KR100424662B1 - Alloying compositions of Lead-Free Solder - Google Patents
Alloying compositions of Lead-Free Solder Download PDFInfo
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- KR100424662B1 KR100424662B1 KR10-2001-0023345A KR20010023345A KR100424662B1 KR 100424662 B1 KR100424662 B1 KR 100424662B1 KR 20010023345 A KR20010023345 A KR 20010023345A KR 100424662 B1 KR100424662 B1 KR 100424662B1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/24—Selection of soldering or welding materials proper
- B23K35/26—Selection of soldering or welding materials proper with the principal constituent melting at less than 400 degrees C
- B23K35/262—Sn as the principal constituent
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K1/00—Soldering, e.g. brazing, or unsoldering
- B23K1/0008—Soldering, e.g. brazing, or unsoldering specially adapted for particular articles or work
- B23K1/0016—Brazing of electronic components
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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
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Abstract
주석(Sn), 은(Ag), 구리(Cu) 금속성분을 기본성분조성으로 하고, 게르마늄(Ge), 셀렌(Se), 스트론듐(Sr) 성분중 어느 하나 또는 하나이상의 조합성분으로된 합금조성물로 이루어지며, 이 합금성분조성범위는 기본적으로 은(Ag):3.0~3.8중량%, 구리(Cu):0.4~0.8중량%, 게르마늄(Ge):0.005~0.02중량%, 셀렌(Se):0.005~0.01중량%, 스트론듐(Sr):0.005~0.1중량%, 나머지 잔부는 주석(Sn)으로 구성되는 것을 특징으로 하는 무연솔더합금조성물을 제공하기 위한 발명이다.Tin (Sn), silver (Ag), copper (Cu) metal components as the basic composition, and one or more combinations of germanium (Ge), selenium (Se), strontium (Sr) components It is composed of alloy composition, and the composition of this alloy composition is basically silver (Ag): 3.0 ~ 3.8% by weight, copper (Cu): 0.4 ~ 0.8% by weight, germanium (Ge): 0.005 ~ 0.02% by weight, selenium (Se) ): 0.005 ~ 0.01% by weight, strontium (Sr): 0.005 ~ 0.1% by weight, the remainder is an invention for providing a lead-free solder alloy composition, characterized in that consisting of (Sn).
Description
본 발명은 통상 전자산업에서 전자부품의 접합제로 사용되는 무연솔더 (Lead-Free Solder)의 합금조성물에 관한 것이다. 본 발명은 특히 그중에서도 주석(Sn), 은(Ag), 구리(Cu), 게르마늄(Ge), 셀렌(Se), 스트로듐(Sr) 등의 성분이 일부 선택적으로 또는 전부포함되는 4원 또는 6원합금에 관한 무연솔더합금조성물에 관한 것이다.BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to alloy compositions of lead-free solders that are commonly used as binders for electronic components in the electronics industry. In particular, the present invention is a four-membered or six-membered element including tin (Sn), silver (Ag), copper (Cu), germanium (Ge), selenium (Se), and strodium (Sr). Lead-free solder alloy composition for raw alloys.
종래에는 주로 납(Pb) 또는 카드뮴(Cd)과 같이 인체에 해로운 중금속함유 솔더를 접합제로 사용하였다. 그러나 납과 카드뮴 등은 대기중에서 산화되어 물 또는 수용액에 용해될 경우 인체와 환경에 치명적인 악영향을 주므로 납(Pb),카드뮴(Cd) 등의 사용을 금하고, 그 대체물을 강구하기에 이르렀다.Conventionally, heavy metal-containing solders such as lead (Pb) or cadmium (Cd), which are harmful to the human body, have been used as a binder. However, when lead and cadmium are oxidized in the air and dissolved in water or aqueous solution, they have a fatal adverse effect on the human body and the environment. Therefore, the use of lead (Pb) and cadmium (Cd) is prohibited, and the substitutes have been devised.
그결과, 납(Pb) 대신 주석(Sn), 비스무스(Bi), 아연(Zn), 구리(Cu), 은(Ag), 인듐(In), 니켈(Ni) 등의 화학성분조성으로 이루어진 Sn-Bi-Ag, Sn-Zn-In, Sn-Ag-Cu 등의 합금조성물이 사용되어 왔다.As a result, instead of lead (Pb), Sn (Sn), bismuth (Bi), zinc (Zn), copper (Cu), silver (Ag), indium (In), nickel (Ni), etc. Alloy compositions such as -Bi-Ag, Sn-Zn-In, Sn-Ag-Cu have been used.
그러나 Sn-Bi-Ag의 경우, 통상 Sn 잔부(중량 %:이하 모두 중량 %임):Bi 5~10%:Ag 0.1~5%로 이루어지고 이 합금조성은 용융범위가 액상선 약 208℃, 고상선약 190℃로 그 용융범위가 넓고, 비스무스(Bi)가 포함되어 있어, 외부로 부터의 충격이나 휘어짐 응력을 받게 되면 접합부위가 파손되기 쉬운 단점이 있다.However, in the case of Sn-Bi-Ag, the balance of Sn (weight%: less than or equal to all% by weight): Bi 5 to 10%: Ag is 0.1 to 5%, and the alloy composition has a melting range of about 208 DEG C, The solid range is about 190 ° C, the melting range is wide, and bismuth (Bi) is included, there is a disadvantage that the joint is easily damaged when subjected to impact or bending stress from the outside.
Sn-Zn-In합금의 경우, 통상 Zn 8~12%, In 2~5%, 잔부 Sn으로 구성되는데. 이 합금조성에는 Zn이 들어 있으므로, 접합성이 떨어지는 큰 문제점을 갖고 있다.In the case of Sn-Zn-In alloys, Zn is usually composed of 8 to 12%, In 2 to 5% and the balance of Sn. Since Zn is contained in this alloy composition, it has a big problem of inferior joinability.
또한, Sn:Ag:Cu의 경우, 통상 Ag 3.5~7.7%, Cu 1.0~4.0%, Sn:잔부 89~94%로 되고, 이중에서 Sn:Ag:Cu=93.6%:4.7%:1.7%인 무연솔더는 공정합금으로서 그융점이 217℃로 유연솔더를 대체하는데는 매우 양호하지만, 웨이브솔더링(Wave soldering) 작업시에는 산화물이 많이 생성되고 표면이 매끄럽지 못한 단점이 있다.In the case of Sn: Ag: Cu, Ag is usually 3.5 to 7.7%, Cu is 1.0 to 4.0%, and Sn is the remainder of 89 to 94%, of which Sn: Ag: Cu = 93.6%: 4.7%: 1.7%. Lead-free solder is a process alloy, its melting point is very good to replace the flexible solder at 217 ℃, but the wave soldering (Wave soldering) has a disadvantage that a lot of oxide is generated and the surface is not smooth.
따라서, 본 발명은 상술한 문제점을 해결하고, 인체에 유해한 납(Pb), 카드뮴(Cd) 등의 성분함유를 배제하면서도 안정된 용융범위(Melting range), 액상선(Liquidus line), 고상선(Solidus line)의 온도범위를 좁게하여 전자부품 등의 접합체에 효율적이고도 안정적으로 작업가능케하는 무연솔더합금조성물을 제공하는데 목적이 있다.Accordingly, the present invention solves the above problems, while excluding stable content of lead (Pb), cadmium (Cd) and the like harmful to the melting range (Melting range), liquid line (Liquidus line), solidus (Solidus) The purpose of this invention is to provide a lead-free solder alloy composition that narrows the temperature range of the line to enable efficient and stable work on junctions such as electronic components.
본 발명은 상술한 목적에 따라 납(Pb), 카드뮴(Cd) 등을 제외한 여러가지 화학조성을 이용한 합금조성물을 제조시험해 본 결과, 기본적으로 주석(Sn), 은(Ag), 구리(Cu)를 추가적으로 게르마늄(Ge), 셀렌(Se), 스트론듐(Sr)중 어느 한가지 또는 세가지 모두를 함유하는 4원화 또는 6원화 합금조성물이 상술한 목적에 부합하여 전자제품 등에 이용되는 접합제로서는 가장 적합하다는 것을 알게 되었다.According to the present invention, as a result of manufacturing and testing alloy compositions using various chemical compositions except lead (Pb), cadmium (Cd), etc., basically, tin (Sn), silver (Ag), and copper (Cu) are additionally added. A quaternized or hexavalent alloy composition containing one or all of germanium (Ge), selenium (Se), and strontium (Sr) is the most suitable binder for use in electronic products and the like in accordance with the above-mentioned purposes. I found out.
시험연구결과, 주석(Sn)과 은(Ag)는 용융시 접합모재에 대한 확산속도를 빠르게 해주며, 구리(Cu)는 인장강도를 높여주고, 게르마늄(Ge), 셀렌(Se), 스트론듐(Sr)이 미량 첨가되면 주석(Sn), 은(Ag), 구리(Cu)의 3원합금으로 웨이브솔더링작업시 발생되는 산화물을 크게 감소시키며, 솔더링작업후 거치른 표면을 매끄럽게 해주는 역할을 하여 준다는 사실을 알게 되었다.As a result of the test research, tin (Sn) and silver (Ag) increase the diffusion speed to the bonded base material during melting, copper (Cu) increases the tensile strength, germanium (Ge), selenium (Se), stront When a small amount of sodium (Sr) is added, the three-component alloy of tin (Sn), silver (Ag), and copper (Cu) greatly reduces oxides generated during wave soldering, and smoothes the surface after soldering. I realized that
따라서, 본 발명은 주석(Sn)-은(Ag)-구리(Cu)의 3원합금조성물을 기본으로 하고, 여기에 게르마늄(Ge), 셀렌(Se), 스트론듐(Sr) 성분조성을 선택적으로 하나 또는 그 이상의 조성을 첨가함으로써 이루어지는 4원화 또는 6원화 합금조성물을 제공함으로써 무연솔더링작업효율의 극대화를 기하고 아울러 작업성외에도 접합성, 환경공해방지성 등에 우수한 전자부품 등의 접합제를 제조할 수 있게한 것이다.Accordingly, the present invention is based on a ternary alloy composition of tin (Sn) -silver (Ag) -copper (Cu), and the germanium (Ge), selenium (Se), and strontium (Sr) component compositions are optional. By providing one or more of the four or six-membered alloy composition by adding one or more compositions to maximize the lead-free soldering work efficiency, it is possible to manufacture a bonding agent for electronic components such as excellent workability and environmental pollution prevention in addition to workability It is.
상기 조성물의 새로운 적정성분 범위를 찾기 위하여 전술한 성분조성상의 특성과 그 성분조성이 미치는 영향, 경제성 등을 고려하여 연구해 본 결과, 은(Ag):구리(Cu):게르마늄(Ge):셀렌(Se):스트론듐(Sr)은 각각 3.0~3.8%:0.4~0.8%:0.005~ 0.02%:0.005~0.01%:0.005~0.1%의 범위가 양호하고, 주석(Sn)은 나머지 잔부 96.3~95.5%에 이르는 합금조성물이 그 용융범위에 있어서는 각각 액상선 218~222℃와 고상선 217~221℃, 특히 집중적으로 각기 219~221℃, 217~218℃를 보여주므로써 종래의 무연솔더에 비해 용융범위가 좁고, 웨이브솔더링작업시 산화물을 적게 배출하여 원가절감이 될뿐더러 작업성 또한 뛰어나서 솔더링작업후 접합표면이 매끄러운 효과가 뛰어난 무연솔더를 제공할 수 있게 되었다.In order to find a new proper ingredient range of the composition, studies on the properties of the above-described ingredient composition, the effects of the ingredient composition, economics, and the like have been conducted. As a result, silver (Ag): copper (Gu): germanium (Ge): selenium (Se): Strontium (Sr) is in the range of 3.0 to 3.8%: 0.4 to 0.8%: 0.005 to 0.02%: 0.005 to 0.01%: 0.005 to 0.1%, respectively, and tin (Sn) is the remainder 96.3. Alloy compositions up to -95.5% show liquid phase lines 218-222 ° C and solidus lines 217-221 ° C, particularly 219-221 ° C and 217-218 ° C, respectively, in the melting range. Compared to this, the melting range is narrow and the oxides are reduced during the wave soldering operation to reduce the cost, and the workability is also excellent.
여기에서, 은(Ag)를 3.0%이하로 할경우 전기, 열전도도가 충분히 확보되지못하고 3.8%를 넘는 경우에는 용융온도조절이 어려워진다. 구리(Cu)는 대체적으로 0.4%미만이 되면 소정의 인장강도를 얻기 어렵고, 반대로 0.8%를 초과하면 조직파손이 쉽게 일어날 정도로 경질의 조직을 만드는 결함이 있다. 게르마늄(Ge)은 0.005%미만일 경우 그 영향력이 거의 없고, 그 이상인 경우 솔더성분금속산화를 방지하나 0.02%를 넘으면 산화를 어렵게 해 주는 대신, 부스러지기 쉽고 취약한 조직을 만들므로, 0.02%이하로 제어하여 첨가하는 것이 좋다.In this case, when silver (Ag) is less than 3.0%, the electrical and thermal conductivity is not sufficiently secured, and when it exceeds 3.8%, melting temperature control becomes difficult. Copper (Cu) is generally less than 0.4% is difficult to obtain a predetermined tensile strength, on the contrary more than 0.8% has a defect that makes the hard tissue so that tissue breakage easily occurs. Germanium (Ge) is less than 0.005%, and its effect is little, and if it is higher than that, it prevents the oxidation of solder metal, but if it exceeds 0.02%, it makes the fragile and fragile tissue instead of difficult to control. It is good to add.
셀렌(Se)은 0.005%이하일 경우조직에아무런 영향을 미치지 않으나 그이상으로 첨가하면 0.01%까지는 그러나 0.01%를 초과할 경우 셀렌(Se)의 강산화력에 따라 오히려 솔더 제품의 과산화를 촉진하므로 그 이상의 첨가를 억제한다. 스트론듐(Sr)은 산화방지는 물론, 용융드로스의 발생을 감소시켜주며, 인장강도 유지에도 효과적인 원소로서 0.005%이하일 경우 그 영향력이 거의없고, 0.1%초과인 경우 조직상 취성을 일으킬 염려가 있다. 주석(Sn)의 경우에는 용융을 용이하게 만들어주므로 작업성 및 솔더링작업후 접합표면의 매끄러운 효과를 가져다 준다.If selenium (Se) is less than 0.005% has no effect on the tissue, but if added above 0.01% but above 0.01% depending on the strong oxidizing power of selenium (Se) rather it promotes the peroxide of the solder product Suppresses addition Strontium (Sr) is an element that prevents oxidation and reduces the occurrence of molten dross, and is effective in maintaining tensile strength. If it is less than 0.005%, it has little effect, and if it exceeds 0.1%, it may cause brittleness. There is. In the case of tin (Sn) it is easy to melt and brings workability and smooth effect of the joining surface after soldering.
본 발명에서는 본 발명상의 합금조성물의 사용대상인 피시비(PCB)기판에 부품을 삽입후 솔더링작업이 가해지는 액상선온도, 고상선온도를 가급적 5℃이하의 극히 좁은 온도범위로 일정하게 유지해 주므로써 상기 피시비(PCB)기판에 가해지는 가열, 용융온도차에 따른 열변형과 열팽창계수의 급격한 변화를 줄이도록 하고, 동시에 솔더링작업시 산화물생성을 억제하여 작업성이 뛰어나며 작업후 접합부에 매끄러운 표면을 형성할 수 있도록한 것이 본 발명이 가진 큰 특징이다.In the present invention, the liquidus temperature and the solidus temperature to which the soldering operation is applied after inserting a component into a PCB substrate, which is the object of use of the alloy composition of the present invention, are maintained at an extremely narrow temperature range of 5 ° C. or less, if possible. The thermal deformation and thermal expansion coefficient due to heating and melting temperature difference applied to PCB substrates can be reduced and at the same time, it is excellent in workability by suppressing oxide generation during soldering work and can form a smooth surface at the joint after work. It is a great feature of the present invention.
이하에 실시예를 들어 본 발명을 보다 구체적으로 설명한다.An Example is given to the following and this invention is demonstrated to it further more concretely.
(실시예 1)(Example 1)
표 1에서 나타나 있는바와 같이 은(Ag):구리(Cu):게르마늄(Ge):주석(Sn)을 각각 3.5%:0.6%:0.008%:잔부%(약 95.8%)로 구성된 4원화 합금조성물을 제조하였다.As shown in Table 1, a quaternary alloy composition composed of silver (Ag): copper (Cu): germanium (Ge): tin (Sn), respectively 3.5%: 0.6%: 0.008%: balance% (about 95.8%). Was prepared.
이를 솔더로 사용해 본 결과 액상선 약 221℃, 고상선 약 219℃로서 종래의 비스무스(Bi)가 함유된 무연솔더와 대비하여 용융온도범위가 좁고 표면이 매끄러우며 솔더링 작업포트(pot)의 산화물 생성이 적은 탁월한 솔더를 제공할 수 있었다.As a result of using this as a solder, the liquidus line is about 221 ℃ and the solidus line is about 219 ℃. Compared with the lead-free solder containing bismuth (Bi), the melting temperature range is narrow, the surface is smooth, and the oxide of the soldering work pot is generated. This little could provide an excellent solder.
(실시예 2)(Example 2)
표 1에 나타난바와 같이 은(Ag):구리(Cu):게르마늄(Ge):셀렌(Se):주석(Sn)은 각각 3.4%:0.5%:0.008%:0.008%:잔부%(약 95.7%)로 구성된 5원합금 조성물을 제조하였다.As shown in Table 1, silver (Ag): copper (Cu): germanium (Ge): selenium (Se): tin (Sn) was 3.4%: 0.5%: 0.008%: 0.008%: balance% (about 95.7%). To prepare a five-membered alloy composition consisting of).
그결과 액상선, 고상선도 218℃~221℃사이에 좁고 안정되게 분포하였으며 산화물 생성량도 적었다.As a result, the liquidus and solidus were narrowly and stably distributed between 218 ℃ and 221 ℃ and the amount of oxide produced was small.
(실시예 3)(Example 3)
표 1에 나타난바와 같이 은(Ag):구리(Cu):게르마늄(Ge):셀렌(Se) :스트론듐(Sr):주석(Sn)은 각각 3.6%:0.6%:0.008%:0.008%:0.007%:잔부%(약 96.3%)로 구성된 6원합금조성물을 제조하였다. 그결과 액상선 고상선도 219℃~221℃사이에 좁고 안정되게 분포하였으며 역시 산화물 생성이 적었다.As shown in Table 1, silver (Ag): copper (Cu): germanium (Ge): selenium (Se): strontium (Sr): tin (Sn) was 3.6%: 0.6%: 0.008%: 0.008%, respectively. A six-membered alloy composition consisting of: 0.007%: balance% (about 96.3%) was prepared. As a result, the liquidus solidity was narrowly and stably distributed between 219 ℃ and 221 ℃ and there was also little oxide formation.
(비교예)(Comparative Example)
표 1에 나타낸바와 같이 상기 실시예와 대비하기 위하여 은(Ag):비스무스(Bi):주석(Sn)을 각각 2%:7%:잔부(91%)로한 합금조성물과 은(Ag):구리(Cu):주석(Sn)을 각각 3.5%:1.5%:94.9%로한 합금조성물 2가지를 각각 제조하여 산화물 생성량과 액상선, 고상선, 솔더링 작업후 표면상태를 검사하여 판정하였다.As shown in Table 1, an alloy composition comprising silver (Ag): bismuth (Bi): tin (Sn) 2%: 7%: residue (91%) and silver (Ag): copper Two alloy compositions containing (Cu): tin (Sn) of 3.5%: 1.5%: 94.9%, respectively, were prepared and determined by inspecting the amount of oxide formation, liquidus, solidus, and surface after soldering.
작업포트(pot)는 솔더 50㎏을 각각 넣었으며 온도는 260℃, 3시간 작업을 한후 산화물 생성량, 표면상태를 검사 판정하였다.Working pot (pot) was put 50kg of solder, respectively, the temperature was 260 ℃, after working for 3 hours, the amount of oxide production, the surface state was determined.
은(Ag):비스무스(Bi):주석(Sn)의 경우 (비교예 1)에는 액상선 고상선 차이가 많이나서 납땜불량현상이 일어나고 은(Ag):구리(Cu):주석(Sn)의 경우(비교예 2)에는 작업포트내에 산화물 생성량이 많이 발생되어 작업성이 저조한 것으로 판정되었다.In the case of silver (Ag): bismuth (Bi): tin (Sn) (Comparative Example 1), there are many differences in liquidus solid phase lines, so that soldering defects occur, and silver (Ag): copper (Cu): tin (Sn) In the case (Comparative Example 2), a large amount of oxide was generated in the work port, and it was determined that workability was poor.
위 실시예 1~실시예 3 및 비교예의 성분조건 및 결과를 다음 표 1에 실었다.Component conditions and results of the above Examples 1 to 3 and Comparative Examples are shown in Table 1 below.
표 1Table 1
위 표 1에서 알 수 있는바와 같이 게르마늄(Ge), 셀렌(Se), 스트론듐(Sr) 등을 첨가하지 않은 비교예 1, 2에서는 산화물 생성량이 대폭 생성된 것을 알 수 있어, 게르마늄(Ge), 셀렌(Se), 스트론듐(Sr) 등은 각각 산화물 생성을 억제하는 것으로 나타났음을 알 수 있다. 또한 게르마늄(Ge), 셀렌(Se), 스트론듐(Sr) 등의 세가지 성분원소중 한가지, 또는 두가지 또는 세가지 모두를 첨가한 경우 산화물 생성량이 적으며, 표면상태 또한 매끄러움을 알 수 있으며, 용융온도범위에도 거의 차이를 보이지 않는 것을 알 수 있었다.As can be seen in Table 1 above, in Comparative Examples 1 and 2, in which germanium (Ge), selenium (Se), strontium (Sr), and the like were not added, it was found that the amount of oxides produced was significantly increased. ), Selenium (Se), strontium (Sr) and the like have been shown to inhibit the formation of oxide, respectively. In addition, when one, two or all three of the three element elements such as germanium (Ge), selenium (Se), strontium (Sr) are added, the amount of oxides generated is small, and the surface state is also smooth. It can be seen that there is almost no difference in the temperature range.
상술한 바와 같이 본 발명은주석(Sn), 은(Ag), 구리(Cu)를솔더합금에서 일반적인기본성분조성으로 하고,여기에게르마늄(Ge), 셀렌(Se), 스트론듐(Sr)중 한가지 또는 두가지, 또는 세가지 종류의 성분이 첨가된 합금조성물로 이루어진 무연솔더의 제조에 의하여 종래의 무연솔더보다 산화물생성량이 적어 작업성이 양호한데다 솔더링작업후 표면이 매끄럽고 특히 표면산화방지 효과가 탁월하여 매우 우수한 품질의 무연솔더 합금을 실제 작업에 제공할 수 있게 되었다.As described above, the present invention uses tin (Sn), silver (Ag), and copper (Cu) as a general basic composition of a solder alloy, and germanium (Ge), selenium (Se), and strontium (Sr). The production of lead-free solders made of alloy compositions containing one, two, or three kinds of components results in less oxide production than conventional lead-free solders, resulting in better workability, smooth surface after soldering, and particularly excellent in surface oxidation prevention. This makes it possible to provide very high quality lead-free solder alloys in practical applications.
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JPH106075A (en) * | 1996-06-13 | 1998-01-13 | Nippon Handa Kk | Lead-free solder alloy |
JPH11129091A (en) * | 1997-10-28 | 1999-05-18 | Ngk Spark Plug Co Ltd | Solder alloy |
JP2000343273A (en) * | 1999-06-01 | 2000-12-12 | Fuji Electric Co Ltd | Soldering alloy |
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JPH106075A (en) * | 1996-06-13 | 1998-01-13 | Nippon Handa Kk | Lead-free solder alloy |
JPH11129091A (en) * | 1997-10-28 | 1999-05-18 | Ngk Spark Plug Co Ltd | Solder alloy |
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