JPWO2010089840A1 - Products with gadolinium-containing metal layers - Google Patents

Abstract

The present invention provides a product having a gadolinium-containing alloy metal layer excellent in corrosion resistance, suitable for an electric / electronic member, and a method for producing the same. Furthermore, it aims at providing the product which has a metal layer with high electrical conductivity with corrosion resistance. Specifically, the present invention is a product having a support and a metal layer formed on the support, the layer being 0.1% to 54% gadolinium based on the weight of the entire metal layer. And 99.9% to 46% of the first metal. The product having the gadolinium-containing metal layer of the present invention has excellent corrosion resistance and can suppress the generation of whiskers.

Description

  The present invention relates to a product having a gadolinium-containing alloy metal layer suitable for an electric / electronic member, a decorative member, and a medical member, and a manufacturing method thereof.

  Plating with a thin layer of metal on the surface of the support is generally used for decorative, corrosion resistance, wear resistance, solder wettability, electrical conductivity, electrical resistance, low contact resistance, magnetic properties, and heat resistance. Etc. can be provided. For example, copper alloy is used as a base material for electronic and electrical parts such as connectors and terminals used in various electronic devices such as automobiles, home appliances, OA equipment, etc., and these include rust prevention, corrosion resistance improvement, electrical property improvement, etc. Plating is performed for the purpose of improving the function (see Japanese Patent Laid-Open No. 8-17683 (Patent Document 1) and the like). Silver has high electrical conductivity, and silver plating is applied to metal surfaces such as electrical parts such as contacts, automobile parts, and aircraft parts (for example, JP 2000-76948 A (Patent Document 2)). JP, 5-287542, A (patent documents 3) etc.).

  However, many of the conventional plating treatments have insufficient corrosion resistance, causing problems such as discoloration, whisker generation, contact resistance failure due to surface oxidation, and electrical shorts.

  For this problem, gold plating is often used (for example, Japanese Patent Laid-Open No. 2005-5716 (Cited Reference 4), Japanese Patent Laid-Open No. 2002-167676 (Cited Reference 5), and Japanese Patent Laid-Open No. 2007-2007. No. 187580 (Cited document 6) and the like, and the cost required is higher than that of normal plating.

Japanese Patent Laid-Open No. 8-17683 JP 2000-76948 A JP-A-5-287542 Japanese Patent Laid-Open No. 2005-5716 JP 2002-167676 A JP 2007-187580 A

  The present invention has been made in view of the above, and an object thereof is to provide a product having a metal layer having high corrosion resistance. Furthermore, it aims at providing the product which has a metal layer with high electrical conductivity with corrosion resistance.

  The present invention provides a product having a gadolinium-containing metal layer excellent in corrosion resistance, suitable for electronic members, decorative members, and medical members, and a method for producing the same.

  Specifically, a product having a support and a metal layer formed on the support, the metal layer being 0.1% to 54% gadolinium and 99.9% based on the total mass. A product comprising ˜46% of a first metal and a method for its manufacture are provided.

  The product having the gadolinium-containing metal layer of the present invention has excellent corrosion resistance and can suppress the generation of whiskers. In addition, the product having a gadolinium-containing metal layer of the present invention has high electrical conductivity, keeps the solder wettability equivalent to that of a conventional plated product, suppresses discoloration of the metal layer, and has a surface having a Vickers hardness of 20 to 165. Can have hardness.

  Embodiments of the present invention will be described below. The following embodiment is merely an example of the present invention, and those skilled in the art can change the design as appropriate.

  The product of the present invention has a support and a metal layer formed on the support. Specifically, the metal layer includes 0.1% to 54% gadolinium and 99.9% to 46% of the first metal, based on the total weight of the metal layer.

(Support)
The support in the present invention is formed using a material that can withstand the conditions (solvent, temperature, etc.) used for forming the metal layer described later.

  When the metal layer is formed by electroplating, the support is conductive and is used as a cathode in the electroplating process. Conductive materials that can be used as the support include, but are not limited to, iron, nickel, copper, chromium, tin, zinc, and alloys thereof. Preferably, stainless steel, 42 alloy, phosphor bronze, nickel, brass material or the like is used.

  On the other hand, when the metal layer is formed by physical vapor deposition, chemical vapor deposition, electroless plating, or the like, and the support does not need to be energized, the support may be non-conductive. Specifically, polyamide, polycarbonate, polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, poly-1,4-cyclohexanedimethylene terephthalate, polyethylene-1,2-diphenoxyethane-4,4′-dicarboxylate, Polyester resins such as polybutylene terephthalate, polyolefins such as polystyrene, polyethylene, polypropylene, and polymethylpentene, acrylic resins such as polymethyl methacrylate, polysulfone, polyethersulfone, polyetherketone, polyetherimide, polyoxyethylene, norbornene resin It can form using polymeric materials, such as. It can also be formed using a semiconductor such as glass or silicon, or ceramic. Naturally, the conductive material may be used as a support.

  The support may be subjected to a surface treatment in order to improve the adhesion of the metal layer.

(Metal layer)
The metal layer in the present invention contains 0.1 to 54% gadolinium and 99.9% to 46% of the first metal based on the mass of the entire metal layer.

  The first metal may be any metal that can form an alloy with gadolinium. Silver, tin, chromium, nickel and copper are preferable. The first metal may be a compound as long as the metal layer can be formed by the metal layer forming method described later. When using a compound as the first metal, the compound includes chloride, bromide, sulfate, sulfite, carbonate, organic sulfonate, sulfosuccinate, nitrate, citrate, tartrate, gluconate, Metal salts such as oxalates and oxides and salts containing mixtures thereof can be used.

  Gadolinium in the present invention may be either a carrier metal or a compound depending on the method for forming a metal layer described later. The gadolinium compounds that can be used in the present invention include, but are not limited to, gadolinium salts such as gadolinium nitrate, gadolinium oxide, gadolinium sulfate, gadolinium chloride, and gadolinium phosphate, and mixtures thereof. Gadolinium oxide is preferred.

  Furthermore, in the present invention, the metal layer may contain a smaller amount of the second metal than the first metal as long as the corrosion resistance is not impaired. Preferably, the second metal is included in an amount of less than 30% based on the mass of the entire metal layer. Specific examples of the second metal that can be used in the present invention include palladium, cobalt, lithium, antimony, bismuth, cadmium, gallium, and germanium. Preferably it contains palladium.

  The metal layer of the present invention can be produced with any film thickness. The film thickness can be preferably 0.01 μm or more and 5 mm or less, more preferably 0.1 μm or more and 1 mm or less.

(Formation of metal layer)
In the present invention, the metal layer can be produced using any method known in the art, provided that it can be produced with a desired configuration and film thickness. Specifically, the metal layer of the present invention can be produced by a method such as electroplating; electroless plating; physical vapor deposition such as vacuum deposition, sputtering, ion plating, etc .; chemical vapor deposition.

a. Electroplating method The method for forming a metal layer of the present invention includes a step of immersing a substrate in a plating bath and a step of applying an electric field to the substrate, wherein the plating bath (a) determines the total metal mass in the plating bath. A compound of a first metal containing 99.9% by mass to 46% by mass of a first metal on the basis, and (b) 0.1% by mass to 54% by mass of gadolinium on the basis of the total metal mass in the plating bath. An electroplating method characterized by containing a gadolinium compound, (c) at least one complexing agent, and (d) a solvent can be used. As the electroplating method, methods generally known to those skilled in the art such as barrel plating, rack plating, high-speed continuous plating, and rackless plating can be used.

  In the electroplating method, a support on which a metal layer is deposited (plated) is used as a cathode. A soluble or preferably insoluble anode is used as the second electrode. In the present invention, pulse plating, DC plating, or a combination of pulse plating and DC plating can be used.

  The plating bath of the present invention includes (a) a first metal compound containing 99.9% by mass to 46% by mass of a first metal based on the total metal mass in the plating bath, and (b) a total amount in the plating bath. A gadolinium compound containing 0.1% to 54% by mass of gadolinium based on the metal mass, (c) at least one complexing agent, and (d) a solvent.

  The total metal ion concentration in the plating bath is in the range of 0.01 g / L to 200 g / L, preferably 0.5 g / L to 100.0 g / L. In general, the first metal ions are present in the plating bath in a concentration of 20 g / L to 200 g / L, preferably 25 g / L to 80 g / L.

  The complexing agent refers to a compound which coordinates to the first metal ion and / or gadolinium ion provided from the first metal compound and / or the gadolinium compound and stabilizes the ion. In the present invention, the complexing agent may have two or more metal coordination sites.

  Complexing agents that can be used in the present invention include, but are not limited to, amino acids having 2 to 10 carbon atoms; polycarboxylic acids such as oxalic acid, adipic acid, succinic acid, malonic acid and maleic acid; nitrilo Aminoacetic acids such as triacetic acid; ethylenediaminetetraacetic acid (“EDTA”), diethylenetriaminepentaacetic acid (“DTPA”), N- (2-hydroxyethyl) ethylenediaminetriacetic acid, 1,3-diamino-2-propanol-N, N , N ', N'-tetraacetic acid, bis- (hydroxyphenyl) -ethylenediaminediacetic acid, diaminocyclohexanetetraacetic acid, or ethylene glycol-bis- (β-aminoethyl ether) -N, N, N', N'- Alkylene polyamine polyacetic acid such as tetraacetic acid; N, N, N ′, N′-tetrakis- (2-hydro Cypropyl) ethylenediamine, ethylenediamine, 2,2 ', 2 "-triaminotriethylamine, triethylenetetramine, diethylenetriamine and polykis such as tetrakis (aminoethyl) ethylenediamine; citrate; tartrate; N, N-di- (2- Hydroxyethyl) glycine; gluconate; lactate; crown ether; cryptand; polyhydroxyl compounds such as 2,2 ′, 2 ″ -nitrilotriethanol; 2,2′-bipyridine, 1,10-phenanthroline and 8-hydroxyquinoline Heteroaromatic compounds such as; thio-containing ligands such as thioglycolic acid and diethyldithiocarbamate; and aminoalcohols such as ethanolamine, diethanolamine, and triethanolamine. Two or more complexing agents may be used in combination.

  The complexing agent of the present invention can be used in various concentrations. For example, the stoichiometric equivalent to the total amount of first metal ions and / or gadolinium ions present in the plating bath, or chemical so as to complex all the first metal ions and / or gadolinium ions. Stoichiometric excess and may be used. The term “stoichiometric” as used herein refers to equimolar.

  The complexing agent may be present in the plating bath at a concentration of 0.1 g / L to 250 g / L. Preferably, it is contained in the plating bath at a concentration of 2 g / L to 220 g / L, more preferably 50 g / L to 150 g / L.

  The electroplating bath solvent that can be used in the present invention may be any solvent that can dissolve the first metal compound, gadolinium compound, and complexing agent. As the solvent, water and a nonaqueous solvent such as acetonitrile, alcohol, glycol, toluene, dimethylformamide, and the like can be used. A solvent from which other metal ions have been removed with an ionic resin or the like is preferable. Most preferred is water that has been subjected to metal ion removal treatment.

  The plating bath usually has a pH of 1 to 14. Preferably, the plating bath has a pH of ≦ 7, more preferably ≦ 4. A buffer may be added to maintain the pH of the plating bath at a desired value. Any compatible acid or base may be used as a buffer, which may be organic or inorganic. A “compatible” acid or base is one that does not cause precipitation of tin ions and / or complexing agents from solution when such acid or base is used in an amount sufficient to buffer pH. Meaning. Exemplary buffering agents include, but are not limited to, alkali metal hydroxides such as sodium hydroxide or potassium hydroxide, carbonates, citric acid, tartaric acid, nitric acid, acetic acid and phosphoric acid.

  The electroplating plating bath that can be used in the present invention optionally further includes various additives such as known surfactants, stabilizers, brighteners, semi-brighteners, antioxidants, and pH adjusters. Can be mixed.

As the _surfactant, C 1 _{-C 20} alkanols, phenol, naphthol, _bisphenol, C 1 _{-C 25} alkyl phenols, aryl _phenols, C 1 _{-C 25} alkyl _naphthol, C 1 _{-C 25} alkoxylated phosphoric acid (salt ), sorbitan esters, styrenated phenols, polyalkylene _glycols, C 1 _{-C 22} aliphatic _amines, C 1 _{-C 22} 2 to 300 moles of aliphatic amides such as ethylene oxide (EO) and / or propylene oxide (PO) Examples include addition-condensed nonionic surfactants, cationic, anionic, and amphoteric surfactants.

  The stabilizer is contained for the purpose of stabilizing or preventing decomposition of the liquid, and specifically, known compounds such as cyanide compounds, thioureas, sulfur-containing compounds such as sulfite and acetylcysteine, and oxycarboxylic acids such as citric acid. Stabilizers are effective. The complexing agents listed above are also useful as stabilizers.

  Examples of the brightener include m-chlorobenzaldehyde, p-nitrobenzaldehyde, p-hydroxybenzaldehyde, 1-naphthaldehyde, salicylaldehyde, paraaldehyde, acrolein, crotonaldehyde, glutaraldehyde, vanillin and other aldehydes, benzalacetone. And ketones such as acetophenone, unsaturated carboxylic acids such as acrylic acid, methacrylic acid and crotonic acid, triazine, imidazole, indole, quinoline, 2-vinylpyridine and aniline.

  Examples of the semi-brightening agent include thioureas, N- (3-hydroxybutylidene) -p-sulfanilic acid, N-butylidenesulfanilic acid, N-cinnamoylidenesulfanilic acid, 2,4-diamino-6- ( 2'-methylimidazolyl (1 ')) ethyl-1,3,5-triazine, 2,4-diamino-6- (2'-ethyl-4-methylimidazolyl (1')) ethyl-1,3,5 -Triazine, 2,4-diamino-6- (2'-undecylimidazolyl (1 ')) ethyl-1,3,5-triazine, phenyl salicylate, or benzothiazole, 2-methylbenzothiazole, 2- (Methyl mercapto) benzothiazole, 2-aminobenzothiazole, 2-amino-6-methoxybenzothiazole, 2-methyl-5-chlorobenzothiazole, 2 Hydroxybenzothiazole, 2-amino-6-methylbenzothiazole, 2-chlorobenzothiazole, 2,5-dimethylbenzothiazole, 2-mercaptobenzothiazole, 6-nitro-2-mercaptobenzothiazole, 5-hydroxy-2- And benzothiazoles such as methylbenzothiazole and 2-benzothiazolethioacetic acid. Examples of the antioxidant include ascorbic acid or a salt thereof, hydroquinone, catechol, resorcin, phloroglucin, cresolsulfonic acid or a salt thereof, phenolsulfonic acid or a salt thereof, naphtholsulfonic acid or a salt thereof.

  Examples of the pH adjuster include various acids such as hydrochloric acid and sulfuric acid, and various bases such as ammonium hydroxide and sodium hydroxide.

A person skilled in the art can appropriately change the design of the current density and electrode surface potential of the electroplating process depending on the support to be plated. Generally, anode and cathode current density varies 0.5~5A / cm ^2. The temperature of the plating bath is maintained in the range of 25 ° C to 35 ° C during the electroplating process. The electrical process is continued for a time sufficient to form a deposit of the desired thickness. By the method of the present invention, a metal layer having a thickness of 0.01 μm to 50 μm can be formed on the support surface.

b. Electroless plating method The electroless plating method is a method capable of plating even non-conductors such as plastics and ceramics. The electroless plating method is preferable because the deposition rate and particle size of the metal particles can be precisely controlled. As a preferable electroless plating method, for example, pretreatment by a method of supporting any suitable catalyst (for example, palladium) on a support as pretreatment, followed by any suitable additive (for example, surfactant, complex). And a method of plating using a plating bath in which metal particles are uniformly dispersed without agglomeration using an agent, a reducing agent). A desired metal layer can be formed on the surface of the support by efficiently combining the method of supporting the catalyst and the method of plating with a plating bath.

  The electroless gadolinium alloy plating bath has a basic composition of a soluble first metal salt, a soluble gadolinium salt, an acid or a salt thereof, and a complexing agent. As the first metal salt, gadolinium salt, acid, and complexing agent, the same electroplating method as that described above can be used.

  Further, a reducing agent may be added to the plating bath. The reducing agent added to the plating bath is oxidized by the catalyst supported on the support surface. The metal ions or metal oxide ions in the plating bath are reduced by the electrons emitted at this time, and metal deposition starts from the vicinity of the catalyst and adheres to the support. As a result, a metal layer can be formed on the support surface. As the reducing agent, hypophosphorous acid, formaldehyde, boron hydride, dimethylamine borane, trimethylamine borane, hydrazine and the like can be used.

  Further, the electroless gadolinium alloy plating bath may optionally include various additives similar to the above electroplating methods, such as known surfactants, stabilizers, brighteners, semi-brighteners, antioxidants, and pH adjusters. Can be further mixed.

  Depending on the support to be plated, the bath temperature can be appropriately changed in design. Generally, the temperature of the plating bath is preferably 5 ° C to 60 ° C, which is lower than usual.

c. Physical vapor deposition As a method of forming the metal layer of the present invention, physical vapor deposition such as vacuum vapor deposition (including resistance heating method and electron beam heating method), sputtering (including facing sputtering, magnetron sputtering, etc.), ion plating, etc. is used. Can do.

The vacuum deposition method is performed using a vacuum deposition apparatus. First, the first metal and gadolinium, which are film forming materials, are put into a vapor deposition source (for example, a crucible or the like). At that time, the first metal and gadolinium may be supplied to separate vapor deposition sources. Next, the vacuum chamber is evacuated to make the atmosphere in the vacuum chamber a reduced pressure atmosphere having a predetermined degree of vacuum. Thereafter, when the inside of the vacuum chamber is depressurized to a predetermined degree of vacuum, the first metal and gadolinium are removed from the vapor deposition source by heating the vapor deposition source and the first metal and gadolinium charged therein in the reduced pressure atmosphere. Evaporate. The first metal and gadolinium evaporated in this way adhere to the surface of the support disposed facing the vapor deposition source. Thereby, a metal layer is formed on the support. When using a vacuum evaporation method, the film-forming speed | rate can be made into the range of 0.1-10 nm / second in the film-forming pressure of 1.0 * 10 < ^-4 > Pa or less.

Sputtering is performed using a sputtering apparatus. First, a target made of a first metal and gadolinium serving as a film forming material is placed in the apparatus. The target may be an alloy mixed in a desired ratio. Moreover, you may install a single 1st metal and gadolinium in a desired ratio, respectively. Next, ions accelerated by glow discharge, ion beam, ECR plasma, or the like are struck against the target material, and sputtered particles are released from the target. The released sputtered particles are deposited on the support to form a metal layer. In the case of using sputtering, the film forming speed can be set within a range of 0.1 to 100 nm / second at a film forming pressure of 5.0 × 10 ⁻⁴ Pa or less.

(Products with gadolinium-containing alloy metal layers)
The product having a gadolinium-containing alloy metal layer produced as described above has a metal layer of 0.1% to 54% gadolinium and 99.9% to 46% first based on the mass of the entire metal layer. Of metals. The product of the present invention having the metal layer has functions such as decoration, corrosion resistance, wear resistance, solder wettability, electrical conductivity, electrical resistance, and low contact resistance. The product having the gadolinium-containing gold metal layer of the present invention can use the metal layer having these functions as an electric / electronic member, a decorative member, and a medical member.

  It is not limited by theory that the product having the gadolinium-containing alloy metal layer of the present invention has such a property excellent in oxidation resistance, but it contains gadolinium having a dense crystal structure by adding gadolinium. This is probably because the alloy metal layer was formed.

  Hereinafter, although an example and a comparative example explain the present invention and an effect, an example does not limit an application range of the present invention.

(Heat resistance test)
A substrate having a gadolinium-containing alloy metal layer on the surface was heated for 5 minutes at the temperature shown in Table 2 or Table 3, and changes in the substrate surface were observed. Furthermore, the substrate surface subjected to the heat treatment was evaluated by a cross-cut method (1 mm interval).

(Contact resistance)
A substrate having a gadolinium-containing alloy metal layer on its surface was sandwiched between a pair of terminal electrodes. The contact area between the terminal electrode and the substrate was 10 cm ^2, and the terminal electrode was pressed against the substrate with a force of 1000 N. In this state, a current of 5.00 A was passed between the terminal electrodes, and the potential difference between one terminal electrode and the substrate was measured. The contact resistance value was determined using the obtained potential difference.

(Measurement method of surface Vickers hardness)
Using a surface hardness tester (DMH-2 type) manufactured by Matsuzawa Co., Ltd., a load of 0.245 N (25 gF) was applied in a normal temperature environment, and the measurement was performed under a load condition of 15 seconds.

(Salt spray test)
Based on JIS H8502, a neutral salt spray test (5% -NaCl aqueous solution) was performed on a substrate having a gadolinium-containing alloy metal layer on the surface. The state of the substrate surface (presence of corrosion) was observed after 1 hour, 24 hours, and 168 hours.

(Solder wettability test)
Based on JIS Z3196, a solder wettability test by a wetting balance method was performed on a substrate on which a metal layer was formed. In the solder bath, tin-lead eutectic solder (tin: lead = 60%: 40%) as lead-based solder, tin-silver-copper solder (tin: silver: copper = 96.5%: 3%) as lead-free solder : 0.5%; Senju Metal M705).

(Electroplating method)
Each component was mixed at the concentrations shown in Table 1 to prepare a plating bath. The prepared plating bath showed strong acidity.

Electrolytic plating was performed on the iron-based substrate and the copper-based substrate in the plating bath. A base material is immersed in a plating bath at 25 to 30 ° C., and a current density of 0.5 to 5.0 A / dm ² is applied for 1 to 2 minutes using the base material as a cathode, and a gadolinium-containing alloy metal is applied to the surface of the base material. A layer was formed. Table 1 shows the gadolinium content of the obtained gadolinium-containing alloy metal layer.

(Sputtering method)
Each metal alloy target shown in Table 3 was prepared and loaded into a sputtering apparatus. After evacuating the inside of the apparatus to 2 × 10 ⁻⁴ Pa, on the iron-based substrate and on the copper base under the conditions of sputtering pressure 0.1 Pa, argon 100%, sputtering output 0.1 W / cm ² , sputtering time 30 seconds. A gadolinium-containing alloy metal layer was formed on each substrate.

(Physical property test)
Regarding the gadolinium-containing alloy metal layer obtained by the electroplating method and the metal layer obtained from the plating baths of Comparative Examples 1 to 3 described in Table 2, regarding heat resistance, contact resistance value, Vickers hardness and salt water durability Table 2 shows the results of the test.

  The film thickness measurement of the gadolinium containing alloy metal layer obtained by the said sputtering method, and the test regarding heat resistance, a contact resistance value, Vickers hardness, and salt water durability were done. The results are shown in Table 3.

  In the substrate (Comparative Examples 1 and 3) on which the metal layer not containing gadolinium was formed, discoloration was observed after the heat resistance test. On the other hand, Examples 1 to 11 of the present invention were confirmed to have sufficient heat resistance without causing discoloration or peeling.

  Moreover, even if it contained gadolinium, in the case of the metal layer containing 0.01% gadolinium (Comparative Example 2), corrosion was observed in the salt spray test. On the other hand, corrosion was not seen in the board | substrate with which the gadolinium containing metal layer of this invention was formed (Examples 1-11).

  Next, a solder wettability test was performed on the obtained alloy metal layer. The results are shown in Table 4.

  As shown in Table 4, the examples of the present invention have good solder wettability for both lead-based solder (tin-lead eutectic solder) and lead-free solder (tin-silver-copper solder). It was found to have

(Production of electrical member 1)
An Ag-Gd alloy metal layer was prepared on the copper-based material terminal for car electronics using the plating bath of Example 2. This terminal maintains the same electrical conductivity as the terminal without the alloy metal layer, and there is no problem in discoloration and adhesion in the heat test and heat shock test, and also discolors after 24 hours in the salt spray test. There wasn't.

(Production of electrical member 2)
An Ag—Gd alloy metal layer was prepared on the copper-based material terminal for outdoor use for electric power using the plating bath of Example 2. This terminal maintained sufficient electrical conductivity and did not discolor after 24 hours in the salt spray test.

Claims (9)

A product having a support and a metal layer formed on the support,
The layer comprises 0.1% to 54% gadolinium and 99.9% to 46% first metal, based on the total weight of the metal layer.   The product of claim 1, wherein the first metal is selected from silver, tin, chromium, nickel, and copper.   The product of claim 1, wherein the layer is 0.01 μm to 5 mm thick.   The product of claim 1, wherein the layer further comprises a second metal.   The product of claim 4, wherein the second metal is included in an amount of less than 30%.   The product of claim 4, wherein the second metal is palladium.   The product according to claim 1, wherein the product is an electronic member, a decorative member, or a medical member. A product having a support and a layer made on the support,
The method of manufacturing a product, wherein the layer includes 0.1% to 54% gadolinium and 99.9% to 46% of the first metal based on the mass of the entire metal layer.   9. The method of claim 8, wherein the method is selected from the group consisting of electroplating, electroless plating, chemical vapor deposition, and physical vapor deposition.