CN1940137A - Heat resistant film, its manufacturing method, and electrical and electronic parts - Google Patents
Heat resistant film, its manufacturing method, and electrical and electronic parts Download PDFInfo
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Abstract
Provided are a film having excellent heat resistance, formability and solderability, and used for coating the surface of a material, its manufacturing method, and further electrical and electronic parts coated with the film. An Ni or Ni-alloy layer, a Cu layer and an Sn or Sn-alloy layer are applied to the surface of the material composed of copper alloy, etc., in the order named from the surface side. Then reflow treatment is applied at 300-900 deg.C for 1-300s. By this method, the heat resistant film having the following layers can be obtained: an Sn or Sn-alloy layer having a thickness X of 0.05-2 &mu m on the outermost surface side; an alloy layer containing an intermetallic compound composed essentially of Cu-Sn and having a thickness Y of 0.05-2 &mu m on the inner side; and further an Ni or Ni-alloy layer having a thickness Z of 0.01-1mu m on the inner side of the above layer ( where 0.2X<=Y<=5X and 0.05Y<=Z<=3Y are satisfied).
Description
The application be No. 01143394.9, Chinese patent application of the same name divide an application the December 21 calendar year 2001 original bill applying date.
[technical field]
The present invention relates to surface treatment and manufacture method thereof with lower terminal.As surface treatment and its manufacture method of the multipole terminals such as automobile electrical gas distribution of lower wearing and tearing when requiring to have thermotolerance concurrently, insert or extract, less frictional coefficient.As require to have good plug number of times performance and surface treatment and its manufacture method of the charging electric motor vehicles plug that big electric current passes through are arranged.Require to have the surface treatment and the manufacture method thereof of brush of the motor of wearability as contacting in rotator.As require to have surface treatment and its manufacture method of the accumulator terminal of wearability erosion resistance.And the connection of printed circuit board (PCB) etc. must be with surface treatment and its manufacture method of the electric electronic element of soldering welding.
[background technology]
In recent years along with the development of electronic industry, electrical wiring is towards complicated, and is highly integrated and make progress, the multipolarization of junctor also along with and make progress.And because outside heat and self-heating etc. also become stricter to stable on heating requirement.
General Sn electroplates junctor when plug, and frictional force can increase, thereby makes junctor be difficult for inserting and have problems.And Sn-plated material is because the influence of heat, Cu from material or lower floor's electrolytic coating can spread, form Cu-Sn based compound layer, and thereby the oxidation film layer of Cu-Sn based compound makes the contact resistance increase cause its stable on heating deterioration, or under the maintaining requirement of high temperature, high humidity, because diffusion and oxidative phenomena produce the low problem of scolding tin welding property.
As reducing the countermeasure that Sn electroplates the insertion force of multipole connector, implement hard Ni in the lower floor of general Sn electrolytic coating and electroplate, or form the Cu-Sn diffusion layer, improve the hardness of lower floor, scheme such as diffusion trapping layer is set is proposed.
But, on the Ni electrolytic coating, implement the galvanized occasion of Sn, the Ni-Sn alloy layer that after heat test, is produced, or the oxidation film layer of Ni-Sn alloy layer makes the contact resistance increase, the resistance toheat reduction.When terminal inserted, Sn was worn and makes Ni expose, and the oxide compound of heating back Ni significantly worsens contact resistance.Usually to electroplate lower thickness be 1～2 μ m to Ni, but be easy to generate the rimose shortcoming when having the connector terminal to carry out bending machining.Even Ni electroplates lower thickness and is thinned to 0.5 μ m, above contact resistance increases phenomenon and can not be satisfactorily resolved.
When utilizing the Cu-Sn diffusion layer, under the situation of long-term heating, produce contact resistance and increase the phenomenon that the soldering welding property is low as the middle layer.With regard to manufacture method, utilize remained on surface Sn layer, its inboard is provided with the method for Cu-Sn diffusion layer and carries out thermodiffusion, but the layer thickness control of diffusion layer is difficulty quite, even carry out layer thickness control, and the influence of temperature environment during use, can not stop the carrying out of diffusion, and make resistance toheat reduce.After forming the Cu-Sn diffusion layer, carry out the galvanized scheme of Sn and also be proposed, but this scheme needs suitable complicated step, and its cost value is improved, and the adherence of surperficial Sn electrolytic coating, shaping processability is low to be subtracted, thereby makes this scheme be difficult to realize.
Present electromobile must carry out once above charging in one day, guaranteed that charging just seems very important with the wear resistant of male component.And the electric current that passes through is very big more than 10A, so thermal value is very big, and problems such as peeling off of electrolytic coating will appear in general methods such as Sn plating.
Printed circuit board (PCB) based on pollution regulation, will have high temperature scolding tin such as the Pb-free solder of use from now on when connecting, and will shift or the tendency of the solvent (scolder) that activity degree is smaller to scolding tin, therefore require to electroplate than general Sn to have better soldering weldability.Particularly, the not moisture that can produce because of when keeping, or hot environment, and make the soldering weldability low, be to keep its good soldering weldability.
At above-mentioned problem, clearly general surface treatment method can not meet the demands.Though Sn or Sn alloy layer, Cu-Sn alloy layer, and the film forming and the film of Cu layer, Ni layer, Ni alloy layer all be suggested,, its optimal combination, and optimal bed thickness also all is not studied.
[summary of the invention]
The invention solves above-mentioned problem, and propose following scheme: the most surperficial formation Sn or Sn alloy layer, its inboard is Cu-Sn alloy layer (Cu
3Sn, Cu
4Sn, Cu
6Sn
5Deng the Cu-Sn intermetallic compounds layer, or the alloy layer of the Cu-Sn-Ni that generates because of thermodiffusion of the Ni of lower floor etc. etc.).Or because of the residual Cu layer of reaction, and Ni layer, the Ni alloy layer of the bed thickness that requires of side formation within it, thereby make its junctor, charging electric vehicle with desired good thermotolerances such as plug, less frictional coefficient and good wearability with multi-pole plug for example.And have surface-treated layer and its manufacture method on good soldering weldability surface, and the electric electronic element that utilizes above material manufacturing.
Particularly, the invention provides the and the following invention.The 1st of the present invention is the heat-resistance protection film, it is characterized in that, by upper layer is Sn layer or the Sn alloy layer of bed thickness X 0.05～2 μ m, its la m is the layer based on the intermetallic compound of Cu-Sn of containing of bed thickness Y 0.05～2 μ m, and innermost layer is that Ni or the Ni alloy layer of bed thickness Z 0.01～1 μ m constitutes; The 2nd is the heat-resistance protection film of the 1st record, wherein 0.2X≤Y≤5X, and 0.05Y≤Z≤3Y; The 3rd is the heat-resistance protection film of the 1st or 2 record, and between above-mentioned intermetallic compounds layer and above-mentioned Ni or the Ni alloy layer, having thickness is the following Cu layer of 0.7 μ m; The 4th is the heat-resistance protection film of wantonly 1 record in the 1st～3, and above-mentioned material or the material of being protected by the heat-resistance protection film is Cu or Cu alloy in the surface at least; The 5th is the manufacture method of the heat-resistance protection film of wantonly 1 record in the 1st～4, it is characterized in that forming Ni or Ni alloy layer successively from material surface, behind Cu layer, Sn or the Sn alloy layer, it is heat-treated; The 6th is the manufacture method of the heat-resistance protection film of wantonly 1 record in the 1st～4, after it is characterized in that forming Ni or Ni alloy layer, Cu layer, Sn or Sn alloy layer successively from material surface, it is carried out remelting handle; The 7th is the manufacture method of the heat-resistance protection film of wantonly 1 record in the 1st～4, it is characterized in that 10 average light slipperies in surface flatness are below 1.5 μ m, and its medullary ray average light slippery is on the material surface below the 0.15 μ m, after forming Ni or Ni alloy layer, Cu layer, Sn or Sn alloy layer successively from material surface, it is heat-treated; The 8th is the manufacture method of the heat-resistance protection film of wantonly 1 record in the 1st～4, it is characterized in that 10 average light slipperies in surface flatness are below 1.5 μ m, and its medullary ray average light slippery is on the material surface below the 0.15 μ m, after forming Ni or Ni alloy layer, Cu layer, Sn or Sn alloy layer successively from material surface, it is carried out remelting handle; The 9th is the manufacture method of the heat-resistance protection film of wantonly 1 record in the 5th～8, it is characterized in that before with above-mentioned Ni or Ni alloy layer film forming, forms Cu or Cu alloy layer earlier; The 10th is electric electronic element, it is characterized in that forming at material surface the heat-resistance protection film of wantonly 1 record in the 1st～4.
[description of drawings]
Fig. 1 is the testing method synoptic diagram of frictional coefficient in the embodiment of the invention.
[explanation of symbol]
1. the upper strata test film that has concave configuration
2. lower floor's test film
3. heavily cut or polish jade with an emery wheel
4. horizontal stand
5. pulley
6. load gauge measuring device
[concrete form of implementation]
Carry out specific description with regard to content of the present invention below.The reason of data area that the present invention limits at first is described.
At first, with the Sn bed thickness of upper layer, the occasion of bed thickness below 0.05 μ m, the stability of contact resistance, the soldering welding property will reduce.Particularly the contact resistance when underload will easily produce wild effect, and the moisture, the high temperature that produce during because of keeping make it that reduction of soldering weldability take place.And, because of H
2S, SO
2The corrosion of gas is having under the situation of moisture NH
3Gas makes problems such as its solidity to corrosion reduction.When the bed thickness of Sn layer surpasses the occasion of 2 μ m, cause when junctor inserts and the turn up friction that produces inserts it into the resistance increase, fatigue characteristic are low, the problem such as unfavorable of economic face.And, if the bed thickness of the Cu-Sn diffusion layer that its inboard forms by thermal treatment is blocked up, be easy to generate cracking man-hour adding, make the shaping processability of material low.Therefore, the bed thickness scope of Sn layer is between 0.05～2 μ m.Preferably in 0.1～1 mu m range.
The formation method of Sn layer has plating, melt impregnation, shot peening, coating method etc., takes all factors into consideration from the control of bed thickness and the aspect of production cost, to electroplate to well.Here the Sn bed thickness of indication is meant the bed thickness of the most surperficial Sn layer after DIFFUSION TREATMENT such as thermal treatment are over, the skin of Cu-Sn intermetallic compound (face side) part.Because of heat treated influence, can contain the Sn element in addition below 20%.Element amount beyond the Sn surpasses 20%, the soldering weldability will take place, problems such as contact resistance after long-term heating.The most surperficial Sn protective film before the DIFFUSION TREATMENT also can be alloy plating such as Sn-Cu, Sn-Ag, Sn-Bi, Sn-Zn, Sn-Pb and Sn-In melt impregnation etc.Certainly, its inboard must be provided with the Cu-Sn intermetallic compounds layer, makes it carry out DIFFUSION TREATMENT, Cu, Ag, Bi, Zn, Pb, In etc. during long-term the heating among the Sn are diffused into the most surperficial, also do not influence its soldering weldability after the oxidation, and cause that contact resistance hangs down inferior phenomenon, this point is quite important.
The lower floor of Sn layer must be provided with the intermetallic compounds layer of 0.05～2 μ m.This formation that contains the intermetallic compounds layer of Cu-Sn alloy forms preferably through the Sn layer formation alloying of diffusion with the surface with the Cu in the Cu layer (for example Cu electrolytic coating) that makes lower floor by thermal treatment.Therefore, the lower floor of Sn layer comprises the residual Cu layer in reaction back.But the thickness of residual Cu layer should be below 0.7 μ m, preferred should be below 0.3 μ m.Residual Cu layer because of long-term heating produces diffusion, grows up the Cu-Sn diffusion layer, causes the thickness minimizing of the Sn layer of upper layer, causes contact resistance, the soldering weldability lowly.
Above-mentioned gained Cu-Sn intermetallic compound has suppressed effectively from the next Ni of diffused inside, thereby has suppressed surperficial Ni-Sn alloy layer, and the formation of oxide compound.Because above effect, successfully suppressed the increase of the contact resistance after the long-term heating.And, because of the formation of the Cu-Sn series intermetallic compound of hard makes it have the effect that reduces insertion force.In order to embody this effect better, the thickness of Cu-Sn intermetallic compounds layer should be more than 0.05 μ m, preferably more than 0.1 μ m.
But, contain the too thick occasion of layer thickness of Cu-Sn intermetallic compound, can make processibility obviously low.Because the increase by the Cu-Sn diffusion layer that forms of diffusion surfaceness, even the most surperficial Sn layer of adjusting also exerts an adverse impact to outward appearance and insertion force easily.Therefore, the thickness of preferred Cu-Sn layer should be below 2 μ m, more preferably below 1 μ m.
And, must form Ni or Ni alloy layer in the inboard of the layer that contains the Cu-Sn intermetallic compound.This Ni or Ni alloy layer not only have the diffusion effect of inhibition from the Cu of copper, copper alloy mother metal, have more inhibition from the interpolation elemental diffusion effect in the copper alloy, prevent contact resistance, soldering weldability, the effect that heat-resisting adherence is low.The for example Zn in the brass, the P in the phosphor bronze etc.
And this Ni or Ni alloy layer have the effect that performances such as the insertion force impedance that makes its outer field Cu-Sn intermetallic compounds layer, thermotolerance, solidity to corrosion make progress.The formation method of this Ni or Ni alloy layer is the most common with electro-plating method, and aforesaid Sn formation method is the same, and the whole bag of tricks can be used.And be not limited to the Ni layer, the Ni alloy layer also can.As Ni-Co, the Ni alloy layer of electric electro-plating method such as Ni-P also can.Also can be to heat-treat the alloy layers such as Ni-Cu that form from mother metal or the diffusion of Cu electrolytic coating that produced when forming the Cu-Sn diffusion layer.
Above technology also can be used in the material beyond copper such as ferrous materials, stainless steel, Al alloy, the copper alloy.In this case, in order to improve the adherence of Ni layer, Ni alloy layer, can implement Cu lower floor electroplates, existence because of Ni layer, Ni alloy layer, can suppress diffusion effectively from the Cu of Cu electrolytic coating, make it have contact resistance under the long-term heating environment of inhibition, the effect of soldering welding property deterioration.
Generally speaking, consider that material serves as preferred with copper, copper alloy, but also is not limited to this from the characteristic surface of necessity such as the electrical conductivity of electric element, elasticity, magnetic.Mother metal is the occasion of copper, copper alloy, must have following structure, and is outside from mother metal, is followed successively by Ni or Ni alloy, (Cu), the alloy that contains the Cu-Sn intermetallic compound, Sn or Sn alloy.Perhaps be followed successively by Cu or Cu alloy, Ni or Ni alloy, (Cu), Cu-Sn intermetallic compound, Sn or Sn alloy.
When mother metal is copper alloy, intensity with regard to material, elasticity, the electrical conductivity degree, processibility, faces such as solidity to corrosion consider that the scope that ideal adds element is Zn:0.01～50wt%, Sn:0.1～12wt%, Fe:0.01～5wt%, Ni:0.01～30wt%, Co:0.01～5wt%, Ti:0.01～5wt%, Mg:0.01～3wt%, Zr:0.01～3wt%, Ca:0.01～1wt%, Si:0.01～5wt%, Mn:0.01～20wt%, Cd:0.01～5wt%, Al:0.01～10wt%, Pb:0.01～5wt%, Bi:0.01～5wt%, Be:0.01～3wt%, Te:0.01～1wt%, Y:0.01～5wt%, La:0.01～5wt%, Cr:0.01～5wt%, Ce:0.01～5wt%, Au:0.01～5wt%, Ag:0.01～5wt%, P:0.005～0.5wt%.Above element is minimum to be contained more than a kind, contains total amount in 0.01～50wt%.
From raw material utilize angle again, it is desirable to contain the copper alloy of Ni, Sn.
Below the thickness of each layer of explanation limits reason.
The thickness (X) of the most surperficial Sn layer or Sn alloy layer, the thickness (Y) that its inboard Cu-Sn layer is the intermetallic compounds layer of main body, its inboard Ni layer or Ni alloy layer (Z), the ideal thickness of each layer is narrated in the above.But,, therefore be necessary to limit the thickness ratio of each layer because of each interlayer has interaction.
Particularly, each elemental diffusion that produces for fear of long-term heating, thereby the deterioration of the electric property that oxidation causes, are being coagulated insertion force are increased at the impedance that causes because of turn up when inserting because of junctor, problems such as abrasion, corrosion must have the best bed thickness ratio.Ideal bed thickness ratio is because of satisfying with following formula
0.2X≤Y≤5X 1 formula
0.05Y≤Z≤3Y 2 formulas
The bed thickness ratio surpasses the upper limit or is lower than the occasion of lower limit, the contact resistance after the heating, and the soldering welding property after the humidity test, the insertion force opposing of connector, wear loss, corrosion resisting property will be low, and can not satisfy various requirement.Therefore, Ceng thickness must satisfy 1 formula and the 2 formulas particularly important that just seems.
About the surfaceness of mother metal, measuring method is according to the regulation of JIS B 0601, and its 10 mean roughness are preferably below 1.5 μ m, and center line average roughness is preferably below 0.15 μ m.By limiting the surfaceness of mother metal, make each laminar surface that forms on the mother metal surface have stable smoothness, and make its adherence, appearance property is improved.Carrying out galvanized occasion,, film thickness distribution also there is good effect to heat-resisting adherence.
Regulation, particularly lower floor to the surfaceness of mother metal are Cu layer or Cu alloy layer, and the middle level is Ni or Ni alloy, the Cu layer, and the surface is Sn or Sn alloy layer, carries out thereafter making it have stable outward appearance and surfaceness after the thermal treatments such as remelting.Surfaceness after the remelting thermal treatment, preferably its 10 mean roughness are below 1.0 μ m, and center line average roughness is preferably below 0.1 μ m.
The oxidated layer thickness of mother metal self has suitable importance to the formation of each layer later on.Special relevant with pre-treatment, with the occasion that electro-plating method comes film forming (layer), influence its adherence, outward appearance, the hole generation during diffusion etc., the oxidated layer thickness of mother metal should be below 20nm, below the preferred 12nm.
Form the thermotolerance film (layer) of following structure effectively according to above method, surface thickness is Sn layer or the Sn alloy layer of 0.05～2 μ m, its inboard is that thickness is that 0.05～2 μ m and the Cu-Sn that satisfies formula 1 are the intermetallic compounds layer or the Cu layer of main body, and side is that thickness is the thermotolerance film (layer) of 0.01～1 μ m and Ni layer that satisfies formula 2 or Ni alloy layer within it.
Below manufacture method is described.
Hereinafter explain the method that obtains the present invention's structure effectively.
At first, prepare to pass through surfaceness, the mother metal that oxidated layer thickness is adjusted will carry out Cu layer film forming earlier in some cases in advance.When being copper, copper alloy as mother metal, the Cu layer of lower floor can omit.Below just preferred film electrochemical plating be that example is introduced.
Mother metal or carry out carrying out Ni or Ni alloy plating on the mother metal after Cu electroplates.Certainly, consider its adherence, must carry out sufficient degreasing, washing procedures such as pickling.Carrying out Cu then electroplates.Should illustrate that in order to improve the outward appearance of Cu electrolytic coating, adherence is preferably carried out pickling between Ni plating and the galvanized operation of Cu.
Carry out top layer Sn or Sn alloy plating thereafter.As mentioned above, form from bottom begin for the essential structure this point of Ni layer, Cu layer, Sn layer considerably important.
Secondly, middle diffusion of electroplating Cu layer and the most surperficial Sn layer obtains the Cu-Sn diffusion layer.This treatment process it would be desirable with the most surperficial Sn fusion remelting processing and carries out simultaneously.Type of heating when particularly, suitably adjusting the remelting processing obtains the thickness of desired Sn, Cu-Sn diffusion layer.Should illustrate that the galvanized thickness of intermediary Cu does not need residual Cu electrolytic coating down can form the Cu-Sn diffusion layer for suitable after the reaction.Concrete speech, residual Cu layer thickness are preferably below 0.7 μ m, more preferably below 0.3 μ m.Remaining Cu layer can spread after through long-term heating, makes the Cu-Sn diffusion layer grow up, thereby the Sn layer thickness on top layer is reduced, causing the contact resistance performance, the soldering welding property lowly.
The condition that remelting is handled, temperature: 300～900 ℃, the time: 1～300 second condition is an ideal conditions.Be lower than 300 ℃ or be higher than 900 ℃ as temperature, control remelting and the diffusion difficulty that just seems simultaneously.From obtaining surface of good state, inhibited oxidation aspect, the control of thickness of diffusion layer suppresses the sharp play of diffusion layer subregion and grows up and the Anomalous Diffusion aspect of formation, and temperature is an important key element.According to different remelting modes, atmosphere can appropriate change.Main remelting mode has, and combustion system, hot air circulation mode, infrared mode, joule heating mode etc. can be selected above any way.But the heat-up time of variety of way is different, under 1 second the situation of less than, can not obtain sufficient diffusion layer, surpasses under 300 seconds the situation, and effect is in state of saturation, and is unfavorable to reducing cost.
And wish that the oxide skin layer thickness after the remelting of Sn layer handled is thin as much as possible, its thickness is wished below 30nm.After the oxidated layer thickness on surface surpassed 30nm, its contact resistance will increase, and extremely unstable, made the electric property deterioration.And the adherence performance of soldering welding property, zone of oxidation is low, produces in manufacturing procedure thereafter and peels off phenomenon.Preferred oxidated layer thickness is wished below 20nm.The zone of oxidation here is based on stannic oxide, comprises diffusion in interpolation element, the Cu in the Cu-Sn diffusion layer, the Ni of lower floor layer or the Ni alloy layer in the Sn layer and diffusion and the composite oxides that contain element and Sn formation that come in the Cu base alloy of the element that comes, mother metal.
The oxide on surface that the surface forms and the Cu-Sn diffusion layer of lower floor, Ni layer or Ni alloy layer interact and have the wear resistant of making, the effect that slipperiness makes progress.But oxide on surface is to contact resistance, and the soldering welding property has bad influence, therefore wishes its thickness of control, more Bao Yuehao.
More than the protective film of Gou Chenging (layer) is applied to the hero of electrical element junctor, and female terminal is fit to be applied to hero, either party of female terminal, or two sides.Also can be applied to part necessary in the junctor.
Below record and narrate embodiments of the invention.
Table 1. has been charged to formation and the thickness of 16 kinds of surface treatment materials that No.1 to No.16 prepares in advance.The formation method of each layer all is electrochemical plating.Particularly, the Ni layer is to bathe with dithiocarbamic acid Ni, and the Cu layer is to bathe with copper sulfate, and the Sn layer is to be used as electroplate liquid with sulfate baths, carrying out Ni electroplating work procedure front and back, carries out pickling.
No.9, No.10, No.15 do not carry out Ni and electroplate, and No.11 does not carry out Ni, Cu and electroplates, and No.12 does not carry out Cu and electroplates, and No.16 does not carry out Sn and electroplates (table 1 is labeled as one).
Mother metal is that amount is the copper alloy plate of 1%Ni, 0.9%Sn, 0.05%P, and thickness of slab is the calendering material of 0.25mm, and surfaceness is, 10 mean roughness 0.9 μ m, center line average roughness 0.08 μ m, the about 7nm of surface oxidation layer thickness of mother metal is little more a lot of than the 20nm thickness that requires.
Change the condition of remelting in the test, carry out temperature range from 450 to 700 degree, the treatment time scope is handled from 4 seconds to 20 seconds continuous remelting, when carrying out the remelting processing, forms diffusion layer.The thickness of the surface oxide layer after remelting is handled use AES, and the measurement result of ESCA method is, the thickness of No.1 to No.14 is 3～8nm, No.15,16 the about 15nm of thickness, more than 16 kinds of materials surface oxide layer thickness all below 30nm a lot.Its surfaceness is 10 mean roughness 0.2～0.7 μ m, center line average roughness 0.05～0.10 μ m.
More than the thickness of each layer, from upper layer, in layer after the dissolving, measure its thickness with electrolytic process by thick mensuration meter of radiopaque layer and electrolytic process.The bed thickness that thickness is relatively thinner, with OJ electronics light-dividing device (AES), photoelectron light-dividing device (ESCA) etc., the cross section is measured with transmission electron microscope (TEM), observes.And the conformability of separating out electric weight and each layer thickness by calculating further improves the mensuration precision.Represent with ND in table for the layer (Sn＜0.05 μ m, Cu-Sn＜0.05m, Cu＜0.05 μ m) that can not measure its thickness.
Projects such as the frictional coefficient of the above test of mensuration investigation material, shaping processability, soldering welding property, heat-resisting adherence, contact resistance, variable color.
The Determination of Friction Coefficient method, as shown in Figure 1, the surface treatment plate of 3 concave configuration with inner radius R=1mm is as upside, place the load of 15N thereon, the speed of dividing with 100mm/ moves on the downside sheet material of handling through similar face, measure frictional force by the load gauge measuring device, calculate frictional coefficient.
90 ° of W pliability tests (is standard with JIS H 3110, R=0.2mm, rolling direction is with the perpendicular direction of rolling direction) are carried out in the be shaped evaluation of processing, observe the protrusion surface of test portion central part with 24 times of stereomicroscopes, estimate.And observe the surface of measuring the concave configuration that frictional coefficient uses with 24 times of stereomicroscopes simultaneously, confirm to have or not cracking.What cracking phenomena was not all observed in above binomial trials is zero seal, and what either party observed cracking phenomena is * seal.
The evaluation of soldering welding property is a standard with MIL-STD-202F-208, and exposure adopted nonactive scolder to carry out test evaluation after 1 hour in the ebullient steam.Test-results is zero seal with the wetted more than 95% of the test portion of test film, is lower than the 95% * seal of being.
The evaluation of heat-resisting adherence, 160 ℃, after the heating in 1000 hours, (with JIS H 3110 is standard, R=0.2mm, rolling direction to carry out 90 ° of W pliability tests, with the perpendicular direction of rolling direction) after, implement stripping test with adhesive plaster, what do not have peeling off phenomenon after the stripping test is zero seal, peeling off phenomenon be * print.Carry out visual surface discolouration inspection simultaneously, with the heating before compare, take place obvious metachromatism for * seal.
The test of contact resistance, test materials, with low current low voltage determinator, are carried out 4 utmost point leads method and are measured after the heating in 1000 hours through 160 ℃.When the maximum of Au contact increases the weight of to 0.5N, measure its resistance value.
Above evaluation of measuring result is shown in the table 2.
[table 1]
| № | The thickness of protective film (layer) (μ m) | ||||
| Sn | Cu-Sn | Cu | Ni | ||
| Material of the | 1 | 0.22 | 0.80 | ND | 0.31 |
| 2 | 0.53 | 0.89 | 0.05 | 0.25 | |
| 3 | 0.08 | 0.51 | ND | 0.63 | |
| 4 | 0.15 | 0.49 | 0.06 | 0.17 | |
| 5 | 0.57 | 0.60 | 0.06 | 0.25 | |
| 6 | 0.20 | 0.65 | 0.18 | 0.54 | |
| 7 | 0.66 | 0.81 | 0.32 | 0.61 | |
| 8 | 1.05 | 0.72 | ND | 0.39 | |
| Compare material | 9 | 0.78 | 0.74 | ND | - |
| 10 | 1.18 | 0.95 | ND | - | |
| 11 | 0.22 | 0.60 | - | - | |
| 12 | 0.30 | - | - | 0.58 | |
| 13 | 0.25 | 0.73 | 0.11 | 1.20 | |
| 14 | 2.26 | 0.75 | 0.30 | 0.46 | |
| 15 | ND | 2.33 | ND | - | |
| 16 | - | ND | 0.48 | 0.70 | |
[table 2]
| № | Frictional coefficient | Shaping processability | The soldering welding property | Thermotolerance | |||
| Adherence | Contact resistance | Variable color | |||||
| Material of the | 1 | 0.23 | ○ | ○ | ○ | 4.7 | ○ |
| 2 | 0.26 | ○ | ○ | ○ | 4.0 | ○ | |
| 3 | 0.21 | ○ | ○ | ○ | 5.3 | ○ | |
| 4 | 0.21 | ○ | ○ | ○ | 5.0 | ○ | |
| 5 | 0.26 | ○ | ○ | ○ | 4.0 | ○ | |
| 6 | 0.24 | ○ | ○ | ○ | 6.8 | ○ | |
| 7 | 0.28 | ○ | ○ | ○ | 4.4 | ○ | |
| 8 | 0.32 | ○ | ○ | ○ | 2.9 | ○ | |
| Compare material | 9 | 0.34 | ○ | ○ | ○ | 40 | × |
| 10 | 0.36 | ○ | ○ | ○ | 34 | × | |
| 11 | 0.24 | ○ | × | ○ | 146 | × | |
| 12 | 0.26 | ○ | × | ○ | 24 | × | |
| 13 | 0.24 | × | ○ | ○ | 3.8 | ○ | |
| 14 | 0.45 | ○ | ○ | ○ | 2.1 | ○ | |
| 15 | 0.25 | × | × | ○ | 158 | × | |
| 16 | 0.37 | ○ | × | ○ | More than 200 | × | |
According to table 1 ' the evaluation of measuring result of table 2, No.1 of the present invention～No. 8 material, its frictional coefficient is very little, and has good shaping processability, soldering welding property, the adherence of heating back protective film (layer), contact resistance, discoloration-resistant performance.Therefore above many good characteristics make it widely be used for the multipole junctor of using, charging terminal, printed circuit board (PCB) etc. the element that continues.
Compare with above result, do not have the frictional coefficient of the No.9 of Ni floor, No. 10 materials just bigger, and the heating back produces contact resistance, problems such as variable color.The No.11 material does not carry out the operation of the Ni of lower floor layer and middle Cu electrolytic coating, therefore mother metal Cu and surperficial Sn layer takes place form diffusion layer, though frictional coefficient is very little, the soldering welding property takes place, heating back contact resistance, problems such as variable color.
Do not carry out centre Cu and electroplate, do not have the No.12 material of Cu-Sn diffusion layer, the soldering welding property takes place, heating back contact resistance, problems such as variable color.
Protective film thickness of the present invention; the No.13 material that the Ni layer thickness is thicker; its shaping processability is just relatively poor; the No.14 material that the Sn layer thickness is thicker, its frictional coefficient is just relatively poor, does not have the thicker No.15 material of thickness of Ni floor and Cu-Sn diffusion layer; shaping processability takes place; the soldering welding property takes place, heating back contact resistance, problems such as variable color.The soldering welding property takes place in the No.13 material that does not have the Sn layer, heating back contact resistance, problems such as variable color.
Having each electric electrolytic coating identical with embodiment 1 forms.But No.17, the mother metal of 18, No. 21 materials are that brass is a kind of, thickness of slab 0.8mm, and No.19, the mother metal of 20, No. 22 materials is phosphor bronzes, thickness of slab 0.2mm.Above mother metal is that brass material and mother metal are that the surfaceness of phosphor bronze material is that 10 mean roughness are respectively 1.0,0.9 μ m, center line average roughness is respectively 0.13,0.08 μ m, the surface oxidation layer thickness of mother metal all is about 8nm, and is thin more many than the 20nm that requires.
Second carries out 350～800 ℃, and 5～20 seconds continuous remelting is handled, and when carrying out the remelting processing, forms the Cu-Sn diffusion layer, is ready to above material as stated above.With the frictional coefficient of test material more than the method researching determining identical, forming process, soldering welding property, heat-resisting adherence, contact resistance, characteristics such as variable color with embodiment 1..
[table 3]
| № | Protective film thickness (μ m) | ||||
| Sn | Cu-Sn | Cu | Ni | ||
| Material of the present invention | 17 | 0.18 | 0.62 | 0.14 | 0.45 |
| 18 | 0.62 | 0.77 | 0.07 | 0.33 | |
| 19 | 0.23 | 0.63 | 0.20 | 0.71 | |
| 20 | 0.60 | 0.81 | 0.11 | 0.64 | |
| Relatively | 21 | 0.85 | 0.81 | 0.61 | - |
| 22 | 1.01 | 0.94 | 0.53 | - | |
[table 4]
| № | Frictional coefficient | Shaping processability | The soldering welding property | Thermotolerance | |||
| Adherence | Contact resistance | Variable color | |||||
| Material of the present invention | 17 | 0.29 | ○ | ○ | ○ | 7.2 | ○ |
| 18 | 0.36 | ○ | ○ | ○ | 5.9 | ○ | |
| 19 | 0.23 | ○ | ○ | ○ | 6.4 | ○ | |
| 20 | 0.30 | ○ | ○ | ○ | 4.8 | ○ | |
| Relatively | 21 | 0.40 | ○ | ○ | ○ | 64 | × |
| 22 | 0.36 | ○ | ○ | × | 43 | × | |
Table 3, table 4 show that very significantly the frictional coefficient of No.17 of the present invention～No. 20 material is very little, and, have good forming process, soldering welding property, heat-resisting adherence, contact resistance, characteristics such as anti-variable color.According to above test-results, no matter mother metal is brass or phosphor bronze, and the present invention has identical effect.
The No.21 that does not have the Ni layer, the frictional coefficient of No. 22 materials is just bigger, and the heating back produces contact resistance, problems such as variable color.No.22 material particularly, the adherence of heating back protective film is deterioration significantly, and with NO.19, No. 20 material compared just can find that effect of the present invention is considerably big.
On embodiment 1 identical materials, carry out the identical plating of embodiment 1, form various electrolytic coatings.The surface electrical coating of No.23,24, No. 27 materials changes to the Sn alloy layer.Lower floor's electrolytic coating of No.23, No. 27 materials changes to the Ni floor.Lower floor's electrolytic coating of No.24 material changes to the Ni alloy layer.The surface electrical coating of No.25,26, No. 28 materials is the Sn floor, and lower floor's electrolytic coating changes to the Ni alloy layer.
The Sn alloy plated layer uses organic complex salt solution, carries out Sn-10%Zn and electroplates.The Ni alloy plated layer uses the watt that adds phosphorous acid to bathe, and carries out Ni-5%P and electroplates.Select the remelting condition identical with embodiment 1. to carry out remelting and handle, Zn can be diffused into the surface in the Sn-Zn alloy plating process, and formation is the oxide compound at center with oxidation Zn, but does not influence the variation of contact resistance.And thickness of oxide layer is approximately 5～11nm, and is more a lot of than the 30nm thin thickness of regulation.
No.23～No. 26 material generates the Cu-Sn diffusion layer because of the heat affecting of remelting, and No.27, No. 28 materials do not generate the Ni-Sn diffusion layer because of there not being the Cu floor so do not generate the Cu-Sn diffusion layer.
[table 5]
| № | Protective film thickness (μ m) | ||||
| Sn(-Zn) | Cu-Sn(Ni-Sn) | Cu | Ni(-P) | ||
| Material of the present invention | 23 | 0.25 | 0.58 | 0.08 | 0.32 |
| 24 | 0.83 | 0.79 | 0.12 | 0.30 | |
| 25 | 0.13 | 0.74 | 0.06 | 0.19 | |
| 26 | 0.98 | 0.66 | 0.21 | 0.34 | |
| Relatively | 27 | 0.18 | 0.88 | - | 0.37 |
| 28 | 0.08 | 0.79 | - | 0.41 | |
[table 6]
| № | Frictional coefficient | Shaping processability | The soldering welding property | Thermotolerance | |||
| Adherence | Contact resistance | Variable color | |||||
| Material of the present invention | 23 | 0.22 | ○ | ○ | ○ | 9.4 | ○ |
| 24 | 0.28 | ○ | ○ | ○ | 6.7 | ○ | |
| 25 | 0.22 | ○ | ○ | ○ | 5.5 | ○ | |
| 26 | 0.33 | ○ | ○ | ○ | 4.3 | ○ | |
| Relatively | 27 | 0.24 | ○ | × | ○ | 49 | ○ |
| 28 | 0.30 | × | × | × | 84 | × | |
At table 5, shown in the table 6 that No.23 of the present invention～No. 26 material has good very little frictional coefficient, and had characteristics such as good shaping processability, soldering welding property, the protective film adherence after the heat test, contact resistance, anti-variable color.Therefore, the Sn layer on surface changes to the Sn alloy layer, and the Ni layer changes to the Ni alloy layer, can not change effect of the present invention for the present invention.
Above relatively result; having or not of interlayer Cu-Sn but has very big influence; the soldering welding property that does not have the No.27 material in Cu-Sn middle layer; the contact resistance performance can be low; the soldering welding property that does not have the No.28 material in Cu-Sn middle layer; protective film adherence after the heat test, the contact resistance performance can be low.Therefore, can illustrate that effect of the present invention is very big.
[effect of invention]
Above embodiment has shown clearly, use surface treatment of the present invention and manufacture method thereof, so that the electric electronic element that uses the present invention to process has good friction opposing, processing and forming, the characteristics such as Welding, and after for a long time overheated, has good adherence, contact resistance, the characteristics such as anti-variable color, the connector such as Hyundai Motor Denso product that can apply to densification, also can apply to require to have wear-resisting consumption, the printed circuit board (PCB) of Welding performance continues and uses connector, so that use material of the present invention to become good electric electronic element material.
Claims (8)
1. heat-resistance protection film; it is characterized in that; by upper layer is Sn layer or the Sn alloy layer of bed thickness X 0.05～2 μ m; its la m is the layer based on the intermetallic compound of Cu-Sn of containing of bed thickness Y 0.05～2 μ m; innermost layer is that Ni or the Ni alloy layer of bed thickness Z 0.01～1 μ m constitutes; wherein 0.2X≤Y≤5X, and 0.05Y≤Z≤3Y.
2. the heat-resistance protection films of claim 1 or 2 records between above-mentioned intermetallic compounds layer and above-mentioned Ni or the Ni alloy layer, have thickness and are the Cu layer below the 0.7 μ m.
Claim 1 or 2 the record the heat-resistance protection films, protected material of above-mentioned heat-resistance protection film or material surface at least are Cu or Cu alloy.
4. the manufacture method of each record heat-resistance protection film of claim 1～3 is characterized in that forming Ni or Ni alloy layer successively from material surface, and the Cu layer behind Sn or the Sn alloy layer, carries out remelting to it and handles.
5. the manufacture method of the heat-resistance protection film of each record of claim 1～3; it is characterized in that forming Ni or Ni alloy layer successively from material surface; the Cu layer; behind Sn or the Sn alloy layer; it is heat-treated; 10 average light slipperies of described material surface slickness are below 1.5 μ m, and its medullary ray average light slippery is below 0.15 μ m.
6. the manufacture method of the heat-resistance protection film of each record of claim 1～3; it is characterized in that forming Ni or Ni alloy layer successively from material surface; the Cu layer; behind Sn or the Sn alloy layer; it is carried out remelting handles; 10 average light slipperies of described material surface slickness are below 1.5 μ m, and its medullary ray average light slippery is below 0.15 μ m.
7. the manufacture method of the heat-resistance protection film of wantonly 1 record in the claim 4～6 is characterized in that forming Cu or Cu alloy layer earlier at material surface before with above-mentioned Ni or Ni alloy layer film forming.
8. electric electronic element is characterized in that the heat-resistance protection film in wantonly 1 record of material surface formation claim 1～3.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP024031/2001 | 2001-01-31 | ||
| JP2001024031A JP2002226982A (en) | 2001-01-31 | 2001-01-31 | Heat resistant film, its manufacturing method, and electrical and electronic parts |
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| CNB011433949A Division CN1325696C (en) | 2001-01-31 | 2001-12-21 | Heat-resistance protection film, its manufacture method and electric electronic element |
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| CN1940137A true CN1940137A (en) | 2007-04-04 |
| CN100528550C CN100528550C (en) | 2009-08-19 |
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| CNB011433949A Expired - Lifetime CN1325696C (en) | 2001-01-31 | 2001-12-21 | Heat-resistance protection film, its manufacture method and electric electronic element |
| CN 200710108823 Pending CN101081554A (en) | 2001-01-31 | 2001-12-21 | Heat resistant film, its manufacturing method, and electrical and electronic parts |
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| CNB011433949A Expired - Lifetime CN1325696C (en) | 2001-01-31 | 2001-12-21 | Heat-resistance protection film, its manufacture method and electric electronic element |
| CN 200710108823 Pending CN101081554A (en) | 2001-01-31 | 2001-12-21 | Heat resistant film, its manufacturing method, and electrical and electronic parts |
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| JP2002226982A (en) * | 2001-01-31 | 2002-08-14 | Dowa Mining Co Ltd | Heat resistant film, its manufacturing method, and electrical and electronic parts |
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2001
- 2001-01-31 JP JP2001024031A patent/JP2002226982A/en active Pending
- 2001-12-21 CN CNB2006101149269A patent/CN100528550C/en not_active Expired - Lifetime
- 2001-12-21 CN CNB011433949A patent/CN1325696C/en not_active Expired - Lifetime
- 2001-12-21 CN CN 200710108823 patent/CN101081554A/en active Pending
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Also Published As
| Publication number | Publication date |
|---|---|
| CN1368562A (en) | 2002-09-11 |
| JP2002226982A (en) | 2002-08-14 |
| CN101081554A (en) | 2007-12-05 |
| CN1325696C (en) | 2007-07-11 |
| CN100528550C (en) | 2009-08-19 |
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