CN101952080A - Solder alloy and process for producing the same - Google Patents
Solder alloy and process for producing the same Download PDFInfo
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- CN101952080A CN101952080A CN2008801202944A CN200880120294A CN101952080A CN 101952080 A CN101952080 A CN 101952080A CN 2008801202944 A CN2008801202944 A CN 2008801202944A CN 200880120294 A CN200880120294 A CN 200880120294A CN 101952080 A CN101952080 A CN 101952080A
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- 229910000679 solder Inorganic materials 0.000 title claims abstract description 157
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 100
- 239000000956 alloy Substances 0.000 title claims abstract description 100
- 238000000034 method Methods 0.000 title claims abstract description 65
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 141
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 137
- 239000000463 material Substances 0.000 claims abstract description 58
- 239000000203 mixture Substances 0.000 claims abstract description 31
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims description 39
- 229910052751 metal Inorganic materials 0.000 claims description 39
- 229910052802 copper Inorganic materials 0.000 claims description 33
- 238000010438 heat treatment Methods 0.000 claims description 31
- 238000004519 manufacturing process Methods 0.000 claims description 29
- 238000004458 analytical method Methods 0.000 claims description 13
- 229910002804 graphite Inorganic materials 0.000 claims description 11
- 239000010439 graphite Substances 0.000 claims description 11
- 238000010309 melting process Methods 0.000 claims description 11
- 239000000446 fuel Substances 0.000 claims description 9
- 229910052709 silver Inorganic materials 0.000 claims description 9
- 239000013078 crystal Substances 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 238000004445 quantitative analysis Methods 0.000 claims description 3
- 238000002844 melting Methods 0.000 abstract description 7
- 230000008018 melting Effects 0.000 abstract description 6
- 238000001816 cooling Methods 0.000 abstract description 4
- 238000005266 casting Methods 0.000 abstract 1
- 239000011369 resultant mixture Substances 0.000 abstract 1
- 239000010949 copper Substances 0.000 description 37
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 20
- 239000003795 chemical substances by application Substances 0.000 description 12
- 229910000765 intermetallic Inorganic materials 0.000 description 11
- 229910020220 Pb—Sn Inorganic materials 0.000 description 9
- 238000001878 scanning electron micrograph Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000005204 segregation Methods 0.000 description 4
- 229910020836 Sn-Ag Inorganic materials 0.000 description 3
- 229910020988 Sn—Ag Inorganic materials 0.000 description 3
- 230000000116 mitigating effect Effects 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 229910018471 Cu6Sn5 Inorganic materials 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical compound C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 description 1
- 229910001573 adamantine Inorganic materials 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 229910000905 alloy phase Inorganic materials 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C13/00—Alloys based on tin
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electric Connection Of Electric Components To Printed Circuits (AREA)
- Crucibles And Fluidized-Bed Furnaces (AREA)
- Furnace Details (AREA)
- Powder Metallurgy (AREA)
- Manufacture Of Alloys Or Alloy Compounds (AREA)
Abstract
A lead-free solder alloy is provided which has bonding reliability and eliminates the problem that conventional lead-free solder alloys are inferior in bond strength to lead-containing solder alloys. The solder alloy is characterized by being obtained through the addition of a given amount of carbon to a lead-free solder material in an environment having a high temperature in the range of 800-1,200 DEG C. Also provided is a process for producing a solder alloy characterized by comprising: a melting step in which a metal-melting furnace for high temperatures into which a lead-free solder material has been charged is heated to a high-temperature environment in the range of 800-1,200 DEG C to melt the lead-free solder material; a carbon addition step in which a given amount of carbon is added to the lead-free solder material which has been melted in the melting step and is held in the high-temperature environment (melted lead-free solder material); a stirring step in which the melted lead-free solder material and the carbon are stirred; and a cooling step in which the resultant mixture obtained in the stirring step by stirring the melted lead-free solder material and the carbon is poured into a casting mold to cool and solidify the mixture.
Description
Technical field
The present invention relates to a kind of soft solder alloy, in more detail, relate to by in solder material, adding the soft solder alloy that carbon obtains.
Background technology
In the past, as the soft solder alloy, known soft solder alloy with Pb-Sn was the soft solder alloy of representative.But there is the problem of plumbous harmfulness in this soft solder alloy, and is influential to environment, therefore uses to be restricted.
Therefore, need not contain the lead-free solder alloy of harmful lead,, propose various schemes (with reference to patent documentation 1～patent documentation 5) for described lead-free solder alloy as the soft solder alloy.As representational lead-free solder alloy, the Sn-Ag class soft solder alloy that contains 3.5% Ag in Sn is for example arranged.The fusing point of this Sn-Ag class soft solder alloy is 221 ℃, and is lower, is extensive use of as the lead-free solder alloy now.
But, described Sn-Ag class soft solder alloy since with the leaded alloy phase of soft solder in the past ratio, bond strength is poor, therefore in the field that requires high joint reliability (for example vehicular field etc.), angle by security considers that postponement is carried out unleaded, also contains Pb soft solder alloy in use now.In view of influence, unleaded no matter which kind of field all should be carried out as soon as possible to environment.Therefore, the expectation exploitation is unlike the lead-free solder alloy of the joint reliability difference that contains Pb soft solder alloy.
Patent documentation 1: TOHKEMY 2007-237252 communique
Patent documentation 2: TOHKEMY 2006-255784 communique
Patent documentation 3: TOHKEMY 2002-346788 communique
Patent documentation 4: TOHKEMY 2001-225188 communique
Patent documentation 5: Japanese kokai publication hei 10-6075 communique
Summary of the invention
In view of the above problems, the bond strength that promptly existing lead-free solder alloy is had is inferior to and contains this problem of Pb soft solder alloy, the objective of the invention is to, and addresses this problem, and the joint reliability of lead-free solder alloy is improved.
In the past, the lead-free solder alloy is made under the low temperature environment of 250～400 ℃ of temperature ranges usually, the present invention is based on inventor's following discovery, promptly, under the hot environment more much higher than 250～400 ℃ of temperature ranges, can be so that the carbon that is added be can practical degree evenly distributing.
In order to reach above-mentioned purpose, the present invention is the soft solder alloy, it is characterized in that, adds the carbon of ormal weight under hot environment in the lead-free solder material.
In addition, it is characterized in that in above-mentioned soft solder alloy, above-mentioned hot environment is in 800～1200 ℃ the temperature range.
In addition, it is characterized in that the carbon amount of afore mentioned rules amount is 0.01～0.7wt%.
In addition, it is characterized in that above-mentioned carbon is the graphite mould of hexagonal crystal system.
In addition, it is characterized in that above-mentioned lead-free solder material is 96.5wt%Sn-3wt%Ag-0.5wt%Cu.
In addition, it is characterized in that above-mentioned lead-free solder material is 99.3wt%Sn-0.7wt%Cu.
In addition, it is characterized in that above-mentioned lead-free solder material is 99.0wt%Sn-0.7wt%Cu-0.3wt%Ag.
In addition, the present invention is the manufacture method of soft solder alloy, it is characterized in that, possesses following operation:
The high temperature that has dropped into the lead-free solder material is heated to hot environment with the metal molten stove, makes the melting process of above-mentioned lead-free solder material fusing;
To by the fusing of above-mentioned melting process and be in lead-free solder material (fusing lead-free solder material) under the above-mentioned hot environment add ormal weight carbon add the carbon operation;
Stir the agitating procedure of above-mentioned fusing lead-free solder material and above-mentioned carbon; With
The above-mentioned fusing lead-free solder material that will stir by above-mentioned agitating procedure and the mixture of above-mentioned carbon inject mold, make the refrigerating work procedure of said mixture cooled and solidified.
In addition, it is characterized in that in above-mentioned manufacture method, above-mentioned hot environment is in 800～1200 ℃ the temperature range.
In addition, it is characterized in that the carbon amount of afore mentioned rules amount is in the scope of 0.01～0.7wt%.
In addition, it is characterized in that, in above-mentioned manufacture method, above-mentioned high temperature is equipped with the metal molten stove and accessory: drop into above-mentioned lead-free solder material and above-mentionedly add the carbon agent kiln portion of (adding the charcoal drug), form the heating space portion of airtight heating space in the top position of above-mentioned kiln portion, heating fuel supplied to the heating part of above-mentioned airtight heating space of heating in the above-mentioned airtight heating space and above-mentioned kiln portion and the exhaust outlet that forms in above-mentioned heating space portion.
In addition, it is characterized in that, in above-mentioned manufacture method, in above-mentioned melting process, regulate the quantity delivered of above-mentioned heating fuel, so that the oxygen amount of being discharged with the above-mentioned exhaust outlet of metal molten stove by above-mentioned high temperature is 0.
In addition, it is characterized in that, in above-mentioned manufacture method, possesses following operation: will put into low temperature at the cakey said mixture of above-mentioned refrigerating work procedure and use in the metal molten stove, under low temperature environment, melt, the above-mentioned lead-free solder material that adds simultaneously ormal weight in the metal molten stove in addition to low temperature, transfers rare so that the carbon amount is for expecting the adjustment operation of concentration; With will re-inject mold by the mixture that above-mentioned adjusting operation has been regulated the carbon amount, make the refrigerating work procedure again of its cooled and solidified.
In addition, it is characterized in that, in above-mentioned manufacture method, has analysis procedure, in above-mentioned adjusting operation, based on the analysis result of above-mentioned analysis procedure, determine the ormal weight of above-mentioned other adding, described analysis procedure is the carbon quantitative analysis operation of analyzing before above-mentioned adjusting operation in the cakey said mixture of above-mentioned refrigerating work procedure.
In addition, it is characterized in that in above-mentioned manufacture method, the carbon amount in the cakey said mixture of above-mentioned refrigerating work procedure is in the high concentration range in 0.01～0.7wt% scope, above-mentioned expectation concentration is in the low strength range in 0.01～0.7wt% scope.
In addition, it is characterized in that in above-mentioned manufacture method, above-mentioned low temperature environment is in 250～400 ℃ the temperature range.
In addition, it is characterized in that in above-mentioned manufacture method, above-mentioned carbon is the graphite mould of hexagonal crystal system.
In addition, the present invention is the soft solder alloy, it is characterized in that, by above-mentioned manufacture method manufacturing.
According to soft solder alloy of the present invention, when passing through unleaded care environment, solve bond strength that existing lead-free solder alloy had and be inferior to and contain this problem of Pb soft solder alloy, improved bond strength tremendously, helped the raising of joint reliability thus.
In addition, according to the manufacture method of soft solder alloy of the present invention, can be simply and obtain the lead-free solder alloy that bond strength improves tremendously effectively.
Description of drawings
Fig. 1 is the SEM image at the interface of sample A when being illustrated in copper base (Cu) and going up in conjunction with sample A (Sn-3.5wt%Ag+0.03wt%C) and copper base.
Fig. 2 is the SEM image at the interface of sample B when being illustrated in copper base (Cu) and going up in conjunction with sample B (Sn-3.5wt%Ag) and copper base.
Fig. 3 is the skeleton diagram of high temperature with the metal molten stove.
Fig. 4 is the skeleton diagram of low temperature with the metal molten stove.
The specific embodiment
Maximum of the present invention is characterised in that, by add carbon in the lead-free solder material under hot environment, obtains the soft solder alloy.Below, the embodiment of the present application is described, but the present application is not limited by it.
Soft solder alloy of the present invention adds ormal weight in the lead-free solder material under hot environment carbon obtains.Wherein, hot environment has the following meaning.Promptly, in the past, the lead-free solder alloy is made under the low temperature environment of 250～400 ℃ of temperature ranges usually, but the present invention is than the much higher hot environment of 250～400 ℃ of temperature ranges (for example, the hot environment of 800～1200 ℃ of temperature ranges) under, can be so that the carbon that is added be can practical degree evenly distributing.
As hot environment of the present invention, in preferred 800～1200 ℃ scope.When in the lead-free solder material, adding carbon, under less than 800 ℃ low temperature environment, the carbon piece is disperseed, therefore can't obtain effective soft solder alloy.In addition, under than 1200 ℃ of high hot environments, high temperature has the tendency of boiling with the solder material in the metal molten stove, is not suitable for actual manufacturing.Therefore, though be necessary under the environment of high temperature more, to add carbon, at 1200 ℃ with the interior form that obtains desirable carbon.Therefore, for than 1200 ℃ of high hot environments,, expend the combustion fuel cost thus even under the environment of high temperature more, add carbon, therefore uneconomical, nonsensical.
The carbon amount of adding in lead-free solder material of the present invention is preferably 0.01～0.7wt%.Because the carbon itself that adds does not directly generate the adhesion with soft solder, therefore the carbon amount of adding exists an amount of.Excessive when bigger than 0.7wt% in the carbon amount, the adhesion of soft solder alloy may die down, if the carbon amount below 0.01wt%, then the carbon amount is very few, to such an extent as to can't bring into play the effect that is produced by the carbon that adds, can't obtain necessary bond strength.
On the contrary, for the carbon amount, think that intensity, the hardness of the soft solder alloy that obtains more at most improves more.But,, when the intensity of measuring soft solder alloy of the present invention etc., when making the carbon amount of interpolation be 0.7wt%, in the present situation of the solder in every field, can guarantee more than the maximum necessary strength for various carbon amounts.In addition, when making the carbon amount bigger than 0.7wt%, electrical conductivity is low excessively, may have problems on practicality.In addition, when making the carbon amount bigger, make carbon evenly spread the very difficulty that becomes, be difficult to guarantee practical quality than 0.7wt%.Wherein, because atomic molar ratio Sn, the Ag etc. of carbon are little, even therefore the carbon amount is the scope of 0.01～0.7wt%, the carbon number of interpolation also may not lack.Therefore, the upper limit for the carbon amount is made as 0.7wt%.
In addition, for described carbon amount,, suitably determine by the intensity of needs, hardness, electrical conductivity etc. according to the purposes of soft solder.
In addition, the preferred carbon that adds is the graphite mould of hexagonal crystal system.When carbon is graphite, because carbon has soft characteristic, therefore in the hot environment of 800～1200 ℃ of temperature ranges) under, can be so that the carbon that is added be can practical degree evenly distributing.Relative therewith, when carbon is the brilliant of cubic system, owing to have an adamantine characteristic,, can not make the carbon that is added can practical degree evenly distributing even therefore under the hot environment of 800～1200 ℃ of temperature ranges.
Below, based on experimental example, the present invention is carried out specific description.Should illustrate,, use Sn-3.5wt%Ag+0.03wt%C (sample A) and Sn-0.7wt%Cu+0.05wt%C (sample C) as the sample of the soft solder alloy of the present invention that uses in the experiment.In addition, the carbon of interpolation is graphite mould.Wherein, Sn-3.5wt%Ag+0.03wt%C (sample A) is illustrated in the carbon C that adds 0.03wt% in the lead-free solder material (Sn-0.7wt%Cu) of Ag of the Sn that contains the female tire of the above conduct of 96wt% and 3.5wt%, and Sn-0.7wt%Cu+0.05wt%C (sample C) is illustrated in the carbon C that adds 0.05wt% in the lead-free solder material (Sn-0.7wt%Cu) of Cu of the Sn that contains the female tire of the above conduct of 99wt% and 0.7wt%.
(experimental example 1)
At first, sample A and sample C are carried out twin shaft X-ray diffraction mensuration.The both has the peak that is considered to carbon as a result.
(experimental example 2)
Then, use SEM (scanning electron microscope) that sample surfaces is observed.If relatively,, in sample B, find to think the existence of the black object of carbon then with respect to the equally distributed basically state of observed carbon in sample A with sample A and the Sn-3.5wt%Ag (sample B) that does not add carbon.In addition, in the comparison of sample C and Sn-0.7wt%Cu (sample D), observe same result,, in sample D, find to think the existence of the black object of carbon with respect to the equally distributed basically state of observed carbon in sample C.Hence one can see that, and the carbon of the hot environment (800～1200 ℃) of fusing point during far above perparation of specimen A and sample C does not melt, and is in the state of imbedding in the sample.
(experimental example 3)
Then, utilize DSC (differential scanning calorimetry) to measure the fusing point of each sample.Measurement result is shown in following table 1～table 4.
[table 1]
[table 2]
[table 3]
[table 4]
As above shown in table 1 and the table 2, if the fusing point of comparative sample A and sample B is found almost no change.In addition, as above shown in table 3 and the table 4, if the fusing point of comparative sample C and sample D is then found almost no change equally.Thus, the interpolation that can confirm carbon does not make the fusing point of soft solder alloy change.This be because, the carbon among sample A and the sample C with melting the existence.That is, therefore the fusing point of sample A and sample C compares no change with sample B with the fusing point of sample D fully not because of carbon changes.
(experimental example 4)
Then, measure the resistivity (μ Ω cm) of Pb-Sn soft solder alloy and each sample (sample A and sample B, sample C and sample D), resistivity is for engaging the electronic unit important factors.Its measurement result is as shown in table 5 below.In table 5, left part represents not add the Pb-Sn soft solder alloy in the past of carbon, and pars intermedia is represented sample A and sample B side by side, and right part is represented sample C and sample DB side by side.
[table 5]
As above shown in the table 5, sample B and the sample D as the lead-free solder alloy is lower than the resistivity of leaded Pb-Sn soft solder alloy as can be known, is good, but has added the sample A of carbon and the resistivity of sample C further improves.As shown in Table 5, Sn-3.5wt%Ag is remarkable because of the effect that interpolation carbon improves electrical conductivity.Think to be that therefore the intermetallic compound of the carbon absorption soft solder that surface area is big suppresses the generation of intermetallic compound, is segmented simultaneously by adding the reason that carbonaceous resistivity descends, electrical conductivity is improved.The improvement of described electrical conductivity very preferably, can be described as and adds the excellent effect that carbon obtains on the characteristic of soft solder.
(experimental example 5)
Then, measure the Vickers hardness of Pb-Sn soft solder alloy and each sample (sample A and sample B, sample C and sample D).Its measurement result is as shown in table 6 below.
[table 6]
As above shown in the table 6, if sample A and sample B are compared with sample C and sample D, then the result is by adding carbon, and hardness is improved.Moreover, if with Pb-Sn soft solder alloy and sample A and sample C comparison, then the result shows the above hardness of Pb-Sn soft solder alloy by adding carbon.Thinking that this result is identical with the situation that above-mentioned resistivity reduces, also is because the big carbon of surface area adsorbs the intermetallic compound of soft solder, therefore suppresses the generation of intermetallic compound, is segmented simultaneously.
(experimental example 6)
Known, when the soft solder alloy for example was bonded to copper base, the copper of substrate (Cu) entered Yin Re and the soft solder alloy and the diffusion of melting, and carries out alloying, carries out combination thus.This alloy is called intermetallic compound (IMC (innermetallic compound)), because this intermetallic compound is hard, crisp, electrical conductivity is also poor, therefore reduce significantly soft solder in conjunction with reliability.Do not have the intermetallic compound just can not be, but preferred this layer approach combination securely as much as possible in conjunction with soft solder alloy and substrate.
Fig. 1 is the SEM image at the interface of sample A when being illustrated in copper base (Cu) and going up in conjunction with sample A (Sn-3.5wt%Ag+0.03wt%C) and copper base.Fig. 2 is the SEM image at the interface of sample B when being illustrated in copper base (Cu) and going up in conjunction with sample B (Sn-3.5wt%Ag) and copper base.The SEM image at the interface of observation sample A and copper base finds that its interface is thin, and shape is even.Relative therewith, in the SEM image at the interface of sample B and copper base, observe its interface roughness and inhomogeneous, each is concavo-convex big.Hence one can see that, and B compares with sample, and the surface area at the interface of sample A and copper base is big, therefore combination more firmly.
In addition, in the SEM image at the interface of the sample B of Fig. 2 and copper base, find on the interface of sample B and copper base, to produce slight crack (Crack).Relative therewith, in the SEM image at the interface of the sample A of Fig. 1 and copper base, find that slight crack (Crack) disappears on the interface of sample A and copper base.
One of big shortcoming that is had as the such lead-free solder material in the past of sample B as shown in Figure 2, can be set forth on the interface with the object member and produce slight crack (Crack), is origin with this slight crack (Crack), produces the fragility of soft solder combination.If consider this, then the meaning of the slight crack on the interface of sample A and copper base (Crack) of Fig. 1 disappearance is very far-reaching.Think not the producing on the interface of sample A and copper base in the intermetallic compound (Cu6Sn5 etc.) that this feature of slight crack (Crack) forms on the interface of sample A and copper base of Fig. 1, the carbon of interpolation is that graphite mould is important.That is, think the carbon of the graphite mould of being added because the crystal structure of its hexagonal crystal system, effect with the mitigation structure on the mechanics.Think in the carbon of graphite mould, with respect at the big covalent bond of the ab-of crystallization face internal bond, present the little combination of passing through Van der Waals force of adhesion on the c-direction of principal axis, intermetallic compound may reside between the axial layer of c-, forms the mitigation structure on the mechanics.Like this, think that the carbon that adds is not the diamond-type of cubic system but this feature of graphite mould is the major reason that slight crack (Crack) disappears.When carbon is the diamond-type of cubic system,, therefore think the leeway of the effect of not bringing into play the mitigation structure on the mechanics because crystal structure is with the strong covalent bond combination.
In addition, if observe the enlarged image element distribution image (not shown) at interface separately, then can more clearly observe and in the SEM image, fail the boundary line of clearly observed Cu and Sn.Thus, can read the area of the mixing of Cu and Sn, the formation zone of its cartographic represenation of area intermetallic compound.For the area of described intermetallic compound, B compares with sample, and it is little to observe sample A, therefore, can confirm reliably further can improve the reliability of combination by adding carbon by enlarged image element distribution image.
(experimental example 7)
Then, by tension test, measure the yield stress and the hot strength of Pb-Sn soft solder alloy and each sample (sample A and sample B, sample C and sample D).Its measurement result is shown in following table 7 and table 8.
[table 7]
[table 8]
As above shown in table 7 and the table 8, find that sample A compares with sample B, yield stress and hot strength all improve, and sample C compares with sample D, and yield stress and hot strength also all improve.That is, as can be known carbon be added with the raising that helps yield stress and hot strength.Particularly the result of the hot strength of sample A is more than the Pb-Sn soft solder alloy.
As mentioned above, in the lead-free solder alloy, find that it is very effective to add carbon in hardness, hot strength, particularly aspect reliability.
Should illustrate, as the lead-free solder material that adds carbon, can use the lead-free solder material of 96.5wt%Sn-3wt%Ag-0.5wt%Cu, the lead-free solder material of 99.3wt%Sn-0.7wt%Cu or 99.0wt%Sn-0.7wt%Cu-0.3wt%Ag etc.
Below, based on embodiment, the manufacture method that carbon is made the soft solder alloy of adding of the present invention is described in order in the lead-free solder material.Should illustrate that the present invention is not subjected to the qualification of these embodiment.
Fig. 3 is a high temperature with the skeleton diagram of metal molten stove, and high temperature is equipped with the metal molten stove and accessory: drop into the lead-free solder material and Powdered or granularly add the kiln portion 2 of carbon agent, form the heating space portion 3 of airtight heating space 6 in the top position of kiln portion 2, supply heating fuel and heat the heating part that comprises a plurality of gas arc lamps 4 of airtight heating space 6 and kiln portion 2 and to airtight heating space 6 at the exhaust outlet 7 that is used to discharge the gas in the airtight heating space 6 of heating space portion 6 formation.Use in the metal molten stove 1 at high temperature, put into the mixture 5 that comprises the lead-free solder material and add the carbon agent in kiln portion 2, mixture 5 is heated 800～1200 ℃ scopes by with the airtight heating space 6 of heating part 4 heating.
Fig. 4 is the skeleton diagram of expression low temperature with metal molten stove 8, and low temperature possesses with metal molten stove 8: be dropped in the low temperature at the cakey mixture 11 of refrigerating work procedure described later with kiln portion 9 be positioned at the low-temperature heat portion 10 that comprise a plurality of gas arc lamps of low temperature with the bottom of kiln portion 9.Use in the metal molten stove 8 at low temperature, in low temperature kiln portion 9, be placed in the cakey mixture 11 of refrigerating work procedure, 250～400 ℃ temperature range mixture 11 is heated by low-temperature heat portion 10.
The manufacture method of soft solder alloy of the present invention possesses: the high temperature that will drop into the lead-free solder material is heated to 800～1200 ℃ hot environment with metal molten stove 1, makes the melting process of lead-free solder material fusing; To by the fusing of above-mentioned melting process and be in that lead-free solder material (fusing lead-free solder material) under the above-mentioned hot environment adds the Powdered or granular carbon that adds the carbon agent of the conduct of ormal weight add the carbon operation; With above-mentioned fusing lead-free solder material and the above-mentioned agitating procedure that adds carbon agent stirring; With will inject molds by above-mentioned fusing lead-free solder material and the above-mentioned mixture 5 that adds the carbon agent that above-mentioned agitating procedure has stirred, make the refrigerating work procedure of said mixture cooled and solidified.Wherein, the carbon amount of afore mentioned rules amount is in the scope of 0.01～0.7wt%.
In above-mentioned melting process, regulate the quantity delivered of the heating fuel of the gas arc lamp in the heating part 4, so that the oxygen amount of being discharged with the exhaust outlet 7 of metal molten stove 1 by high temperature is 0.Thus, can prevent comprising solder material and adding the oxidation of the mixture 5 of carbon agent in the kiln portion 2.
At the cakey mixture of above-mentioned refrigerating work procedure 5 because from 800～1200 ℃ high temperature cooling, so Sn separates easily with Ag, and segregation may take place.Therefore, will drop into low temperature at the cakey mixture 5 of above-mentioned refrigerating work procedure and use in the metal molten stove 8, under the low temperature environment of 250～400 ℃ of temperature ranges, melt.Thus, can make the Sn of segregation and Ag even.
In addition, carry out following adjustment operation: mixture 5 is dropped into low temperature with after in the metal molten stove 8, adds the above-mentioned lead-free solder material of ormal weight in metal molten stove 8 in addition at low temperature, transfers rare so that the carbon amount is for expecting concentration.For example, being manufactured on high temperature is the soft solder alloy of about 10kgw of 0.5wt% with carbon amount in the mixture in the metal molten stove 15, then, in above-mentioned adjustment operation, in using metal molten stove 8, adds low temperature the lead-free solder material of about 90kgw, thus, can obtain the soft solder alloy that the carbon amount is about 100kgw of 0.05wt%.Like this by being arranged on the adjustment operation of low temperature with metal molten stove 8, the final purpose product is that the carbon amount is during for example for the soft solder alloy of 0.05wt%, at first with metal molten stove 1 the carbon amount is set at high concentration in 0.01～0.7wt% scope by high temperature, then be implemented in the adjustment operation of low temperature with metal molten stove 8, compare when only making with metal molten stove 1 thus, can make the soft solder alloy extremely effectively with high temperature.
As mentioned above, with metal molten stove 1 and low temperature metal molten stove 8, can eliminate segregation by use high temperature, can shorten simultaneously and under hot environment, use high temperature to use the service time of metal molten stove 1, in addition, obtaining to reduce manufacturing cost on the final purpose product.
Secondly, in refrigerating work procedure again, will re-inject mold, make its cooled and solidified by the mixture 11 that above-mentioned adjustment operation has been adjusted the carbon amount.Again in the refrigerating work procedure,, above-mentioned segregation is disappeared at this owing under the low temperature environment of 250～400 ℃ of temperature ranges, cool off.
Should illustrate before above-mentioned adjustment operation, can also possess the carbon quantitative analysis operation of analysis in the cakey mixture 5 of above-mentioned refrigerating work procedure.Like this, in above-mentioned adjustment operation,, can determine the ormal weight of above-mentioned other adding more accurately based on the analysis result of above-mentioned analysis procedure.
Embodiment
At first,, 96.5wt%Sn-3wt%Ag-0.5wt%Cu (being generally called 305 alloys) is dropped into high temperature with metal molten stove 1, high temperature is heated to 1000 ℃ hot environment with metal molten stove 1, make 305 alloy meltings (melting process) as the lead-free solder material.
At this moment, regulate the quantity delivered of heating fuel, form the state of fuel completing combustion, so that the exhaust outlet oxygen amount of metal molten stove is 0.If not like this, then carbon burns, and the result adds carbon efficiencies and reduces.
Then, add to 305 alloys (melting 305 alloys) that melted at high temperature by above-mentioned melting process and add carbon agent 0.5wt% (adding the carbon operation) what iron added carbon with metal molten stove 1.
And, in high temperature is used metal molten stove 1, stir fusing 305 alloys and add the carbon agent, evenly mixing (agitating procedure).
Then, fusing 305 alloys that will stir by above-mentioned agitating procedure and the mixture that adds the carbon agent inject mold, make its cooling and solidify (refrigerating work procedure).
Afterwards, analyze by cakey fusing 305 alloys of above-mentioned refrigerating work procedure and add carbon amount (analysis procedure) in the mixture of carbon agent.
Then,, said mixture 5 is dropped into low temperature with also fusing in the metal molten stove 8,, finally adjust the 0.1wt% that the carbon amount is a total amount (adjustment operation) simultaneously to wherein adding 305 alloys based on the carbon amount that obtains by above-mentioned analysis procedure.
At last, will re-inject mold by the mixture 11 that above-mentioned adjustment operation has been adjusted the carbon amount and cooling makes it solidify (refrigerating work procedure again).
Through above each operation, by in the lead-free solder material, adding carbon, can solve bond strength that lead-free solder alloy in the past had and be inferior to and contain this problem of Pb soft solder alloy, make the soft solder alloy that the joint reliability of lead-free solder alloy improves.
Should illustrate that in the present embodiment, the lead-free solder material uses 305 alloys, but is not limited thereto, and can also use 99.3wt%Sn-0.7wt%Cu, 99.0wt%Sn-0.7wt%Cu-0.3wt%Ag.
In addition, in the present embodiment, setting hot environment is 1000 ℃, but is not limited thereto, as long as in 800～1200 ℃ scope.
And in the present embodiment, the carbon agent that adds of interpolation is made as 0.5wt%, but is not limited thereto, as long as in the scope of 0.01～0.7wt%.
And in the present embodiment, adjusting the carbon amount in adjusting operation is the 0.1wt% of total amount, but is not limited thereto, and can suitably adjust the carbon amount according to the purposes of the soft solder alloy of making.
Industrial applicability
The present invention can suitably use this technological thought for field that can utilize technological thought of the present invention etc., particularly goes for vehicular field that requires joint reliability etc., and its possibility of industrially utilizing is big.
Claims (18)
1. the soft solder alloy is characterized in that, adds the carbon of ormal weight under hot environment in the lead-free solder material.
2. soft solder alloy according to claim 1 is characterized in that, in above-mentioned soft solder alloy, above-mentioned hot environment is in 800～1200 ℃ the temperature range.
3. soft solder alloy according to claim 1 is characterized in that, the carbon amount of afore mentioned rules amount is in the scope of 0.01～0.7wt%.
4. soft solder alloy according to claim 1 is characterized in that, above-mentioned carbon is the graphite mould of hexagonal crystal system.
5. soft solder alloy according to claim 1 is characterized in that, above-mentioned lead-free solder material is 96.5wt%Sn-3wt%Ag-0.5wt%Cu.
6. soft solder alloy according to claim 1 is characterized in that, above-mentioned lead-free solder material is 99.3wt%Sn-0.7wt%Cu.
7. soft solder alloy according to claim 1 is characterized in that, above-mentioned lead-free solder material is 99.0wt%Sn-0.7wt%Cu-0.3wt%Ag.
8. the manufacture method of soft solder alloy is characterized in that possessing following operation:
The high temperature that has dropped into the lead-free solder material is heated to hot environment with the metal molten stove, makes the melting process of above-mentioned lead-free solder material fusing;
To by the fusing of above-mentioned melting process and be in lead-free solder material (fusing lead-free solder material) under the above-mentioned hot environment add ormal weight carbon add the carbon operation;
Agitating procedure with above-mentioned fusing lead-free solder material and the stirring of above-mentioned carbon; With
The above-mentioned fusing lead-free solder material that will stir by above-mentioned agitating procedure and the mixture of above-mentioned carbon inject mold, make the refrigerating work procedure of said mixture cooled and solidified.
9. the manufacture method of soft solder alloy according to claim 8 is characterized in that, above-mentioned hot environment is in 800～1200 ℃ the temperature range.
10. the manufacture method of soft solder alloy according to claim 8 is characterized in that, the carbon amount of afore mentioned rules amount is in the scope of 0.01～0.7wt%.
11. the manufacture method of soft solder alloy according to claim 8, it is characterized in that above-mentioned high temperature is equipped with the metal molten stove and accessory: drop into above-mentioned lead-free solder material and above-mentioned carbon kiln portion, form the heating space portion of airtight heating space in the top position of above-mentioned kiln portion, heating fuel supplied in the above-mentioned airtight heating space and heat the heating part of above-mentioned airtight heating space and above-mentioned kiln portion and the exhaust outlet that forms in above-mentioned heating space portion.
12. the manufacture method of soft solder alloy according to claim 11 is characterized in that, in above-mentioned melting process, regulates the quantity delivered of above-mentioned heating fuel, so that the oxygen amount of being discharged with the above-mentioned exhaust outlet of metal molten stove by above-mentioned high temperature is 0.
13. the manufacture method of soft solder alloy according to claim 8 is characterized in that possessing following operation:
To put into low temperature at the cakey said mixture of above-mentioned refrigerating work procedure uses in the metal molten stove, under low temperature environment, melt, the above-mentioned lead-free solder material that adds simultaneously ormal weight in the metal molten stove in addition to low temperature, transfers rare so that the carbon amount becomes the adjustment operation of expecting concentration; With
To re-inject mold by the mixture that above-mentioned adjustment operation has been adjusted the carbon amount, make the refrigerating work procedure again of its cooled and solidified.
14. the manufacture method of soft solder alloy according to claim 13, it is characterized in that, has analysis procedure, in above-mentioned adjusting operation, analysis result based on above-mentioned analysis procedure, determine the ormal weight of above-mentioned other adding, described analysis procedure is before above-mentioned adjustment operation, analyzes the carbon quantitative analysis operation in the cakey said mixture of above-mentioned refrigerating work procedure.
15. the manufacture method of soft solder alloy according to claim 13, it is characterized in that, carbon amount in the cakey said mixture of above-mentioned refrigerating work procedure is in the high concentration range in 0.01～0.7wt% scope, and above-mentioned expectation concentration is in the low strength range in 0.01～0.7wt% scope.
16. the manufacture method of soft solder alloy according to claim 13 is characterized in that, above-mentioned low temperature environment is in 250～400 ℃ the temperature range.
17. the manufacture method of soft solder alloy according to claim 8 is characterized in that, above-mentioned carbon is the graphite mould of hexagonal crystal system.
18. the soft solder alloy is characterized in that, by the manufacture method manufacturing of each described soft solder alloy of claim 8～17.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007321086 | 2007-12-12 | ||
| JP2007-321086 | 2007-12-12 | ||
| PCT/JP2008/072480 WO2009075314A1 (en) | 2007-12-12 | 2008-12-11 | Solder alloy and process for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101952080A true CN101952080A (en) | 2011-01-19 |
| CN101952080B CN101952080B (en) | 2013-11-20 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2008100025982A Pending CN101204761A (en) | 2007-12-12 | 2008-01-10 | Solder alloy and method for manufacturing same |
| CN2008801202944A Expired - Fee Related CN101952080B (en) | 2007-12-12 | 2008-12-11 | Solder alloy and process for producing the same |
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| Application Number | Title | Priority Date | Filing Date |
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| CNA2008100025982A Pending CN101204761A (en) | 2007-12-12 | 2008-01-10 | Solder alloy and method for manufacturing same |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US20100296965A1 (en) |
| JP (1) | JP5408589B2 (en) |
| CN (2) | CN101204761A (en) |
| WO (1) | WO2009075314A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102251140A (en) * | 2011-07-15 | 2011-11-23 | 广州先艺电子科技有限公司 | Gold-tin solder protective smelting method |
| CN109548407A (en) * | 2017-07-21 | 2019-03-29 | 大丰工业株式会社 | Sliding component and sliding bearing |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101378202B1 (en) | 2009-09-07 | 2014-03-26 | 고쿠리쯔 다이가쿠 호징 츠쿠바 다이가쿠 | Copper alloy and method for producing same |
| JP2013018010A (en) * | 2011-07-07 | 2013-01-31 | Fuji Electric Co Ltd | Lead-free solder |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4695428A (en) * | 1986-08-21 | 1987-09-22 | J. W. Harris Company | Solder composition |
| US5127969A (en) * | 1990-03-22 | 1992-07-07 | University Of Cincinnati | Reinforced solder, brazing and welding compositions and methods for preparation thereof |
| US5089356A (en) * | 1990-09-17 | 1992-02-18 | The Research Foundation Of State Univ. Of New York | Carbon fiber reinforced tin-lead alloy as a low thermal expansion solder preform |
| JP3226213B2 (en) * | 1996-10-17 | 2001-11-05 | 松下電器産業株式会社 | Solder material and electronic component using the same |
| KR20010072364A (en) * | 1999-06-11 | 2001-07-31 | 이즈하라 요조 | Lead-free solder |
| US6805974B2 (en) * | 2002-02-15 | 2004-10-19 | International Business Machines Corporation | Lead-free tin-silver-copper alloy solder composition |
| JP4514581B2 (en) * | 2004-10-06 | 2010-07-28 | 忠正 藤村 | Lead-free solder composite powder and lead-free solder solder paste |
| JP2007237212A (en) * | 2006-03-07 | 2007-09-20 | Alps Electric Co Ltd | Solder adhesive and electronic component packaging structure using the solder adhesive |
-
2008
- 2008-01-10 CN CNA2008100025982A patent/CN101204761A/en active Pending
- 2008-12-11 CN CN2008801202944A patent/CN101952080B/en not_active Expired - Fee Related
- 2008-12-11 US US12/735,038 patent/US20100296965A1/en not_active Abandoned
- 2008-12-11 WO PCT/JP2008/072480 patent/WO2009075314A1/en active Application Filing
- 2008-12-11 JP JP2009545442A patent/JP5408589B2/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102251140A (en) * | 2011-07-15 | 2011-11-23 | 广州先艺电子科技有限公司 | Gold-tin solder protective smelting method |
| CN102251140B (en) * | 2011-07-15 | 2012-10-03 | 广州先金新材料科技有限公司 | Gold-tin solder protective smelting method |
| CN109548407A (en) * | 2017-07-21 | 2019-03-29 | 大丰工业株式会社 | Sliding component and sliding bearing |
| CN109548407B (en) * | 2017-07-21 | 2021-05-14 | 大丰工业株式会社 | Sliding member and sliding bearing |
| US11396910B2 (en) | 2017-07-21 | 2022-07-26 | Taiho Kogyo Co., Ltd. | Sliding member and sliding bearing |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2009075314A1 (en) | 2009-06-18 |
| CN101204761A (en) | 2008-06-25 |
| US20100296965A1 (en) | 2010-11-25 |
| JP5408589B2 (en) | 2014-02-05 |
| CN101952080B (en) | 2013-11-20 |
| JPWO2009075314A1 (en) | 2011-04-28 |
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