CN105940463B - Electric contact material and its manufacture method - Google Patents

Electric contact material and its manufacture method Download PDF

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Publication number
CN105940463B
CN105940463B CN201480074640.5A CN201480074640A CN105940463B CN 105940463 B CN105940463 B CN 105940463B CN 201480074640 A CN201480074640 A CN 201480074640A CN 105940463 B CN105940463 B CN 105940463B
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layer
precious metal
alloy
electric contact
contact material
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CN105940463A (en
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小林良聪
铃木智
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Furukawa Electric Co Ltd
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Furukawa Electric Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/30—Electroplating: Baths therefor from solutions of tin
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/48—Electroplating: Baths therefor from solutions of gold
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/50—Electroplating: Baths therefor from solutions of platinum group metals
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/10—Electroplating with more than one layer of the same or of different metals
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/10—Electroplating with more than one layer of the same or of different metals
    • C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/60—Electroplating characterised by the structure or texture of the layers
    • C25D5/605—Surface topography of the layers, e.g. rough, dendritic or nodular layers
    • C25D5/611—Smooth layers
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/627—Electroplating characterised by the visual appearance of the layers, e.g. colour, brightness or mat appearance
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01H—ELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
    • H01H1/00—Contacts
    • H01H1/02—Contacts characterised by the material thereof
    • H01H1/021—Composite material
    • H01H1/023—Composite material having a noble metal as the basic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01H—ELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
    • H01H1/00—Contacts
    • H01H1/02—Contacts characterised by the material thereof
    • H01H1/04—Co-operating contacts of different material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01H—ELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
    • H01H1/00—Contacts
    • H01H1/06—Contacts characterised by the shape or structure of the contact-making surface, e.g. grooved
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01H—ELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
    • H01H37/00—Thermally-actuated switches
    • H01H37/02—Details
    • H01H37/32—Thermally-sensitive members
    • H01H37/323—Thermally-sensitive members making use of shape memory materials

Abstract

The problem of the present invention is to provide a kind of high electric contact material of long-term reliability and its manufacture method, even if the electric contact material also shows that excellent abrasion performance in the case where sliding load is more than 50gf, such as 100gf or so high load condition, it can also particularly be used in the case where long-time is exposed to severe rugged environment as air simultaneously, such as in H2S gases or SO2Also the contact resistance that can significantly suppress electric contact material after accelerated test under the inferior corrosive environment of gas atmosphere rises.The present invention relates to a kind of electric contact material and its manufacture method, the electric contact material has the 1st layer of precious metal (2) on the surface of conductive base (1), there is the 2nd layer of precious metal (3), Ra=A μm of the arithmetic average roughness and A on the surface of the 1st layer of precious metal on the surface of the 1st layer of precious metal (2)<1, and the hardness Hv of the 1st layer of precious metal is more than 150, and the thickness of the 2nd layer of precious metal is more than A μm and for less than 1 μm, and Ra=B μm of the arithmetic average roughness on the surface of the 2nd layer of precious metal and B≤0.1.

Description

Electric contact material and its manufacture method
Technical field
The present invention relates to electric contact material and its manufacture method.More particularly, it relates to a kind of be coated with by mutually different expensive The electric contact material and its manufacture method for 2 layer of precious metal that metal or its alloy are formed.
Background technology
In the past, the copper or copper alloy of excellent electric conductivity are make use of in electric contact part, still, contact characteristic is not in recent years It is disconnected to improve, reduced using the situation of naked copper or naked copper alloy, and using having carried out various surface treatments on copper or copper alloy Material.Particularly, as a large amount of materials for being used as electric contact material, it there are and be plated with the electric contact of noble metal in electric contact portion Material.Wherein, the noble metal such as gold, silver, palladium, platinum, iridium, rhodium, ruthenium is due to showing stability or excellent electrical conductivity etc., thus quilt For in various electric contact materials.
As nearest electric contact material, for suitable for automobile mounted indoor and outdoor self-cleaning contact or reed switch (reed Switch), video camera seating (camera mount) contact switch etc., as example except the common contact based on extruding Also it make use of the electric contact material that abrasion performance is good with the electric contact material slided repeatedly in addition.On abrasion performance Improve, in general material, generally using hard silver or the electric contact material of hard gold.It is and then also scattered in research and development Fine-grained plating or covering material etc., in order to improve sliding properties of electric contact material etc., the various tables just in development and implementation The electric contact material of face processing.
Such as the present inventor provides a kind of electric contact material in patent document 1, the electric contact material is in electric conductivity base Be provided with the 1st layer of precious metal and the 2nd layer of precious metal on body, the 1st layer of precious metal by surface arithmetic average roughness Ra=(A) μm and (A) be that 0.05~0.5 noble metal or the alloy using noble metal as main component are formed, the 2nd noble metal is arranged at this The upper strata of 1st layer of precious metal, by leather film thickness be more than 0.001 × (A) μm and (A) μm below noble metal or using noble metal as The alloy of main component is formed, and the noble metal for forming above-mentioned 1st layer of precious metal is selected from gold, silver, palladium and platinum, above-mentioned relative to being formed The noble metal of the noble metal of 1st layer of precious metal or main component as the alloy for forming above-mentioned 1st layer of precious metal, formed above-mentioned The noble metal of 2nd layer of precious metal or noble metal as the main component for the alloy for forming above-mentioned 2nd layer of precious metal are different members Element.The electric contact material is sliding properties, excellent wear resistance, long lifespan, the electric contact material that can be manufactured with low cost.
Prior art literature
Patent document
Patent document 1：No. 5128153 publications of Japanese Patent No.
The content of the invention
The invention problem to be solved
However, electric contact material is made according to the composition of patent document 1 and evaluated, it is as a result it is recognized that while visible The very excellent effect of the lower sliding properties of light load, if but such as load reach more than 50gf, then, it is seen that sliding properties variation Tendency, and the corrosion resistance after environmental test can be deteriorated sometimes.Understand：Carrying out hydrogen sulfide (H2S) gas or sulfur dioxide (SO2) gas etc. high capacity environment under experiment when, from above-mentioned 1st layer of precious metal and 2 layers of layer of precious metal of the 2nd layer of precious metal Pin hole or the pin hole of the substrate metal layer being arranged between above-mentioned 1st layer of precious metal and conductive base can be formed from substrate The corrosion product of the composition of metal or matrix, sometimes result in contact resistance variation.
The problem of the present invention is to solve the above problems, there is provided a kind of high electric contact material of long-term reliability and its manufacture Method, even if the electric contact material also shows that in the case where sliding load is more than 50gf, such as 100gf or so high load condition Excellent abrasion performance, while can also particularly be used under severe rugged environment of the long-time exposed to air, such as in H2S gas Body or SO2Also can significantly it suppress on the contact resistance of electric contact material after accelerated test under the inferior corrosive environment of gas atmosphere Rise.
For solving the scheme of problem
The present inventor conducts in-depth research exploitation to above-mentioned problem, as a result finds：For being arranged at conductive base On the 1st layer of precious metal and the 2nd layer of precious metal each metal level, by suitably adjusting its surface roughness, the thickness of layer, layer Hardness etc., it is excellent so as to provide a kind of abrasion performance under not only high capacity and sliding properties, and corrosion resistance is also excellent Different electric contact material.The present invention is completed based on the opinion.
That is, according to the present invention, there is provided following technical proposals.
(1) a kind of electric contact material, the electric contact material have the 1st layer of precious metal on the surface of conductive base, There is the 2nd layer of precious metal on the surface of above-mentioned 1st layer of precious metal,
The electric contact material is characterised by,
Ra=A μm of the arithmetic average roughness and A on the surface of above-mentioned 1st layer of precious metal<1, and the 1st layer of precious metal Hardness Hv be more than 150,
The thickness of above-mentioned 2nd layer of precious metal is more than A μm and for less than 1 μm, and the arithmetic on the surface of the 2nd layer of precious metal Average roughness Ra=B μm and B≤0.1.
(2) electric contact material as described in (1) item, wherein, above-mentioned A value is for 0.001 less than 0.500.
(3) electric contact material as described in (1) or (2) item, wherein, above-mentioned 1st layer of precious metal and the 2nd layer of precious metal difference By gold, billon, silver, silver alloy, platinum, platinum alloy, indium, indium alloy, tin, tin alloy, palladium, palldium alloy, ruthenium, ruthenium alloy, rhodium, rhodium Any of alloy, osmium, osmium alloy, iridium, iridium alloy are formed.
(4) electric contact material as any one of (1)~(3), wherein, above-mentioned 1st layer of precious metal is closed by palladium, palladium Any of gold, ruthenium, ruthenium alloy, rhodium, rhodium alloy, osmium, osmium alloy, iridium, iridium alloy are formed.
(5) electric contact material as any one of (1)~(4), wherein, above-mentioned 2nd layer of precious metal is by gold, Jin He Any of gold, silver, silver alloy, platinum, platinum alloy, indium, indium alloy, tin, tin alloy are formed.
(6) electric contact material as any one of the item of (1)~(5), wherein, in above-mentioned conductive base and above-mentioned the There is at least 1 layer of substrate metal layer between 1 layer of precious metal.
(7) electric contact material as described in (6) item, wherein, above-mentioned substrate metal layer is by nickel, nickel alloy, cobalt, cobalt alloy Any composition.
(8) electric contact material as described in (6) or (7) item, wherein, the thickness of above-mentioned substrate metal layer for 0.05 μm~ 3.00μm。
(9) electric contact material as any one of (1)~(8), wherein, above-mentioned conductive base by copper, copper alloy, Any of iron, ferroalloy, aluminium, aluminium alloy are formed.
(10) electric contact material as any one of (1)~(9), wherein, the parent phase of above-mentioned conductive base is put down Equal crystallite dimension is less than 5 μm.
(11) manufacture method of the electric contact material as any one of (1)~(10), it is characterised in that utilize plating Method sets at least one layer in above-mentioned 1st layer of precious metal and the 2nd layer of precious metal.
Herein, in the present invention, " noble metal " refers to than electric conductivity base in above-mentioned 1st layer of precious metal or the 2nd layer of precious metal The valuable metal of the material of body.
Invention effect
According to the present invention it is possible to which provide one kind shows abrasion performance or sliding properties and corrosion resistance under high load, enter And the electric contact material that contact resistance is small.Although in addition, material of the electric contact material of the present invention more for example described in patent document 1 The thicker ground platings such as material, but also there is the tone of most surface to be not easily deteriorated, the long-term good effect of outward appearance.
The above and other feature and advantage of the present invention can be further clear and definite by following contents suitably referring to the drawings.
Brief description of the drawings
Fig. 1 is the sectional view for schematically showing an embodiment of the invention.
Fig. 2 is the sectional view for schematically showing another embodiment of the invention.
Fig. 3 is the sectional view for schematically showing the further embodiment of the present invention.
Fig. 4 is the border of the 1st layer of precious metal and the 2nd layer of precious metal that schematically show an embodiment of the invention Enlarged partial sectional figure.
Fig. 5 is the side of the 1st layer of precious metal and the 2nd layer of precious metal that schematically show another embodiment of the invention The enlarged partial sectional figure on boundary.
Embodiment
The present invention relates to a kind of electric contact material, the electric contact material has the 1st your gold on the surface of conductive base Belong to layer, there is the 2nd layer of precious metal on the surface of above-mentioned 1st layer of precious metal, wherein, the calculation on the surface of above-mentioned 1st layer of precious metal Art average roughness Ra=(A) μm and (A)<1, and the hardness Hv of the 1st layer of precious metal is more than 150, above-mentioned 2nd your gold The thickness for belonging to layer exceedes (A) μm and for less than 1 μm, and the arithmetic average roughness Ra=on the surface of the 2nd layer of precious metal μm and (B)≤0.1 (B).Herein, arithmetic average roughness Ra refers to according to JIS B 0601:2013 arithmetic average roughness Ra。
It should be noted that in the present invention, the 1st layer of precious metal and the 2nd layer of precious metal are individually its composition (that is, noble metal The species of element) mutually different layer.1st layer of precious metal and the 2nd layer of precious metal each can be by single noble metal species institutes Form, can also be made up of the alloy comprising noble metal.In the case where being made up of the alloy comprising noble metal, in the layer The maximum element species of mass ratio be necessary for noble metal.In 1 layer of precious metal by the alloy institute comprising two or more noble metals In the case of composition, total mass ratio of whole noble metals needs for maximum ratio in this layer in this layer.Wherein, in noble metal The ratio of alloy when being exactly 50%, be also regarded as layer of precious metal.
Herein, in the case where the 1st layer of precious metal and the 2nd layer of precious metal are made up of single noble metal species respectively, The precious metal element species needs mutually different.On the other hand, in the 1st layer of precious metal with the 2nd layer of precious metal respectively by comprising expensive In the case that the alloy of metal is formed, forming the maximum precious metal element species of the mass ratio in the above-mentioned layer of the alloy-layer needs It is mutually different.
The electric contact material of the present invention is illustrated using accompanying drawing.
Fig. 1 is the sectional view for schematically showing an embodiment of the invention.In the embodiment, in electric conductivity base The surface of body 1 is provided with the 1st layer of precious metal 2, and then is provided with the 2nd layer of precious metal 3 in its surface.
Fig. 2 is the sectional view for schematically showing another embodiment of the invention.Herein, in conductive base 1 Surface is provided with the substrate metal layer 4 for the coating being made up of the 1st layer of precious metal 2 and the 2nd layer of precious metal 3.
Fig. 3 is the sectional view for schematically showing the further embodiment of the present invention.Herein, in conductive base 1 Surface is provided with substrate metal layer 4, is provided with the upper part of substrate metal layer 4 by the 1st layer of precious metal 2 and the 2nd layer of precious metal 3 The coating of composition, to realize that the cost under the conditions of saving noble metal reduces.It should be noted that it is relevant with Fig. 3, can part Property ground substrate metal layer 4 on conductive base 1 is set, such as can be only arranged at provided with by the 1st layer of precious metal 2 and the 2nd The position (consistent with the shape of coating) for the coating that layer of precious metal 3 is formed.
In Fig. 1~Fig. 3, the border of the 1st layer of precious metal 2 and the 2nd layer of precious metal 3 is simplifiedly represented by straight line, but it is real On border, as being schematically illustrated in Fig. 4 enlarged partial sectional figure, the 1st layer of precious metal on the surface of conductive base 1 2 surface has arithmetic average roughness Ra=(A) μm of a bumps, the thickness of the 2nd layer of precious metal 3 with more than (A) μm and 1 μm with Under mode formed.
It should be noted that as being schematically illustrated in Fig. 5 enlarged partial sectional figure, to the 2nd layer of precious metal 3 , can also be thicker and in convex portion according to the recess of the face side in the 1st layer of precious metal 2 when using the situation such as gloss plating Relatively thin mode sets the 2nd layer of precious metal 3.In addition, now for example surface can also lightly be polished after plating and carried out Grinding, only it is coated to the 2nd layer of precious metal 3 in the recess of the face side of the 1st layer of precious metal 2.Herein, by the 2nd layer of precious metal 3 thicker When being arranged at the recess of the face side of the 1st layer of precious metal 2, being arranged at convex portion compared with unfertile land, the thickness of the 2nd layer of precious metal 3 now It is defined by arithmetic average.
In addition, conductive base, preferably copper or copper alloy, iron or ferroalloy, aluminum or aluminum alloy system used in being used as Conductive base, wherein the preferably conductive base of the good copper of conductance or copper alloy.
Such as the example as copper alloy, it can use：As CDA (Copper Development Association, Copper industry develop association) published alloy " C14410 (Cu-0.15Sn, The Furakawa Electric Co., Ltd. manufacture, trade name： EFTEC-3) ", " C19400 (Cu-Fe systems alloy material, Cu-2.3Fe-0.03P-0.15Zn) ", " C18045 (Cu-0.3Cr- 0.25Sn-0.5Zn, The Furakawa Electric Co., Ltd.'s manufacture, trade name：EFTEC-64T) ", " C26800 (Cu-35%Zn) ", " C71500 (Cu-30%Ni) " etc..It should be noted that the digital unit before each element is quality %.These copper alloys The conductive base of system suitably characteristic as requested can select to use because respective conductance or intensity are different, from carrying From the viewpoint of high conductivity or thermal diffusivity, it is 5%IACS (International Annealed to be preferably made conductance Copper Standard, International Annealed Copper Standard) more than copper alloy web.It should be noted that by copper or copper alloy system Copper is represented into " matrix composition " during conductive base.
In addition, as iron or ferroalloy, such as use 42 alloys (Fe-42 mass %Ni) or stainless steel etc..Base now Body composition represents iron.
The thickness of conductive base is not particularly limited, usually 0.05~2.00mm, preferably 0.10~1.00mm.
And then as the conductive base in the present invention, by using the average crystalline substance of conductive base mother metal (matrix) Particle size is less than 5 μm of material, and precipitation can be made to separate out thereon the plated layer compact of layer, as a result can be formed with multiple crystalline substances Grain coating and disperse grain boundary decision, so as to significantly postpone matrix composition the time being diffused into up to top layer.As a result, can With provide can suppress to have diffused to matrix composition in the top layer of the 2nd layer of precious metal burn into suppress contact resistance rising, So as to the high electric contact material of reliability.In addition, as multiplication effect, the average crystal grain chi of conductive base mother metal also can obtain The more excellent effect of the bendability of very little smaller then conductive base.
The average grain size of conductive base mother metal is preferably less than 5 μm, in order to further improve the compactness of plating, More preferably less than 3 μm, more preferably less than 1 μm.Its lower limit is not particularly limited, usually more than 0.001 μm.
In the present invention, as the 1st layer of precious metal of formation and the metal of the 2nd layer of precious metal or the example of its alloy, Ke Yiju Go out：Gold, billon, silver, silver alloy, platinum, platinum alloy, indium, indium alloy, tin, tin alloy, palladium, palldium alloy, ruthenium, ruthenium alloy, rhodium, Rhodium alloy, osmium, osmium alloy, iridium, iridium alloy etc..
Herein, the effect of the 1st layer of precious metal is the abrasion performance for improving the 2nd layer of precious metal formed in most surface, And then improve corrosion resistance.Its reason is：By the way that the arithmetic average roughness Ra=(A) μm on the 1st layer of precious metal surface is set to (A)<1, abrasion performance can be improved, and by the way that its hardness Hv is set into more than 150, is preferably set to more than 200, one can be entered Step improves abrasion performance.
Additionally, it is preferred that the value of above-mentioned (A) is set to 0.001 less than 0.500, it is hereby achieved that corrosion resistance is more excellent Different electric contact material.
Particularly, for ease of reaching this abrasion performance and corrosion proof raising, as the 1st layer of precious metal, preferably by Any of palladium, palldium alloy, ruthenium, ruthenium alloy, rhodium, rhodium alloy, osmium, osmium alloy, iridium, iridium alloy are formed, due to can be further Reduce abrasion performance and contact resistance, the 1st layer of precious metal is further preferably by any of palladium, palldium alloy, rhodium, rhodium alloy structure Into.(A) value is preferably 0.001 less than 0.5, more preferably 0.005~0.1.By the way that the value of (A) is set into this Scope, can make to be subsequently formed and be easy to smooth in the surface of the 2nd layer of precious metal on the 1st layer of precious metal.
It should be noted that the coated thickness on the 1st layer of precious metal is not particularly limited, if considering cost or bending Processability, then preferably 0.001~3 μm, more preferably 0.05~1 μm.
The 2nd layer of precious metal noble metal different by the noble metal from forming the 1st layer of precious metal is formed.2nd layer of precious metal It is the most surface coating of the electric contact material of the present invention, the leather film thickness of the 2nd layer of precious metal exceedes as the 1st layer of precious metal (A) of the arithmetic average roughness (Ra) on surface μm and for less than 1 μm, and the arithmetic average on the surface of the 2nd layer of precious metal is thick Rugosity Ra=(B) μm and B≤0.1.2nd layer of precious metal is as the 1st layer of precious metal of protection and the good with conductive characteristic the 1st The different layer of precious metal of layer of precious metal and set.The surface of 2nd layer of precious metal turns into the sliding surface at initial stage, by being used as the The 2nd layer of precious metal is buried in the bumps of (A) of the arithmetic average roughness (Ra) on 1 layer of precious metal surface μm, so as to as under Coating layer exhibiting function is stated, the coating has concurrently as the low contact resistance characteristic required for electric contact material and connect as slip Function required for point is surface lubrication/abrasion performance.2nd layer of precious metal is not only with the concavo-convex of the 1st layer of precious metal of landfill Degree is present, and by making its thickness exceed above-mentioned (A) μm and for less than 1 μm, is further carried so as to which corrosion resistance is made High epithelium.And then by the way that the arithmetic average roughness Ra=(B) μm on the 2nd layer of precious metal surface is set into (B)≤0.1, so as to It can play and suppress abrasion caused by bumps, prevent the 1st layer of precious metal effect that even conductive base exposes.So will 2nd layer of precious metal is set to be thicker than arithmetic average roughness (Ra)=(A) μm of electric contact material of the invention of the 1st layer of precious metal In, be more than patent document 1 due to forming the dosage of noble metal of coating, thus cost raises, but from the corrosion proof sight of raising It is excellent from the point of view of point, thus can reduces the totle drilling cost under long-term use of environment.
As the material of above-mentioned 2nd layer of precious metal, it is adapted to using gold, billon, silver, silver alloy, platinum, platinum alloy, indium, indium Alloy, tin, tin alloy etc., particularly in corrosion proof purposes is required, preferably gold, billon, platinum, platinum alloy.On the other hand, If the few electric contact material of misgivings of the electric contact through resin moulded and in the air, then can also use silver, silver alloy, The material of indium, indium alloy, tin, tin alloy as the 2nd layer of precious metal.These metals or its alloy are due to showing excellent solder Wetability or contact resistance behavior, thus can suitably be selected according to purposes or situation.
, can be in conductive base and the 1st noble metal in the electric contact material (such as sliding contact material) of the present invention Substrate metal layer is set between layer, can also be not provided with.By setting by any of such as nickel, nickel alloy, cobalt, cobalt alloy The substrate metal layer formed, the diffusion of the 1st layer of precious metal and matrix composition can be stopped or improve adaptation, thus preferably. Above-mentioned 1st layer of precious metal or the 2nd noble metal are particularly being regard the metal more valuable than conductive base as by plating processing Layer and formed the present invention in, in order to improve adaptation or prevent from replacing, pass through flash or strike plating in the plating before processing It is effective that substrate metal layer is pre-set etc. base treatment.In addition, substrate metal layer can be more than two layers, can basis Above-mentioned 1st layer of precious metal or the coated specification of the 2nd layer of precious metal or purposes etc., various compositions are used as by conventional method to set Put.The gross thickness for being made simple layer or the substrate metal layer of multilayer is preferably 0.05 μm~3 μm, more preferably 0.5 μm~1 μm.
In order to manufacture the electric contact material of the present invention, the various skins such as plating, covering (clad), evaporation, sputtering can be utilized Film forms method, and as the method for being especially susceptible to be formed film, the 1st layer of precious metal and the 2nd noble metal are set preferably by galvanoplastic At least one layer in layer, more preferably formed using galvanoplastic the 1st layer of precious metal and the 2nd layer of precious metal two layers.The group of electroplate liquid It can be determined according to conventional methods and suitably into plating condition.In addition, in order to suppress required amount of metal, by the 1st layer of precious metal Or the 2nd the noble metal of layer of precious metal or both to be coated to layer segment to be arranged to strip or point-like etc. be also useful.
On the present invention electric contact material in the coating being made up of above-mentioned 1st layer of precious metal and the 2nd layer of precious metal, Gloss, semi-glossy, lacklustre outward appearance species are not particularly limited, and can apply.In addition, even if the invention described above is only made Form, effect is also abundant, and in order to further improve effect, being also preferably formed makes conventionally used various additives, dispersant, divides Scattered seed etc. contains more than 1 in the coating and intermediate layer being made up of above-mentioned 1st layer of precious metal and the 2nd layer of precious metal Formed in layer composite coated.
Embodiment
Below, the present invention is described in more detail based on embodiment, but the present invention is not limited to these embodiments.
(embodiment 1)
To thickness 0.3mm, width 50mm table 1 shown in conductive base carry out pre-treatment as shown below after, by table 1 Shown substrate metal layer, the 1st layer of precious metal, the 2nd layer of precious metal pass sequentially through galvanoplastic and are arranged on conductive base, obtain The electric contact material of example, comparative example and conventional example shown in table 1.
It should be noted that the coated thickness on each layer, uses fluorescent X-ray film thickness measuring device (SFT-9400, business The name of an article, the manufacture of SII companies), collimator diameter is set to 0.5mm and to being measured at any 10, calculates its average value, as Coated thickness.
(Pretreatment)
[catholyte degreasing]
Degreaser：NaOH 60g/l
Degreasing condition：2.5A/dm2, temperature 60 C, degreasing time 60 seconds
[pickling]
Pickle：10% sulfuric acid
Acid washing conditions：30 seconds dippings, room temperatures
(substrate metal layer plating condition)
[plating Ni]
Plating solution：Ni(SO3NH2)2·4H2O 500g/l、NiCl2 30g/l、H3BO3 30g/l
Plating condition：Temperature 50 C
[plating Co]
Plating solution：Co(SO3NH2)2·4H2O 500g/l、CoCl2 30g/l、H3BO3 30g/l
Plating condition：Temperature 50 C
(the 1st layer of precious metal plating condition)
[plating Pd 1 (Pd1)]
Plating solution：Pd(NH3)2Cl2 45g/l、NH4OH 90ml/l、(NH4)2SO450g/l, Parasigma polishing material (trade name, Matsuda Industrial Co., Ltd.'s manufacture) 10ml/l
Plating condition：Current density 5A/dm2, temperature 60 C
[plating Pd 2 (Pd2)] additive-free bath：Used in comparative example 2
Plating solution：Pd(NH3)2Cl2 45g/l、NH4OH 90ml/l、(NH4)2SO4 50g/l
Plating condition：Current density 3A/dm2, temperature 60 C
[plating Rh]
Plating solution：RHODEX (trade name, Electroplating Engineers of Japan Ltd. manufactures)
Plating condition：1.3A/dm2, temperature 50 C
[plating Ru]
Plating solution：RUTHENEX100 (trade name, Electroplating Engineers of Japan Ltd. manufactures)
Plating condition：Current density 1A/dm2, 65 DEG C of temperature
[plating Ir]
Plating solution：IRIDEX100 (trade name, Electroplating Engineers of Japan Ltd. manufactures)
Plating condition：0.2A/dm2, 85 DEG C of temperature
(the 2nd layer of precious metal plating condition)
[plating Au]
Plating solution：KAu(CN)2 14.6g/l、C6H8O7 150g/l、K2C6H4O7 180g/l
Plating condition：40 DEG C of temperature
[plating Pt]
Plating solution：Pt(NO2)(NH3)2 10g/l、NaNO2 10g/l、NH4NO3 100g/l、NH3 50ml/l
Plating condition：80 DEG C of temperature
[plating Ag]
Plating solution：AgCN 50g/l、KCN 100g/l、K2CO3 30g/l
Plating condition：Current density 1A/dm2, 30 DEG C of temperature
[plating Ag-Se alloys]
Plating solution：KCN 150g/l、K2CO3 15g/l、KAg[CN]2 75g/l、Na2O3Se·5H2O 5g/l
Plating condition：Current density 2A/dm2, temperature 50 C
[plating Sn]
Plating solution：SnSO4 80g/l、H2SO4 80g/l
Plating condition：Current density 2A/dm2, 30 DEG C of temperature
On resulting each electric contact material, various characteristics are tested under following experimental condition, evaluated.Will As a result it is shown in table 2.
The average grain size (GS) of (1A) conductive base：
3 visuals field of the cross-section samples of conductive base are made by FIB (Focused Ion Beam, focused ion beam) Afterwards, SIM image viewings are carried out, for 3 Site Determination particle diameters in every 1 visual field, value is averaged and is shown in table 1.
(1B) thickness measurement：The thickness of 1st layer of precious metal, the 2nd layer of precious metal and substrate metal layer passes through SII Fluorescent X-ray film thickness gauge (the trade name of NanoTechnology companies manufacture：SFT9400) it is measured.By collimator diameter 0.5mm is set to, any 10 positions are measured, its average value are calculated, as coated thickness.Show the result in table 1.
(1C) Determination of Hardness：According to JIS Z 2244：2009, to the 1st noble metal being set to measure load during 0.005N The Vickers hardness (Hv) of layer is measured.It should be noted that this is the hardness before coated 2nd layer of precious metal.Show the result in Table 1.
(1D) arithmetic average roughness Ra：The surface that arithmetic average roughness Ra is manufactured by Co., Ltd. of little Ban research institutes Roughmeter (trade name：Surfcorder SE3500) it is measured.In 2 μm of contact pilotage front-end radius, measure below power 0.75N Condition determination under, determine the 1st layer of precious metal arithmetic average roughness Ra=(A) μm of arithmetic average with the 2nd layer of precious metal Roughness Ra=(B) μm.Show the result in table 1.
(2A) coefficient of kinetic friction determines：Use sliding test device (HEIDON Type：14FW, trade name, new eastern science Company manufactures) carry out coefficient of kinetic friction measure.Condition determination is as described below.
R=2.0mm steel ball probe (probe), sliding distance 10mm, sliding speed 100mm/ minutes, slip number is past Return 100 times, load 100gf
In above-mentioned sliding test, determine to come and go and slide number as each coefficient of kinetic friction after 1 time, 50 times, 100 times, and It is shown in table 2.
(2B) wears away depth：Abrasion depth after terminating for above-mentioned sliding test, use microscope (VH8000, commodity Name, the manufacture of KEYENCE companies), the depth (μm) of measure slide mark central cross section.Table is shown in using its bosom as abrasion depth 2。
(2C) contact resistance determines：Measure contact resistance as follows is evaluated as corrosion proof index.In shape Into after most top layer (above-mentioned 2nd layer of precious metal), contact resistance is determined by four-terminal method.In measure, with most top layer it is newly formed after (initial stage), sulfurous acid gas test (SO210ppm, 40 DEG C, 80%RH, 168 hours) afterwards, hydrogen sulfide production test (H2S 3ppm、40℃、 80%RH, 168 hours) after 3 horizontal carry out.In evaluation, actionradius 2mm Ag probes, in 10mA energizations, load 10gf Under conditions of contact resistances are determined to 10 measuring points, calculate its average value as contact resistance.As evaluation, by 10m Ω with Under be set to " excellent " and table 2 be shown in " A ", 10m Ω will be exceeded and be set to " good " for below 50m Ω and table 2 is shown in " B ", will More than 50m Ω and it is set to "available" for below 100m Ω and table 2 is shown in " C ", will be set to more than 100m Ω " can not " and with " D " It is shown in table 2.Practical grade is determined as " C " or " B " or " A ".
(2D) bendability：For each sample, under conditions of bending machining radius 0.9mm (R/t=3) relative to After striped (pressor unit) is rolled as the direction implementation V bend tests at right angle, microscope (VH8000, trade name, KEYENCE are utilized Company manufactures) observe its spine to observe 200 times of multiplying power.To have no crackle, person is set to " excellent " and is shown in table 2 with " A ", will produce Slight line trace person is set to "available" and is shown in table 2 with " B ", will produce larger crackle person be set to " can not " and table 2 is shown in " C ". Practical grade is determined as " B " or " A ".
(2E) solder wettability：Using MODEL SAT-5100 (trade name, Rhesca companies manufacture), above-mentioned plating will be passed through Apply and handle each test film obtained in Sn-3Ag-0.5Cu solder baths, in 245 DEG C of bath temperature, dipping distance 10mm, dipping speed Spend under conditions of the 25mm/ seconds, be impregnated in the quality % of isopropanol -25 rosin flux (rosin flux).Determine from immersion test Time (zero cross time, zero-crossing timing) of the piece untill wetting power zero passage.The zero-crossing timing (second) of its result is shown in Table 2.Zero-crossing timing is set to " excellent " less than 1 second person, person within more than 1 second and 3 seconds is set to "available", more than 3 seconds persons are set to " can not ", evaluate solder wettability.
【Table 1】
Table 1
【Table 2】
Table 2
From the above results, in each example, even if also showing that stable move under 100gf high sliding load Coefficient of friction and sliding properties are good, the excellent wear resistance that abrasion performance depth is shown, what is gone out shown by contact resistance is anti-corrosion Property is excellent, and bendability is also good with solder wettability.
It is the result of any characteristic difference in contrast, in each comparative example and conventional example.
Comparative example 1 is because the surface roughness Ra (B) of the 2nd layer of precious metal is too high, if thus in 100gf high sliding load Lower slider number is changed into 100 times from 50 times, then contact resistance increase, in addition, bendability is poor.Comparative example 2 is due to the 1st your gold It is too low to belong to the hardness of layer, if thus being changed into 100 times from 50 times in 100gf high sliding load lower slider number, contact resistance Increase, in addition, abrasion performance is poor.Conventional example 1 is thinner than the surface of the 1st layer of precious metal due to the coated thickness of the 2nd layer of precious metal Arithmetic average roughness Ra=(A) μm, if thus be changed into 100 times from 50 times in 100gf high sliding load lower slider number, Contact resistance increases.These comparative examples use grade with conventional example less than full.
Industrial applicibility
As long as the present invention electric contact material be common contact electric contact, then no matter which kind of type can be suitably Use.Particularly because of abrasion performance and corrosion resistance excellent, thus can be especially suitable for being for example suitable for automobile mounted interior Outer self-cleaning contact or reed switch, motor commutator (commutator) contact and brush (brush) material, video camera seating The material of the use in electric contact such as contact switch.
Although the present invention is described for combined embodiments thereof, it is applicant's understanding that as long as no special Statement, then it is of the invention to be not limited at any details of explanation, the invention shown in appended claims should not violated Wide in range explanation is carried out under conditions of spirit and scope.
Symbol description
1 conductive base
2 the 1st layer of precious metal
3 the 2nd layer of precious metal
4 substrate metal layers

Claims (8)

1. a kind of electric contact material, the electric contact material has the 1st layer of precious metal on the surface of conductive base, described There is the 2nd layer of precious metal on the surface of 1 layer of precious metal,
The electric contact material is characterised by,
Ra=A μm of the arithmetic average roughness and A on the surface of the 1st layer of precious metal<1, and the 1st layer of precious metal is hard It is more than 150 to spend Hv,
2nd layer of precious metal is gold plate, and its thickness is more than A μm and for less than 1 μm, and the surface of the 2nd layer of precious metal Ra=B μm of arithmetic average roughness and B≤0.1,
The average grain size of the parent phase of the conductive base is less than 1 μm, and grain boundary decision disperses in coating,
Using galvanoplastic, at least one layer in the 1st layer of precious metal and the 2nd layer of precious metal is set.
2. electric contact material as claimed in claim 1, wherein, the value of the A is for 0.001 less than 0.500.
3. electric contact material as claimed in claim 1, wherein, the 1st layer of precious metal by gold, billon, silver, silver alloy, Platinum, platinum alloy, indium, indium alloy, tin, tin alloy, palladium, palldium alloy, ruthenium, ruthenium alloy, rhodium, rhodium alloy, osmium, osmium alloy, iridium, iridium close Any of gold is formed.
4. electric contact material as claimed in claim 1, wherein, the 1st layer of precious metal by palladium, palldium alloy, ruthenium, ruthenium alloy, Any of rhodium, rhodium alloy, osmium, osmium alloy, iridium, iridium alloy are formed.
5. electric contact material as claimed in claim 1, wherein, between the conductive base and the 1st layer of precious metal With at least 1 layer of substrate metal layer.
6. electric contact material as claimed in claim 5, wherein, the substrate metal layer is by nickel, nickel alloy, cobalt, cobalt alloy Any composition.
7. electric contact material as claimed in claim 5, wherein, the thickness of the substrate metal layer is 0.05 μm~3.00 μm.
8. such as electric contact material according to any one of claims 1 to 7, wherein, the conductive base by copper, copper alloy, Any of iron, ferroalloy, aluminium, aluminium alloy are formed.
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