 3 ] 3− .
2 . The electrodeposited metallic material of claim 1 which further comprises at least one additional non-metallic element selected from the group consisting of B and S.
3 . The electrodeposited metallic material of claim 1 which comprises at least 100 ppm of at least one of elemental P and elemental S.
4 . The electrodeposited metallic material of claim 1 wherein the metallic elements present further comprise Fe.
5 . The electrodeposited metallic material of claim 1 wherein the at least one additional non-metallic element further includes S.
6 . The electrodeposited metallic material of claim 5 wherein the non-metallic elements comprise at least 100 ppm of P and at least 100 ppm of at least one of S and O.
7 . The electrodeposited metallic material of claim 1 wherein the at least one additional non-metallic element further includes B.
8 . The electrodeposited metallic material of claim 1 wherein the non-metallic elements further comprise B and S.
9 . The electrodeposited metallic material of claim 1 wherein the non-metallic elements further comprise at least 100 ppm of at least one of B and P which are present in elemental form.
10 . The electrodeposited metallic material according to claim 1 , containing particulate additions representing between 1 and 30% per volume.
11 . An article including the electrodeposited metallic material according to claim 1 , wherein said electrodeposited metallic material has a total thickness in the deposition direction of at least 25 microns and is deposited on a permanent substrate.
12 . An article including the electrodeposited metallic material according to claim 1 , wherein said electrodeposited metallic material forms at least one layer comprised of the at least two metallic elements and having a total thickness in the deposition direction of at least 25 microns and is deposited on a temporary substrate which is removed after electroplating so that the article is a free-standing article.
13 . The electrodeposited metallic material according to claim 1 , containing particulate additions representing between 1 and 30% per volume.
14 . The electrodeposited metallic material according to claim 1 , wherein said electrodeposited metallic material is configured as a nano-laminate comprising at least 25 individual layers.
15 . The electrodeposited metallic material according to claim 14 , wherein each of said individual layers has a thickness in a range of about 5 nm to about 250 nm.
16 . The electrodeposited metallic material according to claim 14 , wherein the composition of directly adjacent sub-layers of at least one metallic element and/or at least one of the non-metallic elements varies by at least 5%.
17 . The article of claim 1 wherein O is present as MeO x and/or MeO x H y , wherein Me is the grain-refined electrodeposited metallic element selected from the group consisting of Co, Cu, Fe, Ni and Zn.
18 . An article comprising:
an electrodeposited metallic material consisting of:
(i) at least one metallic layer having a microcrystalline grain structure with an average grain-size in the range of 2 to 1,000 nm;
(ii) metallic elements including Co and Ni combined comprising at least 95% per weight of the metallic alloy layer;
(iii) at least one non-metallic element selected from the group consisting of B, O, P and S;
(iv) the non-metallic elements in total comprising between 50 ppm and 10,000 ppm per weight of the metallic alloy layer; and
(v) wherein the hardness of said electrodeposited metallic material after heat-treatment for 12 hours at a temperature of 200° C. in an inert atmosphere retains at least 90% of the as-deposited hardness,
(vi) wherein said electrodeposited metallic material contains P and O, the metallic alloy composition includes [PO 3 ] 3− and less than 90 ppm of [PO 3 ] 3− .
19 . The article according to claim 18 wherein said electrodeposited metallic material is subjected to one or more heat-treatments in the temperature range of between 100° C. and 650° C.
20 . The article of claim 18 wherein the non-metallic elements further contain between 100 ppm and 1000 ppm of S.
21 . The article of claim 20 wherein said electrodeposited metallic material further contains at least 300 ppm of S.
22 . The article of claim 18 wherein said electrodeposited metallic material is subjected to one or more annealing heat-treatments in the temperature range of between 200° C. and 650° C.
23 . An article comprising:
an electrodeposited metallic alloy layer, a composition of the metallic alloy layer consisting of:
(i) a microcrystalline grain structure with an average grain-size in the range of 2 to 1,000 nm;
(ii) two metallic elements consisting of Co and Ni, and each of said metallic elements comprising at least 5% per weight of the metallic alloy composition;
(iii) a non-metallic element consisting of P comprising between 100 ppm and 20,000 ppm per weight of the metallic alloy composition, wherein P is in elemental form having an oxidation state of zero, and is an alloying element with the electrodeposited metallic alloy layer;
(iv) particulates in the range of 0 to 95% per volume;
(vii) wherein if the composition of the metallic alloy layer includes at least one additional non-metallic element consisting of O comprising between 50 ppm and 20,000 ppm per weight of the metallic alloy composition, the metallic alloy composition includes [PO 3 ] 3− and less than 75 ppm of P is present in the form of [PO 3 ] 3− .
24 . The electrodeposited metallic material of claim 23 , wherein the non-metallic elements comprise at least 100 ppm of P and at least 100 ppm of O.
25 . The electrodeposited metallic material according to claim 23 , wherein said electrodeposited metallic material is configured as a nano-laminate comprising at least 25 individual layers.
26 . The electrodeposited metallic material according to claim 25 , wherein each of said individual layers has a thickness in a range of about 5 nm to about 250 nm.
27 . The electrodeposited metallic material according to claim 25 , wherein the composition of directly adjacent sub-layers of at least one metallic element and/or at least one of the non-metallic elements varies by at least 5%.
28 . The article according to claim 23 , wherein said electrodeposited metallic material is subjected to one or more heat-treatments in the temperature range of between 100° C. and 650° C.
29 . The article of claim 23 , wherein O is present as MeO x and/or MeO x H y , wherein Me is the grain-refined electrodeposited metallic element selected from Co and Ni.