Metal structure, metal structure manufacturing process, spring, chronograph coupling lever for timep

专利摘要:
A metal structure (6) includes, as a percentage of mass, 10% to 30% iron; 0.005% to 0.2% sulfur; and the remainder of nickel, excluding impurities, wherein a maximum grain size of the metal structure (6) is 500 nm or less. The present structure is adapted to be used as a spring in the field of watchmaking.
公开号:CH707724B1
申请号:CH00368/14
申请日:2014-03-12
公开日:2018-10-31
发明作者:Konishi Miei；Kishi Matsuo；Niwa Takashi
申请人:Seiko Instr Inc；
IPC主号:

专利说明:

Description
Technical Field [0001] The present invention relates to a metal structure, a method of manufacturing a metal structure, a spring, a chronograph coupling lever for a timepiece and a timepiece.
Prior Art [0002] In the prior art, many small machine components such as a gear and a spring are mounted on a mechanical timepiece which is a small precision instrument.
In the prior art, these kinds of machine components are mainly manufactured by machining such as punching. However, in recent years, a method of manufacturing these machine components using electroplating has been adopted. This is because in electroplating, the manufacturing tolerance is smaller compared to the machining, and even in a complex external form, the manufacture can be carried out with precision. As a result, electroplating is a particularly suitable method in the manufacture of fine and precise machine components.
One of the methods of manufacturing a small component with a high dimensional accuracy is, for example, the LIGA technology in which photolithography (lithography) and electroplating (Galvanoformung) are combined (for example, in the document non-patent 1).
Here, among small machine components constituting a mechanical timepiece, a component such as a chronograph coupling lever spring has a spring function (hereinafter referred to as a "component of spring"). In this spring component, excellent fatigue properties and high strength are required to improve excellent connectivity with other components. In addition, since the spring component controls the connection to other components by repeating the arming and disarming, restoration properties of the original form during disarming are required. That is, properties capable of reducing the amount of permanent stress that remains as deformation after disarming, ie, stress relief properties are required for the spring component.
Document of the prior art
Non-Patent Document [0006] Non-Patent Document 1: Journal of the Surface Finishing Society of Japan, Vol. 55 (2004), No. 4, pp. 226-231 Summary of the invention
[0007] In recent years, nickel (Ni) has been widely used as a representative electroplating material, and a structure made of nickel has been used in a spring component.
However, the present inventors have examined the stress relaxation resistance properties of a spring component manufactured by nickel electroplating. From the investigations, the present inventors have found that even at a load equal to or smaller than the elastic limit, namely a load in a zone of elastic deformation, it is difficult to obtain excellent properties of resistance to stress relaxation. That is, the present inventors have found that the spring component made by nickel electroplating has a problem in that even when the spring unit is disarmed after being deformed for a long time, the component spring does not return to its original form. In addition, in a device that uses these spring components, there is the risk that a failure may occur.
The invention has been made in consideration of the circumstances described above, and its object is to create a metal structure which is highly accurate and capable of suppressing the stress relaxation rate, a method of manufacturing a metal structure, a spring component, a chronograph coupling lever for a timepiece, and a timepiece.
Means for Solving Problems [0010] The present inventors have conducted a thorough examination to solve the problems described above, and the present inventors have found that when the fabrication is carried out with electroplating of nickel alloy and iron ( Ni-Fe), and when the heat treatment conditions after electroplating, in particular, the heat treatment temperature and the heat treatment time, are optimized, the stress relaxation rate can be greatly reduced.
In addition, the present inventors have found that, when the heat treatment conditions are optimized, the magnification of the grains is suppressed and therefore mechanical properties such as the Young's modulus, the elastic limit, and the hardness of the Vickers can be improved.
The present invention was carried out on the basis of the findings described above and the essence of the present invention is as follows.
[0013] [1] A metal structure according to one aspect of the present invention includes, in percent by weight, 10% to 30% iron (Fe); 0.005% to 0.2% sulfur (S); and the remainder composed of nickel (Ni), apart from impurities, wherein the maximum grain size of the metal structure is 500 nm or less and wherein the stress relaxation rate of the metal structure (6 ) is 10% or less.
In the metal structure according to [1], the network constant of the metal structure can be 3.53510-10 m to 3.5610 "10 m.
In the metal structure according to any of the points [1] or [2], the elastic limit of the metal structure may be 1500 MPa or more and the Young's modulus of the metal structure can be 150 GPa or more.
In the metal structure according to any of the points [1] to [3], the Vickers hardness of the metal structure can be Hv 580 or less.
[0017] [5] A method of manufacturing a metal structure according to another aspect of the present invention includes electroplating of the metal structure including, in weight percent, 10% to 30% iron (Fe). ); 0.005% to 0.2% sulfur (S); and the remainder composed of nickel (Ni), apart from impurities, and then carrying out a heat treatment to the metal structure under conditions in which the heat treatment temperature is 140 ° C to 350 ° C and the parameter P = Tx (C + log (t)) is in a range of 7500 to 9500, T, C and t being respectively the temperature in Kelvin of the termic treatment, the constant of material present in the formula making it possible to calculate the parameter of Larson-Miller and the duration in hours of heat treatment.
In the method of manufacturing a metal structure according to item [5], the heat treatment temperature may be equal to or higher than 140 ° C and lower than 275 ° C.
[0019] [7] A spring according to yet another aspect of the present invention includes the spring formed by the metal structure according to any of the points [1] to [4].
[0020] [8] A chronograph coupling lever for a timepiece according to yet another aspect of the present invention includes the chronograph coupling lever for a timepiece formed by the spring according to point [7] .
[0021] [9] A timepiece according to yet another aspect of the present invention is the timepiece which comprises the spring according to point [7] as an assembly component.
[0022] [10] A timepiece according to yet another aspect of the present invention is the timepiece which comprises the chronograph coupling lever for a timepiece according to point [8] as a component of assembly.
Effects of the invention [0023] According to the present invention, it is possible to create a metal structure being able to greatly reduce the stress relaxation rate by defining heat treatment conditions, particularly, the Larson-Miller parameter, after electroplating.
In addition, when the heat treatment conditions are optimized, the magnification of the grains is removed in comparison with a nickel electroplating known in the prior art and therefore mechanical properties such as the Young's modulus, the limit of elasticity, and the hardness of Vickers can be improved.
In addition, according to the method of manufacturing a metal structure of the present invention, the technology for manufacturing a small, highly accurate component is applicable to a spring component, and therefore the accuracy of a device (for example, a timepiece), which uses the highly accurate component, is also improved. Moreover, since the method of manufacturing a metal structure according to the present invention adopts electroplating, the mineral structure can be designed more flexibly in shape. Therefore, the method makes possible a mechanism or miniaturization, which is not achieved by a material in the prior art.
Brief description of the drawings [0026]
Fig. 1 is a graph illustrating the relationship between the iron content and the stress relaxation rate in a metal structure.
Fig. 2 is a graph illustrating the relationship between the iron content (as a percentage of mass) and the lattice constant (10_1 ° m) in a metal structure.
Fig. 3 is a graph illustrating the relationship between the lattice constant (10 m) and the stress relaxation rate (%) in a metal structure.
Fig. 4 is a flowchart (schematic sectional view of a metal structure) illustrating a method of manufacturing a metal structure.
Fig. 5A is a schematic view of a configuration of an electroplating device.
Fig. 5B is a schematic view of a configuration of an electroplating device.
Fig. 6 is a graph illustrating the relationship between LMP and the stress relaxation rate in examples.
Fig. 7 is a graph illustrating the relationship between LMP and the Young's modulus in examples.
Fig. 8 is a graph illustrating the relationship between LMP and the yield strength in examples.
Fig. 9 is a graph illustrating the relationship between LMP and Vickers hardness in examples.
Fig. 10 is a graph illustrating the relationship between LMP and the maximum grain size in examples.
Fig. 11 is the X-ray diffraction spectrum of conditions 1,2, 5, and 8 of Table 1.
Fig. 12 is a graph illustrating the relationship between LMP and the lattice constant obtained from the X-ray diffraction spectrum of FIG. 11.
Fig. 13 is a graph illustrating the relationship between LMP and the full width at the maximum half of the plane (111) that is obtained from the X-ray diffraction spectrum of FIG. 11.
Fig. 14 is a graph illustrating the relationship between LMP and the full width at the maximum half of the plane (200) that is obtained from the X-ray diffraction spectrum of FIG. 11.
Description of Embodiments [0027] In the following, embodiments of the present invention will be described.
Metal Structure [0028] First, a metal structure according to the present invention will be described.
The metal structure of the present invention includes, as a percentage of mass, 10% to 30% iron (Fe); 0.005% to 0.2% sulfur (S); and the balance of nickel (Ni), excluding impurities, wherein the maximum grain size is 500 nm or less.
In addition, the constant of the network of the metal structure is preferably in a range of 3.535 10_1 ° m to 3.56 10_1 ° m to reduce the stress relaxation rate. In addition, it is effective for the network constant of the metal structure after a heat treatment to be 99.95% or less of the network constant as formed by electroplating to further increase the effect of reducing the relaxation rate of constraints.
[0031] Hereinafter, the configuration of a metal structure according to the embodiment will be described.
10% to 30% iron, in weight percent [0033] From the review of the present inventors, the present inventors found that when the iron content in the metal structure is in a range of 10% to 30%, the stress relaxation rate of the metal structure can be reduced.
[0034] Hereinafter, details of the examination, the results of the examination and a mechanism for reducing the stress relaxation rate by iron will be described.
FIG. 1 is a graph illustrating the relationship between the iron content (as a percentage of mass) and the stress relaxation rate in the metal structure. In the graph, nickel electroplating data points represent "condition 0" results in the following Table 1, and nickel-iron electroplating data points represent results of using metal structures in which the Iron content is varied when the heat treatment temperature after electroplating is 250 ° C, the heat treatment time is 3 hours and the Larson-Miller parameter (LMP) is 8618.
In addition, the stress relaxation rate can be obtained by the following expression (2) according to JIS B27122006 Method of stress relaxation test for the plates for springs. Compared to the test conditions, deformation for 48 hours can be applied with a constant amount of displacement in a thermostatic bath set at 80 ° C. Details of the LMP will be described later.
Stress relaxation rate (%) = (θ / δ0) x 100 (2) Furthermore, in expression (2), δ 0 represents the initial stress (mm) and <> represents the permanent stress (mm) ) which remains after the charge release.
As shown by the expression (2), the greater the permanent stress (the smaller the recovery force), the higher the stress relaxation rate becomes, and therefore the stress relaxation resistance properties. deteriorate.
In the graph of FIG. 1, in the case of nickel electroplating of the prior art, the stress relaxation rate shows a high value exceeding 40%. On the other hand, in the case of nickel-iron electroplating, it can be observed that the stress relaxation rate decreases as well as an increase in the iron content and it is therefore possible to control the stress relaxation rate at 10%. or less.
As described above, in the metal structure according to the embodiment, the iron content is set at 10% to 30%, as a percentage of mass. In addition, as a weight percentage, the iron content is preferably 15% or more, and more preferably 20% or more, to further reduce the stress relaxation rate. In addition, when the upper limit of the iron content is 30%, as a percentage of mass, it is possible to show the effect of sufficient reduction of the stress relaxation rate. However, from the point of view of productivity and saturability of the stress relief reduction effect, the upper limit can be 28% or less per mass.
[0041] Hereinafter, a mechanism for reducing the stress relaxation rate by addition of iron will be described.
As is the case with nickel electroplating in the prior art, the present inventors considered that the reason for the defect in shape to be caused by the remainder as a permanent constraint even with a low load equal to or smaller of the elastic limit in addition to the increase of the stress relaxation rate is a deformation (sliding) of a lattice defect generated in the grain boundary. In addition, from one review, the present inventors have found that the occurrence of stress relaxation at an early stage is affected by a failure of the intragranular network and the like rather than a defect of the intergranular network.
[0043] Next, the present inventors have found that the generation of sliding can be suppressed by regulating the intragranular atomic arrangement and reducing the defect of the intragranular network in order to reduce intragranular sliding.
A nickel-iron alloy takes a form in which the iron is mixed in solid solution in nickel and the iron is completely mixed in solid solution in a crystal lattice of nickel up to approximately 30%, as a percentage of mass. In a state as electroplated prior to the heat treatment, since the arrangement of iron atoms mixed in solid solution in the nickel crystal lattice is random (irregular), it is in a state in which sliding is likely to occur by facilitating the migration of atoms due to multiple sliding directions caused by the crystalline nickel lattice which is cubic to center-face (fcc). Therefore, when the heat treatment is carried out after the electroplating to arrange the iron atoms to a regular and stable position, it is possible to suppress the generation of sliding.
Especially, when the relationship between nickel and iron (Ni: Fe) (the percent mass ratio) is 3: 1, in a Ni crystal array that is a face centered cubic lattice (fcc), the state in which the iron is arranged at each vertex of fcc becomes a regular arrangement. In this way, a state in which iron is arranged at each vertex of fcc represents a state in which a nickel atom and an iron atom, which have different atom sizes from each other, are arranged alternatively when they are observed from the plane (111) which is a sliding plane. That is, a pitch difference is generated between the nickel atom and the iron atom and this pitch difference is aligned in a regular manner, and thus it is possible to realize a state in which the sliding caused by an atom migration is not likely to appear. That is, when one approaches a composition in which the relationship between nickel and iron (Ni: Fe) (the percent mass percentage) is 3: 1, the iron is arranged at each At the top of fcc, the sliding plane becomes irregular due to the step difference, and therefore, it is possible to prevent the generation of elastic deformation.
In addition, as described in the assumption that the state in which iron is arranged at each vertex of fcc becomes regular when the mass percentage ratio between nickel and iron is 3: 1, but precisely the regular arrangement is obtained when the ratio between nickel and iron in atomic percentage is 3: 1. Therefore, the assumption that the percent atomic percent ~ mass percent ratio may be possible because nickel and iron are elements having a similar atomic weight.
[0047] S: 0.005% to 0.2%, by weight percent [0048] In the metal structure according to the embodiment, 0.005% to 0.2% sulfur (S) as a percentage of mass is contained. Sulfur is derived from nickel sulfamate tetrahydrate, ferrous sulfamate pentahydrate, surfactant, primary brightener, and the like in an electroplating bath during the electroplating process. In the electroplating process, metal ions react in a negative electrode and thus the metal precipitates. However, non-metallic ions and the gloss agent, which adhere to the surface of the negative electrode, are also captured in an electroplated material. Accordingly, elements such as sulfur, oxygen (O) and hydrogen (H), which are contained in the bath composition and which are typically regarded as unavoidable impurities, are eutectoid. That is, in the embodiment, it is possible to control the sulfur content in the metal structure by adjusting the composition of nickel sulfamate tetrahydrate, ferrous sulfamate pentahydrate, surfactant, and the like. .
In addition, sulfur is an impurity, and smaller is its content, more it is preferable from the point of view of the properties of the metal structure. As a result, the upper limit of the sulfur content is preferably set to 0.1%, in percent by weight. On the other hand, when the sulfur content is excessively reduced, there is the risk that an increase in electroplating costs may be caused. Therefore, the lower limit of the sulfur content is preferably set to 0.01% or more per mass.
As described above, the body formed by electroplating according to the embodiment has a composition including 10% to 30% iron and 0.005% to 0.2% sulfur, as a percentage by weight, and the rest consists of nickel. and unavoidable impurities. However, trace elements may be included in a range that does not deteriorate the effect of the present invention.
In addition, the maximum grain size of the metal structure according to the embodiment is 500 nm or less.
The maximum grain size has a great effect on the mechanical properties such as yield strength and Vickers hardness. When the maximum grain size is reduced, that is, when the enlargement of the grain size is removed, it is possible to reduce the stress relaxation rate by maintaining the mechanical properties described above. To expose these effects, it is important that the maximum grain size of the metal structure is 500 nm or less. In addition, the maximum grain size of the metal structure is preferably 400 nm or less, and still more preferably 300 nm or less. On the other hand, from the point of view of the effects described above, the smaller the grain, the better. In the embodiment, the lower limit of the maximum grain size is not particularly limited, but substantially the maximum grain size is 10 nm or more.
In addition, the lattice constant of the metal structure is preferably set in a range of 3.535 10_1 ° m to 3.56 10_1 ° m to reduce the stress relaxation rate of the metal structure.
FIG. 2 shows a graph illustrating the relationship between the iron content (as a percentage of mass) and the lattice constant (10_1 ° m) in the metal structure. In addition, FIG. 3 is a graph illustrating the relationship between the lattice constant (10 -10 m) and the stress relaxation rate (%) in the metal structure. Nickel plating data points represent "condition 0" results in the following Table 1, and nickel-iron electroplating data points represent results of use of metal structures in which the iron content is varied when the heat treatment temperature after electroplating is 200 ° C, the heat treatment time is 3 hours and the LMP is 7794. In addition, the lattice constant is obtained from a diffraction ray spectrum. X of each metal structure that is obtained.
From the graph of FIG. 2, in one case of the metal structure obtained by nickel-iron electroplating, it can be observed that in addition to an increase in the iron content, the network constant tends to increase. This is believed to be due to the fact that a nickel-iron alloy takes a form in which iron is mixed in solid solution in nickel. That is, in the case of the metal structure obtained by electroplating nickel-iron, the iron element larger than the nickel elements is mixed in solid solution in the crystal lattice of nickel. As a result, it is considered that when the iron content in the metal structure increases, the network constant also increases.
In addition, the graph of FIG. 3, it can be observed that in addition to an increase in the lattice constant, the stress relaxation rate tends to decrease.
From the foregoing, the lattice constant of the metal structure according to the embodiment is preferably set in a range of 3.535 10_1 ° m to 3.56 10_1 ° m.
In addition, the present inventors conducted a further examination of the lattice constant of the nickel-iron alloy (metal structure). From this examination, the present inventors have found that, when one approaches a state in which the iron is regularly arranged in the crystal lattice of nickel as described above, it is possible to make the network constant smaller in size. comparison to the state as formed by electroplating (where the iron atoms are arranged randomly). That is, since the state in which the iron atoms are randomly arranged, the iron atoms become arranged regularly due to a heat treatment, and therefore it is considered that it is possible to reduce the network constant.
As described above, when the heat treatment is carried out at the metal structure to convert the arrangement of the atoms from a state where this arrangement is irregular to a state where this arrangement is regular, and therefore when the state The network in which the iron is mixed in solid solution in the crystal lattice of nickel can be stable and solid, and therefore it is possible to reduce the stress relaxation rate.
The constant of the network of the metal structure after the heat treatment is preferably 99.95% or less with respect to the constant of the network as formed by electroplating to have the effect of reducing the stress relaxation rate.
Then, the mechanical properties of the metal structure will be described.
The stress relaxation rate of the metal structure according to the embodiment is preferably 10% or less. As described above, when the composition of the metal structure is set to include 10% to 30% iron and 0.005% to 0.2% sulfur and the maximum grain size is set to 500 nm or less, it is possible to greatly reduce the rate of stress relaxation. In addition, the stress relaxation rate is preferably 5% or less.
In addition, when the constant of the network of the metal structure is set in a range of 3.535 10_1 ° m to 3.56 10_1 ° m, and the network constant of the metal structure after the heat treatment is 99.95% or less than the lattice constant as formed by electroplating, it is possible to further reduce the stress relaxation rate.
In addition, from the point of view of the guarantee of excellent fatigue properties and high strength, the yield strength of the metal structure according to the embodiment is preferably 1500 MPa or more and the Young's modulus is preferably 150 GPa or more. More preferably, the yield strength is 1600 MPa or more and the Young's modulus is 160 GPa.
In addition, the Vickers hardness of the metal structure according to the embodiment is preferably Hv 580 or higher. For example, when the metal structure is applied to the machine components and the like, high strength is required. As a result, it is preferable to guarantee Vickers hardness of Hv 580 or more for the metal structure, and more preferably of Hv 600 or higher.
Method of Manufacturing a Metal Structure [0066] Next, a method of manufacturing the metal structure described above will be described.
The method of manufacturing the metal structure according to the embodiment includes the electroplating formation of the metal structure including, as a percentage of mass, 10% to 30% iron (Fe); 0.005% to 0.2% sulfur (S); the rest composed of nickel (Ni) and unavoidable impurities; and performing a heat treatment to the metal structure at the conditions at which the heat treatment temperature is 140 ° C to 350 ° C and the Larson-Miller parameter is in a range of 7500 to 9500. In addition, from the point In view of the compatibility of the reduction of stress relaxation rate and high strength, the heat treatment temperature is preferably equal to or higher than 140 ° C and lower than 275 ° C.
[0068] Hereinafter, respective conditions in the manufacturing method according to the embodiment will be described in detail with reference to the attached drawings.
FIG. 4A is a view illustrating a method of forming an electrode for electroplating.
First, as shown in FIG. 4A, an electrode 3 which is a negative electrode is formed on a substrate 2 in an electroplating process.
For the substrate 2, silicon, quartz, sapphire, various materials such as stainless steel and titanium can be used. As electrode material 3, copper, gold, chromium, titanium, and the like can be used. In addition, when a metallic material is adopted as the substrate 2, the electrode 3 can not be formed. In this case, the substrate 2 can function as the electrode (negative electrode) for electroplating.
The thickness of the substrate 2 is preferably between 100 μm and 1 mm to be easily shaped in subsequent processes. In addition, the thickness of the electrode 3 is preferably 10 nm or more from the point of view of guaranteeing stable electrical conduction and minimum strength required in the following electroplating process. On the other hand, when the thickness of the electrode 3 is too wide, there is the risk that detachment may occur due to the action of a constraint or time is needed for a formation of movie. Accordingly, the thickness of the electrode 3 is preferably 10 μm or less.
FIG. 4B is a view illustrating a method of forming a resin.
Then, as shown in FIG. 4B, a photoresist 4 is formed on the electrode 3. The photoresist 4 may be of a negative type or a positive type, and may be formed using a spin coating method or an immersion coating method. In addition, when a photoresist is used as a photoresist, the photoresist may be formed using a lamination process.
The thickness of the photoresist resin 4 is equal to or greater than the thickness of the metal structure 6 (see Fig. 4F) which is formed in a subsequent treatment.
[0076] Hereinafter, the following case when a negative type is used as photoresist resin will be described.
FIG. 4C represents a view illustrating a development process.
Then, as shown in 4C, first, a photomask (not shown) having the outer pattern of the metal structure 6 (refer to Fig. 4F) to be formed in a subsequent process is used, and the resin The photoresist 4 is irradiated with ultraviolet light, thereby drying the photoresist 4 elsewhere than in an area in which the electroplating material is allowed to precipitate in a subsequent electroplating process. Then, the photoresist resin 4 (of the area in which the electroplating material is allowed to precipitate) which is not dried is removed to form an electroplating mold 7 having a pattern unit 1 to form the outer shape of the metal structure 6 (refer to Fig. 4F). The pattern unit 1 shown has a concavity 1a to form the outer shape of the metal structure 6 and a column 1b which is supported by a bottom surface of the concavity 1a to form a penetration hole 10a (refer to FIG. Fig. 4F) in the metal structure 6. In addition, although not shown, it is assumed that the plurality of pattern units 1 are formed in the die direction in the electroplating mold 7.
In addition, as a method of forming the electroplating mold 7 in the embodiment, a description is made with reference to the process of forming the electrode for electroplating in the development process as shown in FIGS. 4A to 4C. However, the present invention is not limited thereto, and a known method can be adopted as a method of forming the electroplating mold 7.
FIG. 4D represents a view illustrating the electroplating process.
Then, as shown in FIG. 4D, the electroplating mold 7 is placed in an electroplating device 20 (see Fig. 5A) to form an electroplated material 5 formed of a nickel-iron alloy on the electrode 3 which is exposed.
[0082] Hereinafter, the electroplating process using the electroplating device 20 shown in FIGS. 5A and 5B will be described in detail.
Figs. 5A and 5B show schematic configuration views of the electroplating device 20.
As shown in FIG. 5A, the electroplating device 20 includes an electroplating tank 21 in which an electroplating liquid W containing nickel ions and iron ions is stored, a positive electrode 22 which is immersed in the electroplating liquid W, and a unit energy source 24 which is connected to the positive electrode 22 and the electrode (negative electrode) 3 which is formed in the electroplating mold 7 by an electrical interconnection 23.
Since the electroplating material is formed of a nickel-iron alloy, as electroplating liquid W according to the embodiment, an electroplating liquid containing nickel ions and iron ions is used. In addition, in the embodiment, it is important to precipitate an electroplated body having a composition containing 10% to 30% iron and 0.005% to 0.2% sulfur, the remainder consisting of nickel, excluding impurities. . As a result, a composition or mixing adjustment of the electroplating liquid W is made to obtain the composition described above.
Nickel sulphate, nickel chloride, nickel sulphamate, and the like can be used as a source of nickel, and ferrous sulphate, ferrous chloride, ferrous sulphamate, and the like can be used as the source of iron. . In addition, boric acid, acetic acid, citric acid, and the like may be added as a buffering agent. In addition, a surfactant based on the sulfuric acid ester, a surfactant based on the alkylarylsulfonic acid, and the like can be added as a pit-prevention agent. In addition, sodium saccharinate, sodium naphthalene sulphonate, and para-toluene sulphonamide may be added as the primary brightener, and butynediol, formaldehyde, and the like may be added as a secondary brightener. In addition, an antioxidant such as ascorbic acid and isoascorbic acid, or a complexing agent such as malonic acid, tartaric acid, and succinic acid may be added.
[0087] Hereinafter, preferred examples of an electroplating bath composition and electroplating conditions will be described. However, the bath composition and conditions can be suitably changed in a range not detrimental to the effect of the present invention, namely, in an electroplating bath composition and electroplating conditions that allow a shaped body. by electroplating containing 10% to 30% iron and 0.005% to 0.2% sulfur precipitate, and the present invention is not limited to the following examples.
Electroplating Bath Composition [0088]
- Nickel sulphamate tetrahydrate: 200 g / L to 300 g / L
- Nickel chloride hexahydrate: 2 g / L to 10 g / L
- Ferrous sulphamate pentahydrate: 5 g / L to 50 g / L
- Boric acid: 10 g / L to 50 g / L
- Surfactant: 0.1 g / L to 10 g / L
- Primary gloss agent: 1 g / L to 15 g / L
- Secondary gloss agent: 0.05 g / L to 5 g / L
- Antioxidant: 0.1 g / L to 10 g / L - pH: 2 to 4
- Bath temperature: 40 ° C to 60 ° C
Electroplating Conditions [0089] Current Density of the Negative Electrode: 1A / dm2 to 10A / dm2 [0090] The electroplating process is performed using the electroplating device 20 configured as described above.
Firstly, in a state of being mounted on a jig 26, the electroplating mold 7 provided with the electrode (negative electrode) 3 is immersed in the electroplating liquid W stored in the electroplating tank 21, and then the energy source unit 24 is turned on to apply a voltage between the positive electrode 22 and the negative electrode 3. In this case, nickel ions and iron ions in the electroplating liquid W migrate. in the liquid to the side of the negative electrode 3, and precipitate as a nickel-iron alloy on a surface of the negative electrode 3 as shown in Figs. 5A and 5B and grow further, when the electroplated body 5 is obtained. In the embodiment, the electroplated body 5 is formed on the entire main surface (within the concavity 1a and on the surface of the resin 4) of the electroplating mold 7.
The body formed by electroplating 5 having a thickness wider than the thickness of the metal structure 6 is precipitated. That is, since the depth of the concavity 1 a is equal to the thickness of the metal structure 6, the nickel-iron alloy is allowed to grow at least until the concavity 1 a the electroplating mold 7 is filled with the body formed by electroplating 5. However, when the sanding and polishing process shown in FIG. 4E is omitted in the subsequent process, the electroplated body 5 is allowed to precipitate to have the same thickness as the metal structure 6.
FIG. 4E is a view illustrating the sanding and polishing process. The electroplated body 5 obtained in the electroplating process described above grows to have the thickness of the metal structure 6, and the surface of the electroplated body 5 is polished and finished to have a mirror surface.
Then, as shown in FIG. 4E, the sanding and polishing process is carried out. Specifically, the electroplating mold 7, in which the electroplated body 5 is formed, is removed from the electroplating tank 21 (see Figs 5A and 5B), and the electroplated body 5 obtained in the electroplating process. is ground so that the electroplating mold 7 has the thickness dimension of the metal structure 6. In the embodiment, the sanding is performed so that the electroplated body 5 formed on the surface of the electroplating mold 7 is removed (so that the formed electroplating body 5 formed inside the concavity 1 has left). In addition, in the embodiment, it is preferable that the electroplated body is crushed to have the thickness of the metal structure 6 and the surface of the electroplated body 5 is polished to become a surface. mirror.
FIG. 4F represents a view illustrating the process of gripping the body formed by electroplating.
Finally, as shown in FIG. 4F, in the process of gripping the electroplated body, the electroplated body 5 remaining inside the pattern unit 1 (concavity 1a) of the electroplating mold 7 is pulled out of the electroplating mold 7. Specifically , the substrate 2, the electrode 3, and the photoresist resin 4 are removed to remove the body formed by electroplating 5. However, the suppression method is not particularly limited, and for example, the deletion can be performed by etching . In addition, a physical force can be applied to release the electroplated body 5. According to this, it is possible to obtain the metal structure 6 formed by the electroplated body 5 made of the nickel-iron alloy.
In the embodiment, after the metal structure 6 is out of the electroplating mold 7, a heat treatment is performed with respect to the metal structure 6.
Specifically, the metal structure 6 that is obtained is subject to heat treatment at the conditions at which the temperature is 140 ° C to 350 ° C, and the Larson-Miller parameter is in a range of 7500 to 9500. The Heat treatment device is not particularly limited, and for example, a heating furnace that is used in a typical heating process can be used. Moreover, with respect to the atmosphere during the heat treatment, the heat treatment is preferably carried out under vacuum or in an inert gas such as argon and nitrogen (N2) from the point of view of the oxidation prevention of surface of the metal structure 6.
[0099] Hereinafter, the reason why the heat treatment conditions are limited will be described.
Generally, the heat treatment of a metal structure obtained by electroplating is carried out for the improvement of strength, the removal of residual stress, the grain size adjustment, and the like. That is, to obtain a metal structure having desired properties, it is important to optimize the heat treatment conditions, particularly, the heat treatment temperature and the duration of the heat treatment.
Therefore, the present inventors have made a thorough investigation with respect to the heat treatment conditions which are capable of greatly reducing the stress relaxation rate in the metal structure which is formed of the nickel-iron alloy and which are obtained by electroplating, which are capable of suppressing the grain magnification in comparison with the nickel electroplating of the prior art, and which are capable of improving mechanical properties such as the Young's modulus, the yield strength , and the hardness of Vickers. Therefore, the present inventors have found that even when trying to define respective appropriate ranges of heat treatment temperature and heat treatment time by its matrix to find the appropriate ranges of heat treatment temperature and heat treatment time the behavior of the stress relaxation rate that is obtained is complex, and therefore it is difficult to optimize the conditions only with the heat treatment temperature and the heat treatment time. Therefore, the present inventors have collected results that are obtained at various conditions of the heat treatment temperature and heat treatment times, in terms of stress relaxation rates, and they have found that it is possible to define the conditions with the parameter Larson-Miller (LMP).
[0102] The Larson-Miller process is one of the thermal acceleration test methods for estimating long-term properties from short-term test results. In addition, the parameter Larson-Miller P can be obtained by the following expression (1). In addition, in the expression (1), T represents the test temperature (in Kelvin), C represents the material constant, and t represents the test time (in hours).
(1) [0103] The present inventors have found that by performing the heat treatment under the conditions at which the Larson-Miller parameter P is in a range of 7500 to 9500 more at the definition of a suitable range of temperature of heat treatment, it is possible to greatly improve the mechanical properties including the stress relaxation rate of the metal structure.
Here, the material constant C is different depending on the material. Generally, a metal is set to 20 and a weld is set to 10 in many cases. However, documents, discoveries, and the like that define the material constant C of the electroplating material are not disclosed. Accordingly, in the present invention, the material constant C is obtained from a steering curve of the stress relaxation rate which is created by setting the LMP to the horizontal axis and adjusting the stress relaxation rate (%) to the vertical axis. Therefore, in the case of the metal structure formed by the nickel-iron alloy according to the present invention, when the material constant C is set to 16, the corresponding property of the guide curve is sufficient. Accordingly, in the present invention, the expression of the Larson-Miller parameter P is calculated by setting the material constant C to 16.
In the embodiment, the heat treatment is performed under the conditions at which the Larson-Miller parameter (LMP) is in a range of 7500 to 9500 and the heat treatment temperature is in a range of 140 ° C to 350 ° vs. When the heat treatment is performed at the conditions at which the LMP is 7500 or higher, the stress relaxation rate can be reduced, and the Young's modulus and yield strength can be improved. On the other hand, when the heat treatment is performed under the conditions at which the LMP is excessively wide, there is a risk that the yield strength and the hardness of Vickers may deteriorate, and thus the LMP is 9500 or less. In addition, the LMP is preferably in a range of 8000 to 9500 to obtain a stable Young's high modulus.
In addition, in the manufacturing method of this embodiment, the heat treatment temperature is in a range of 140 ° C to 350 ° C. However, from the point of view of the compatibility between a reduction of the stress relaxation rate and a high resistance, the heat treatment temperature is preferably set at a temperature equal to or higher than 140 ° C and lower than 275 ° C. ° C.
The present inventors have conducted an investigation of the relationship between the heat treatment conditions and the Vickers hardness in detail. Since this investigation, the present inventors have obtained the following new discovery. Compared to the metal structure obtained by electroplating nickel-iron, even when the LMP is in a range of 7500 to 9500, when the treatment is carried out at a high temperature, the hardness of Vickers tends to deteriorate.
In the following, a mechanism for reducing the hardness of Vickers due to the high temperature heat treatment will be described.
As described above, even at the same LMP condition, when the heat treatment temperature is high, the Vickers hardness tends to decrease. This is considered to be caused by the fragility of sulfur.
In the nickel electroplating of the prior art, it is known that a decrease in hardness due to the brittleness of the sulfur appears with a heat treatment of 215 ° C. or more, and therefore the decrease in hardness. is considered to occur due to a small amount of diffuse sulfur along the nickel grain boundary and is coupled with nickel, and decreases the cohesive force between grains. On the other hand, in nickel-iron electroplating, iron blocks the coupling between nickel and sulfur, and therefore it is considered that when heating is not performed at a temperature exceeding 275 ° C, which is higher than in the case of nickel electroplating, the brittleness of sulfur is not generated.
From the foregoing, the heat treatment temperature after electroplating is preferably a temperature equal to or higher than 140 ° C and lower than 275 ° C.
In addition, it is considered that the relaxation of stresses is affected by a defect inside a grain, and therefore it is considered that the brittleness of sulfur which is a phenomenon occurring in the grain boundary n ' has no effect on stress relaxation.
The metal structure according to the embodiment can be manufactured by the manufacturing method described above.
As described above, according to the manufacturing method, the metal structure of the present invention, in addition to the heat treatment temperature, the Larson-Miller parameter is optimized, and therefore it is possible to manufacture the structure metal capable of greatly reducing the stress relaxation rate.
In addition, according to the metal structure of the present invention, a grain magnification is suppressed in comparison with the nickel electroplating of the prior art, and therefore it is possible to improve the mechanical properties such as the module. of Young, the yield strength, and the hardness of Vickers.
In addition, according to the manufacturing method of a metal structure of the present invention, the technology for manufacturing a highly accurate small component is applicable to a spring component, and therefore the accuracy of a device (for example, a timepiece), which uses the highly accurate component, is also improved. In addition, since the method of manufacturing a metal structure according to the present invention adopts electroplating, the metal structure can be designed more flexibly in shape. Therefore, the process makes the mechanism or miniaturization, which was not achieved by the material in the prior art, possible.
In addition, the metal structure according to the present invention is applicable to an assembly component of a mechanical timepiece. For example, the metal structure can be adopted as a spring component for a chronograph mechanism. In addition, in a case of using the metal structure as a chronograph coupling lever spring among spring components, the spring unit is deformed during standby and is released during use. of the chronograph mechanism. However, the stress relaxation resistance properties are excellent, and thus the component is not likely to deform plastically, and it is possible to create a timepiece with high accuracy.
Examples [0118] Next, the present invention will be described in more detail with reference to the examples, but the present invention is not limited to the conditions used in the following examples.
First, an electroplating mold was formed according to the process shown in FIGS. 4A to 4C. When forming the electroplating mold, a silicon substrate having a thickness of 525 μm was used as the substrate, and a gold electrode was used as the electrode.
Subsequently, electroplating materials (metal structures) formed of a nickel-iron alloy having the composition shown in Table 1 (conditions 0 to 15 in Table 1) were manufactured by the electroplating device shown in FIG. in figs. 5A and 5B, and using the electroplating mold that was obtained. In addition, the "condition 0" shown in Table 1 represents a body formed by electroplating nickel (the comparative example), and represents an embodiment of an electroplating without adding "ferrous sulphamate pentahydrate" as a source of iron in the electroplating bath. In addition, the iron content in the table is measured by a fluorescent x-ray analyzer and represents a mass ratio of iron when nickel + iron is equal to 100.
[0121] Hereinafter, the electroplating bath composition and electroplating conditions will be described.
Composition of electroplating bath [0122]
- Nickel sulphamate tetrahydrate: 200 g / L to 300 g / L
- Nickel chloride hexahydrate: 2 g / l to 10 g / l
- Ferrous sulphamate pentahydrate: 5 g / L to 50 g / L
- Boric acid: 10 g / L to 50 g / L
- Surfactant: 0.1 g / L to 10 g / L
- Primary gloss agent: 1 g / L to 15 g / L
- Secondary gloss agent: 0.05 g / L to 5 g / L
- Antioxidant: 0.1 g / L to 10 g / L - pH: 2 to 4
- Bath temperature: 40 ° C to 60 ° C
Electroplating conditions [0123] Negative electrode current density: 1 A / dm2 at 10 A / dm2 [0124] Electroplating time: 320 minutes (when the negative current density is 4 A / dm2) [0125] The surface of the metal structure (thickness: 220 μm) that was obtained was polished to 200 μm and was shaped to obtain a mirror surface, the metal structure was removed from the electroplating mold, and a heat treatment was carried out at In addition, the "condition 1" metal structure represents an example of electroplating (the comparative example) without carrying out the heat treatment.
[0126]
Table 1
LU cs
UJ Ε ~ Ξ C_3
READ
S ζε α C_3
3E tzn c = 5
ZZI C3 C_3 ± 5
UU c = a <= c
LU 03
'UUI case
LU ca LXJ t-- 33 - = C oa zzz Cd C_3 55 5d Ä Cd ULJ UU d <χ Z_4 cxj »I 'LU LU ± UUJ = d • y ca <a:« ex Cd C_3 z3 -i 3 = - SC ca ca J-d -¾ <= £ = 3Z KiTi 03 r * -1 'LUI - GC -y UUJ = 3 1 = 3
I__ LLJ 33
i ± i 3 S oo Ξ5> 1_U Cd CS C_3 C- 1 I 1 § <= s
LU 03 03 GO GO 5
Ξχ 2-J
ULJ LU CX3 ZBZ <£ LUI H ± 03! ± j '^ 03 Eu CS - = C - ca *
Next, with respect to the metal structures (conditions 0 to 15), the stress relaxation rate, the Young's modulus, the elastic limit, the Vickers hardness, the maximum grain size, the network, and the full width to the maximum half were obtained. Results are shown in Table 1, and in FIGS. 6 to 14. "Condition 0" in Table 1 is an example (the comparative example) made by nickel electroplating. In addition, "condition 1" represents an example (the comparative example) in which the electroplating was performed without performing the heat treatment process after electroplating. However, in figs. 6 to 14, the "condition 1" LMP (as formed by electroplating) was initially zero, and the investigation was conducted in comparison with an electroplating material after another heat treatment on the assumption that the heat treatment was carried out at room temperature (25 ° C) for 3 hours and the LMP was 4910.
In addition, data relating to the respective properties shown in Table 1 were measured by adopting a chronograph coupling lever spring of a mechanical timepiece as an example of the metal structure formed by a formed material. by electroplating. In addition, the "rate of change (%) of the network constant" in Table 1 represents the rate of change of the network constant in the case of setting the network constant of "condition 1" as a reference.
In addition, data points in FIGS. 6 to 14 correspond to conditions 0 to 15, or are taken from conditions 0 to 15 in Table 1. "Lower than 275 ° C" and "275 ° C or higher" in Figs. 6 to 9 represent heat treatment temperatures.
The stress relaxation rate was obtained by the following expression (2) conforming to JIS B 27 122 006 method of stress relaxation tests for springs. Compared to the test conditions, a deformation was applied. relative to a spring unit of the chronograph coupling lever spring with a constant displacement amount for 48 hours in a thermostatic bath in which its temperature was 80 ° C. Moreover, in expression (2), δ 0 represents the initial tension (mm) and represents the permanent stress (mm) remaining after the release of the load.
(2) [0131] The load displacement curve of the spring unit of the chronograph coupling lever spring was created, and then the Young's modulus was obtained from the gradient of the elastic deformation zone.
In addition, with respect to the elastic limit, the amount of deformation with respect to the spring unit was increased for each cycle of the repetitive folding test, and the maximum tension in the amount of deformation when the load became zero before the spring unit returned to an initial position was set as a yield constraint required by analysis. In addition, in the embodiment, the load was measured by pressing a distal end of the spring unit of the chronograph coupling lever spring using a terminal mounted on a load cell, and the amount of displacement was measured. by a laser displacement meter.
The hardness of Vickers was obtained by measuring the surface of the three-point metal structure using a Vickers hardness micrometer and averaging the resulting measurement values.
In addition, the maximum grain size was obtained by observing a cross section of the spring unit of the chronograph coupling lever spring using a focused ion beam (FIB).
[0135] FIG. 6 represents a relationship between the LMP and the stress relaxation rate.
As can be seen in the graph of FIG. 6, when the metal structure is obtained by nickel-iron electroplating, the stress relaxation rate before the heat treatment (condition 1) was 35%, but when the heat treatment was performed under conditions at which LMP was 7500 or more, the stress relaxation rate was reduced to 5% or less. In addition, by comparing nickel electroplating and nickel-iron electroplating which were prone to heat treatment at the same LMP, it could be seen that in a case of nickel-iron electroplating, the stress relaxation rate could be reduced to approximately 1/10.
[0137] FIG. 7 represents the relationship between the LMP and the Young's modulus.
As can be seen in the graph of FIG. 7, Young's modulus before heat treatment was approximately 150 GPa, and showed a tendency to increase due to heat treatment and was saturated with LMP from 9000 to 9500. In addition, Young's modulus tended to increase rapidly in the vicinity of the 9500 LMP, but conversely, the Young's modulus changed to a LMP decrease trend of 9500 or more. Moreover, in nickel electroplating and nickel-iron electroplating which were prone to heat treatment at the same LMP, the Young's modulus was substantially the same in each case.
[0139] FIG. 8 represents the relationship between the LMP and the yield strength.
[0140] As it can be seen in the graph of fig. 8, the yield strength before the heat treatment was 800 MPa, and the yield strength showed a tendency to increase due to the heat treatment and was saturated with LMP from 9000 to 9500. In addition, the limit of yield elasticity decreased rapidly to LMP at 9500 or higher. Comparing the

权利要求:
Claims (10)
[1]
nickel electroplating and nickel-iron electroplating which were prone to heat treatment at the same LMP, it could be seen that in the case of nickel-iron electroplating, the yield strength increased twice or more. From these results, it could be seen that it is necessary to adjust the LMP in a range of 7500 to 9500 to make a metal structure having the yield strength of 1500 MPa or more. [0141] FIG. 9 represents the relationship between LMP and Vickers hardness. As can be seen in the graph of FIG. 9, the Vickers hardness prior to heat treatment was approximately Hv 580, and the hardness increased to 9000 LMP due to heat treatment. However, when the heat treatment temperature was 275 ° C or higher, the Vickers hardness showed a decreasing tendency. Moreover, by comparing nickel electroplating and nickel-iron electroplating which were subject to heat treatment with the same LMP condition, it could be seen that in the case of nickel-iron electroplating the hardness increased to about 20%. FIG. 10 represents the relationship between the LMP and the maximum grain size. [0144] Up to the 9500 LMP, the maximum grain size was approximately 500 nm without variation, and at the LMP of 9500 or higher, grain growth occurred rapidly and the maximum grain size increased rapidly. In addition, by comparing nickel electroplating and nickel-iron electroplating which were prone to heat treatment at the same LMP condition, the grain size in nickel-iron electroplating was approximately half the grain size in the nickel electroplating. [0145] FIG. 11 shows the X-ray patterns of conditions 1, 2, 5, and 8 of Table 1. As can be seen in FIG. 11, all the peaks that were observed related to a face-centered cubic nickel structure, and the iron was thoroughly mixed in solid solution in the crystal lattice of nickel. FIG. 12 represents the relationship between the LMP and network constants obtained by the X-ray diffraction spectrum of FIG. 11 and the network constant at condition 0. The network constant decreased due to the heat treatment, and became approximately constant in an LMP range of 7500 to 9500. In addition, in all cases, the rate of change of the network constant was 99.95% or less. Figs. Figures 13 and 14 show the relationship between the LMP and full widths at a peak half of the peaks (111) and the plane (200) that were obtained by the X-ray diffraction spectrum of FIG. 11. [0150] It could be seen that full widths at a maximum half of plane (111) and plane (200) decrease due to heat treatment. Explanation of references [0151] 1: Reason 2: Substrate 3: Electrode (negative electrode) 4: Photoresist 5: Body formed by electroplating 6: Metal structure 7: Electroplating mold
1. Metal structure (6) comprising, in percent by mass: 10% to 30% iron; 0.005% to 0.2% sulfur; and the remainder of nickel, excluding impurities, wherein a maximum grain size of the metal structure (6) is 500 nm or less, and wherein the stress relaxation rate of the metal structure ( 6) is 10% or less.
[2]
The metal structure (6) according to claim 1, wherein the lattice constant of the metal structure (6) is 3.535 10_1 ° m to 3.56 10_1 ° m.
[3]
Metal structure (6) according to one of claims 1 or 2, wherein the elastic limit of the metal structure (6) is 1500 MPa or more and the Young's modulus of the metal structure ( 6) is 150 GPa or more.
[4]
The metal structure (6) according to one of claims 1 to 3, wherein the Vickers hardness of the metal structure (6) is Hv 580 or higher.
[5]
A method of manufacturing a metal structure (6), the method comprising: electroplating the metal structure (6) including, in percent by mass, 10% to 30% iron; 0.005% to 0.2% sulfur; and the rest composed of nickel, apart from impurities; then carrying out a heat treatment to the metal structure (6) under conditions in which the heat treatment temperature is 140 ° C to 350 ° C and the parameter of P = Tx (C + log (t)) is in a range of 7500 to 9500, T, C and t being respectively the Kelvin temperature of the thermal treatment, the material constant present in the formula for calculating the Larson-Miller parameter and the time in hours of the heat treatment.
[6]
The method of manufacturing a metal structure (6) according to claim 5, wherein the heat treatment temperature is equal to or higher than 140 ° C and lower than 275 ° C.
[7]
7. Spring which is formed by the metal structure (6) according to one of claims 1 to 4.
[8]
8. Chronograph coupling lever for a timepiece which is formed from the spring according to claim 7.
[9]
9. Timepiece using the spring according to claim 7 as an assembly component.
[10]
10. Timepiece comprising the chronograph coupling lever for a timepiece according to claim 8 as an assembly component.

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法律状态:

优先权:

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申请号 | 申请日 | 专利标题

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JP2013051866|2013-03-14|

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JP2014000375A|JP6296491B2|2013-03-14|2014-01-06|Metal structure, method for manufacturing metal structure, spring component, start / stop lever for watch, and watch|

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