JP4857641B2 - Lead-free soldering equipment made of Fe-based alloy with excellent corrosion resistance against molten lead-free solder - Google Patents
Lead-free soldering equipment made of Fe-based alloy with excellent corrosion resistance against molten lead-free solder Download PDFInfo
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この発明は、溶融鉛フリーはんだ、特に溶融状態のＳｎ−Ａｇ系はんだに対する耐侵食性に優れたＦｅ基合金からなる鉛フリーはんだ付け装置部材に関するものである。 This invention relates to molten lead-free solder, in particular Fe-based alloy gold or Ranaru lead-free soldering apparatus member having excellent corrosion resistance against Sn-Ag based solder in a molten state.
近年、環境問題に関する関心が高まり、例えば、ヨーロッパでは電子機器などへの有害物質の含有を規制することが決定されている。その規制物質の１つとして鉛が取り上げられている。鉛は電子部品の接合に用いられているはんだの主成分であることから、鉛を全く使用しないＳｎ−Ａｇ系の鉛フリーはんだ（鉛フリーはんだであるＳｎ−Ａｇ系はんだの組成としてＳｎ−３．５％Ａｇ、Ｓｎ−３．０％Ａｇ−０．１％Ｃｕなどが知られている）が開発され、従来の鉛はんだとの置き換えが進みつつある。したがって、現在では鉛フリーはんだと言えば前記Ｓｎ−Ａｇ系はんだを一般に示している。ところが、鉛フリーはんだである前記Ｓｎ−Ａｇ系はんだは、従来の鉛はんだに比べて反応性が高くかつ溶融温度が高く、そのために従来から使用されているＳＵＳ３０４（Ｃｒ：１８〜２０質量％、Ｎｉ：８〜１０．５質量％、残部：Ｆｅおよび不可避不純物）、ＳＵＳ３０９Ｓ（Ｃｒ：２２〜２４質量％、Ｎｉ：１２〜１５質量％、残部：Ｆｅおよび不可避不純物）、ＳＵＳ３１６（Ｃｒ：１６〜１８質量％、Ｎｉ：１０〜１４質量％、Ｍｏ：２〜３質量％、残部：Ｆｅおよび不可避不純物）などのステンレス鋼などのＦｅ基合金で作製したはんだ付け装置では溶融鉛フリーはんだに対する侵食に耐えられず、したがって、従来のステンレス鋼などのＦｅ基合金で作製したはんだ付け装置では損傷して短期間で使用寿命に至り、早期にはんだ付け装置の交換を余儀なくされることが明らかとなってきた。 In recent years, interest in environmental issues has increased, and in Europe, for example, it has been decided to regulate the inclusion of harmful substances in electronic devices. Lead is one of the regulated substances. Since lead is the main component of solder used for joining electronic components, Sn-Ag lead-free solder that does not use lead at all (Sn-3 is a composition of Sn-Ag solder that is lead-free solder). 0.5% Ag, Sn-3.0% Ag-0.1% Cu, etc. are known) and replacement with conventional lead solder is progressing. Therefore, at present, the Sn-Ag solder is generally shown for lead-free solder. However, the Sn-Ag solder, which is a lead-free solder, has higher reactivity and higher melting temperature than conventional lead solder, and therefore SUS304 (Cr: 18 to 20% by mass, conventionally used) Ni: 8 to 10.5% by mass, balance: Fe and inevitable impurities), SUS309S (Cr: 22 to 24% by mass, Ni: 12 to 15% by mass, balance: Fe and inevitable impurities), SUS316 (Cr: 16 to 18 mass%, Ni: 10-14 mass%, Mo: 2-3 mass%, balance: Fe and inevitable impurities), etc. In soldering devices made of Fe-based alloys such as stainless steel Therefore, the conventional soldering device made of Fe-based alloy such as stainless steel is damaged and reaches the service life in a short period. It is possible to be forced to exchange of attached devices have become clear.
ここで、溶融鉛フリーはんだである溶融Ｓｎ−Ａｇ系はんだによるステンレス鋼の侵食について説明する。一般に、ステンレス鋼の表面には不働態皮膜と呼ばれる酸化皮膜などの非反応性物質が形成されており、この酸化皮膜などの非反応性物質により溶融Ｓｎ−Ａｇ系はんだが直接金属面に接することを防ぎ、損傷を免れている。しかし、使用中に溶融金属の対流などにより摩耗を受けて表面皮膜が消滅すると、溶融Ｓｎ−Ａｇ系はんだとメタルが直接反応するようになり、損傷の原因となる。すなわち、融点の高いＦｅ、Ｎｉなどの金属がその融点より低い温度で低融点のＳｎと反応すると、低融点金属であるＳｎが高融点金属であるＦｅ、Ｎｉなどに固体内拡散し、Ｓｎと反応生成物を形成し、この反応生成物のＳｎ含有量が高まるに従い、融点が下がり、最終的には溶融金属中に溶融して損傷の原因となる。 Here, erosion of stainless steel by molten Sn-Ag solder that is molten lead-free solder will be described. In general, a non-reactive substance such as an oxide film called a passive film is formed on the surface of stainless steel, and the molten Sn-Ag solder contacts the metal surface directly by the non-reactive substance such as the oxide film. Prevent and avoid damage. However, when the surface film disappears due to convection of the molten metal during use, the molten Sn—Ag solder and the metal directly react with each other, causing damage. That is, when a metal such as Fe or Ni having a high melting point reacts with Sn having a low melting point at a temperature lower than the melting point, Sn, which is a low melting point metal, diffuses into the solid, such as Fe or Ni, which has a high melting point, and Sn and As the reaction product is formed and the Sn content of the reaction product increases, the melting point decreases and eventually melts into the molten metal causing damage.
そのため、鉛フリーはんだに対するはんだ付け装置の損傷を少しでもやわらげるために、はんだ付け装置を構成するステンレス鋼等のＦｅ基合金の表面をセラミックコーティングしたり、ステンレス鋼等のＦｅ基合金の表面に窒化層を設けるなどして装置の溶融鉛フリーはんだに対する耐侵食性を改善しようとしている（非特許文献１、非特許文献２、非特許文献３、非特許文献４などを参照）。
しかし、セラミックコーティングまたは窒化処理などの表面処理を施すと、溶接などによる補修が容易にできなかったり、チューブ部材内面などの複雑形状の部材にはこうした処理が施せないなどの課題があり、そのために、コーティングまたは窒化処理などの表面処理せずに使用できる溶融鉛フリーはんだに対する耐侵食性の高い材料が求められていた。 However, if surface treatment such as ceramic coating or nitriding treatment is performed, there are problems such as that repair by welding or the like cannot be easily performed, and that complicated treatment such as the inner surface of the tube member cannot be performed. Therefore, there has been a demand for a material having high erosion resistance against molten lead-free solder that can be used without surface treatment such as coating or nitriding.
そこで、本発明者等は、溶融鉛フリーはんだに対する耐侵食性に優れたＦｅ基合金を得るべく鋭意研究を行った。その結果、
（イ）Ｃｏ：１５〜４８％質量％（以下、％は質量％を示す）およびＣｒ：１３〜２８％を含み、さらにその他種々の添加元素を最適化して含んだＦｅ基合金は、Ｆｅ基合金であっても溶融鉛フリーはんだに対する耐侵食性に優れたものとなり、その成分組成は、Ｃｏ：１５〜４８％、Ｃｒ：１３〜２８％、Ｓｉ：０．２〜３．５％、Ａｌ：０．０５〜０．４％、Ｍｎ：０．０２〜２％、Ｃ：０．０２〜０．５％、Ｎ：０．０１〜０．３％を含有し、残部がＦｅおよび不可避不純物からなることが好ましい、
（ロ）前記（イ）記載のＦｅ基合金に、さらに必要に応じて下記の、
（ａ）ＷおよびＭｏの内の１種または２種以上を合計で１〜１０％、
（ｂ）ＮｂおよびＴａの内の１種または２種以上を合計で０．１〜３％、
（ｃ）Ｙおよび希土類元素の内の１種または２種以上を合計で０．００１〜０．３％、
の（ａ）〜（ｃ）内の１種または２種以上を含有し、残部がＦｅおよび不可避不純物からなる組成を有するＦｅ基合金は、溶融する鉛フリーはんだに対する耐侵食性にが一層優れるようになる、などの知見を得たのである。
この発明は、かかる知見に基づいてなされたものであって、
（１）質量％で、Ｃｏ：１５〜４８％、Ｃｒ：１３〜２８％、Ｓｉ：０．２〜３．５％、Ａｌ：０．０５〜０．４％、Ｍｎ：０．０２〜２％、Ｃ：０．０２〜０．５％、Ｎ：０．０１〜０．３％を含有し、残部がＦｅおよび不可避不純物からなる組成を有するＦｅ基合金からなる溶融鉛フリーはんだに対する耐侵食性に優れた鉛フリーはんだ付け装置部材、
（２）質量％で、Ｃｏ：１５〜４８％、Ｃｒ：１３〜２８％、Ｓｉ：０．２〜３．５％、Ａｌ：０．０５〜０．４％、Ｍｎ：０．０２〜２％、Ｃ：０．０２〜０．５％、Ｎ：０．０１〜０．３％を含有し、さらにＷおよびＭｏの内の１種または２種以上を合計で１〜１０％含有し、残部がＦｅおよび不可避不純物からなる組成を有するＦｅ基合金からなる溶融鉛フリーはんだに対する耐侵食性に優れた鉛フリーはんだ付け装置部材、
（３）質量％で、Ｃｏ：１５〜４８％、Ｃｒ：１３〜２８％、Ｓｉ：０．２〜３．５％、Ａｌ：０．０５〜０．４％、Ｍｎ：０．０２〜２％、Ｃ：０．０２〜０．５％、Ｎ：０．０１〜０．３％を含有し、さらにＮｂおよびＴａの内の１種または２種以上を合計で０．１〜３％含有し、残部がＦｅおよび不可避不純物からなる組成を有するＦｅ基合金からなる溶融鉛フリーはんだに対する耐侵食性に優れた鉛フリーはんだ付け装置部材、
（４）質量％で、Ｃｏ：１５〜４８％、Ｃｒ：１３〜２８％、Ｓｉ：０．２〜３．５％、Ａｌ：０．０５〜０．４％、Ｍｎ：０．０２〜２％、Ｃ：０．０２〜０．５％、Ｎ：０．０１〜０．３％を含有し、さらにＹおよび希土類元素の内の１種または２種以上を合計で０．００１〜０．３％含有し、残部がＦｅおよび不可避不純物からなる組成を有するＦｅ基合金からなる溶融鉛フリーはんだに対する耐侵食性に優れた鉛フリーはんだ付け装置部材、
（５）質量％で、Ｃｏ：１５〜４８％、Ｃｒ：１３〜２８％、Ｓｉ：０．２〜３．５％、Ａｌ：０．０５〜０．４％、Ｍｎ：０．０２〜２％、Ｃ：０．０２〜０．５％、Ｎ：０．０１〜０．３％を含有し、さらにＷおよびＭｏの内の１種または２種以上を合計で１〜１０％含有し、さらにＮｂおよびＴａの内の１種または２種以上を合計で０．１〜３％含有し、残部がＦｅおよび不可避不純物からなる組成を有するＦｅ基合金からなる溶融鉛フリーはんだに対する耐侵食性に優れた鉛フリーはんだ付け装置部材、
（６）質量％で、Ｃｏ：１５〜４８％、Ｃｒ：１３〜２８％、Ｓｉ：０．２〜３．５％、Ａｌ：０．０５〜０．４％、Ｍｎ：０．０２〜２％、Ｃ：０．０２〜０．５％、Ｎ：０．０１〜０．３％を含有し、さらにＷおよびＭｏの内の１種または２種以上を合計で１〜１０％含有し、さらにＹおよび希土類元素の内の１種または２種以上を合計で０．００１〜０．３％含有し、残部がＦｅおよび不可避不純物からなる組成を有するＦｅ基合金からなる溶融鉛フリーはんだに対する耐侵食性に優れた鉛フリーはんだ付け装置部材、
（７）質量％で、Ｃｏ：１５〜４８％、Ｃｒ：１３〜２８％、Ｓｉ：０．２〜３．５％、Ａｌ：０．０５〜０．４％、Ｍｎ：０．０２〜２％、Ｃ：０．０２〜０．５％、Ｎ：０．０１〜０．３％を含有し、さらにＮｂおよびＴａの内の１種または２種以上を合計で０．１〜３％含有し、さらにＹおよび希土類元素の内の１種または２種以上を合計で０．００１〜０．３％含有し、残部がＦｅおよび不可避不純物からなる組成を有するＦｅ基合金からなる溶融鉛フリーはんだに対する耐侵食性に優れた鉛フリーはんだ付け装置部材、
（８）質量％で、Ｃｏ：１５〜４８％、Ｃｒ：１３〜２８％、Ｓｉ：０．２〜３．５％、Ａｌ：０．０５〜０．４％、Ｍｎ：０．０２〜２％、Ｃ：０．０２〜０．５％、Ｎ：０．０１〜０．３％を含有し、さらにＷおよびＭｏの内の１種または２種以上を合計で１〜１０％含有し、さらにＮｂおよびＴａの内の１種または２種以上を合計で０．１〜３％含有し、さらにＹおよび希土類元素の内の１種または２種以上を合計で０．００１〜０．３％含有し、残部がＦｅおよび不可避不純物からなる組成を有するＦｅ基合金からなる溶融鉛フリーはんだに対する耐侵食性に優れた鉛フリーはんだ付け装置部材、に特徴を有するものである。
Therefore, the present inventors conducted intensive research to obtain an Fe-based alloy having excellent erosion resistance against molten lead-free solder. as a result,
(B) Fe-based alloy containing Co: 15 to 48% by mass (hereinafter,% indicates mass%) and Cr: 13 to 28%, and further including various other additive elements optimized, Even if it is an alloy, it has excellent erosion resistance against molten lead-free solder, and its component composition is Co: 15 to 48%, Cr: 13 to 28%, Si: 0.2 to 3.5%, Al : 0.05 to 0.4%, Mn: 0.02 to 2%, C: 0.02 to 0.5%, N: 0.01 to 0.3%, the balance being Fe and inevitable impurities Preferably consisting of
(B) In addition to the Fe-based alloy described in (a) above,
(A) 1 to 10% in total of one or more of W and Mo,
(B) A total of 0.1 to 3% of one or more of Nb and Ta,
(C) 0.001 to 0.3% in total of one or more of Y and rare earth elements,
Fe-based alloys containing one or more of (a) to (c) and having the balance consisting of Fe and inevitable impurities are more excellent in erosion resistance against molten lead-free solder. I got the knowledge of becoming.
This invention has been made based on such knowledge,
(1) By mass%, Co: 15-48%, Cr: 13-28%, Si: 0.2-3.5%, Al: 0.05-0.4%, Mn: 0.02-2 %, C: 0.02 to 0.5%, N: 0.01 to 0.3%, with the balance being resistant to erosion against molten lead-free solder made of an Fe-based alloy having a composition consisting of Fe and inevitable impurities Lead-free soldering equipment with excellent properties,
(2) By mass%, Co: 15-48%, Cr: 13-28%, Si: 0.2-3.5%, Al: 0.05-0.4%, Mn: 0.02-2 %, C: 0.02 to 0.5%, N: 0.01 to 0.3%, further containing 1 or 10% in total of one or more of W and Mo, A lead-free soldering device member excellent in erosion resistance with respect to molten lead-free solder composed of an Fe-based alloy having the composition of the balance consisting of Fe and inevitable impurities,
(3) By mass%, Co: 15-48%, Cr: 13-28%, Si: 0.2-3.5%, Al: 0.05-0.4%, Mn: 0.02-2 %, C: 0.02 to 0.5%, N: 0.01 to 0.3%, and further 0.1 to 3% of one or more of Nb and Ta A lead-free soldering device member having excellent erosion resistance against molten lead-free solder comprising a Fe-based alloy having a composition comprising the balance Fe and inevitable impurities,
(4) By mass%, Co: 15-48%, Cr: 13-28%, Si: 0.2-3.5%, Al: 0.05-0.4%, Mn: 0.02-2 %, C: 0.02 to 0.5%, N: 0.01 to 0.3%, and one or more of Y and rare earth elements in total are 0.001 to 0.001. A lead-free soldering device member having excellent corrosion resistance against molten lead-free solder comprising a Fe-based alloy containing 3% and the balance being composed of Fe and inevitable impurities;
(5) By mass%, Co: 15-48%, Cr: 13-28%, Si: 0.2-3.5%, Al: 0.05-0.4%, Mn: 0.02-2 %, C: 0.02 to 0.5%, N: 0.01 to 0.3%, further containing 1 or 10% in total of one or more of W and Mo, Furthermore, it contains one or two or more of Nb and Ta in a total amount of 0.1 to 3%, with the remaining part being resistant to erosion with respect to molten lead-free solder made of an Fe-based alloy having a composition consisting of Fe and inevitable impurities. Excellent lead-free soldering device parts ,
(6) By mass%, Co: 15-48%, Cr: 13-28%, Si: 0.2-3.5%, Al: 0.05-0.4%, Mn: 0.02-2 %, C: 0.02 to 0.5%, N: 0.01 to 0.3%, further containing 1 or 10% in total of one or more of W and Mo, Furthermore, the resistance to molten lead-free solder composed of an Fe-based alloy containing 0.001 to 0.3% in total of one or more of Y and rare earth elements, with the balance being composed of Fe and inevitable impurities. Lead-free soldering equipment with excellent erosion,
(7) By mass%, Co: 15-48%, Cr: 13-28%, Si: 0.2-3.5%, Al: 0.05-0.4%, Mn: 0.02-2 %, C: 0.02 to 0.5%, N: 0.01 to 0.3%, and further 0.1 to 3% of one or more of Nb and Ta Further, molten lead-free solder made of an Fe-based alloy containing a total of 0.001 to 0.3% of one or more of Y and rare earth elements, with the balance being composed of Fe and inevitable impurities Lead-free soldering equipment with excellent erosion resistance,
(8) By mass%, Co: 15-48%, Cr: 13-28%, Si: 0.2-3.5%, Al: 0.05-0.4%, Mn: 0.02-2 %, C: 0.02 to 0.5%, N: 0.01 to 0.3%, further containing 1 or 10% in total of one or more of W and Mo, Further, one or more of Nb and Ta are contained in a total of 0.1 to 3%, and one or more of Y and a rare earth element are further added in a total of 0.001 to 0.3%. It is characterized by a lead-free soldering device member excellent in erosion resistance against molten lead-free solder composed of an Fe-based alloy having a composition comprising Fe and inevitable impurities.
この発明の溶融鉛フリーはんだに対する耐侵食性に優れたＦｅ基合金は、鉛フリーはんだ付け装置の部材として使用した場合、溶接部を含め、溶融する鉛フリーはんだに対する耐侵食性が格段に上昇することから、鉛フリーはんだ付け装置およびその部品、例えば、鉛フリーはんだ付け装置のはんだ槽、噴射ノズル、プロペラ、シャフト、ダクト、ヒーター保護管、ヒーター被覆管など鉛フリーはんだ付け装置の各種構成部品の寿命が格段に向上する、などの知見を得たのである。
したがって、この発明は、
（９）前記（１）〜（８）の内のいずれかに記載の溶融鉛フリーはんだに対する耐侵食性に優れた鉛フリーはんだ付け装置部材を用いた鉛フリーはんだ付け装置用はんだ槽、
（１０）前記（１）〜（８）の内のいずれかに記載の溶融鉛フリーはんだに対する耐侵食性に優れた鉛フリーはんだ付け装置部材を用いた鉛フリーはんだ付け装置用噴射ノズル、
（１１）前記（１）〜（８）の内のいずれかに記載の溶融鉛フリーはんだに対する耐侵食性に優れた鉛フリーはんだ付け装置部材を用いた鉛フリーはんだ付け装置用プロペラ、
（１２）前記（１）〜（８）の内のいずれかに記載の溶融鉛フリーはんだに対する耐侵食性に優れた鉛フリーはんだ付け装置部材を用いた鉛フリーはんだ付け装置用シャフト、
（１３）前記（１）〜（８）の内のいずれかに記載の溶融鉛フリーはんだに対する耐侵食性に優れた鉛フリーはんだ付け装置部材を用いた鉛フリーはんだ付け装置用ダクト、
（１４）前記（１）〜（８）の内のいずれかに記載の溶融鉛フリーはんだに対する耐侵食性に優れた鉛フリーはんだ付け装置部材を用いた鉛フリーはんだ付け装置用ヒーター保護管、
（１５）前記（１）〜（８）の内のいずれかに記載の溶融鉛フリーはんだに対する耐侵食性に優れた鉛フリーはんだ付け装置部材を用いた鉛フリーはんだ付け装置用ヒーター被覆管、に特徴を有するものである。
When used as a member of a lead-free soldering apparatus, the Fe-based alloy having excellent erosion resistance against molten lead-free solder according to the present invention significantly increases the erosion resistance against molten lead-free solder, including welds. Therefore, lead-free soldering equipment and its components, such as solder tanks, spray nozzles, propellers, shafts, ducts, heater protection tubes, heater cladding tubes, etc. They obtained knowledge that the lifespan was improved significantly.
Therefore, the present invention
(9) A solder bath for a lead-free soldering device using the lead-free soldering device member excellent in erosion resistance to the molten lead-free solder according to any one of (1) to (8),
(10) An injection nozzle for a lead-free soldering device using a lead-free soldering device member having excellent erosion resistance against molten lead-free solder according to any one of (1) to (8),
(11) A propeller for a lead-free soldering apparatus using a lead-free soldering apparatus member having excellent erosion resistance against molten lead-free solder according to any one of (1) to (8),
(12) A shaft for a lead-free soldering device using a lead-free soldering device member having excellent erosion resistance against molten lead-free solder according to any one of (1) to (8),
(13) A duct for a lead-free soldering device using a lead-free soldering device member having excellent erosion resistance against molten lead-free solder according to any one of (1) to (8),
(14) A heater protection tube for a lead-free soldering device using a lead-free soldering device member having excellent erosion resistance against molten lead-free solder according to any one of (1) to (8),
(15) To a heater cladding tube for a lead- free soldering device using the lead- free soldering device member having excellent erosion resistance against molten lead-free solder according to any one of (1) to (8) It has characteristics.
次に、この発明の溶融鉛フリーはんだに対する耐侵食性に優れたＦｅ基合金および鉛フリーはんだ付け装置部材の合金組成における各元素の限定理由について詳述する。
Ｃｏ：
Ｃｏは、Ｆｅ基合金に含有させることにより耐摩耗性を向上させると同時に、溶融Ｓｎに対しする熱力学的反応を抑制し、それによって溶融鉛フリーはんだによる損傷を抑制する効果があるので添加するが、Ｃｏの含有量が１５％未満では特にＳｎとのOLE_LINK3反応性抑制効果OLE_LINK3が十分でなく、一方、４８％を越えて含有しても、反応性抑制効果効果が飽和してしまうことから経済的に好ましくない。従って、この発明のＦｅ基合金およびＦｅ基合金からなる鉛フリーはんだ付け装置部材に含まれるＣｏは１５〜４８％に定めた。一層好ましくは、２０〜４５％である。
Ｃｒ：
Ｃｒは、表面に濃縮して薄くて緻密なＣｒ２Ｏ３を 主体とする不働態被膜を形成することにより、溶融する鉛フリーはんだである溶融するＳｎ−Ａｇ系はんだが直接はんだ付け装置部材と接して反応してしまうことを阻害する効果があるが、Ｃｒを１３％未満含有しても所望の効果が得られず、一方、２８％を超えて含有すると、Ｃｒ−アルファ相の析出を促進することになり、その結果、加工が困難となる。従って、この発明のＦｅ 基合金からなる鉛フリーはんだ付け装置部材に含まれるＣｒは１３〜２８％に定めた。一層好ましくは、１５〜２５％である。
Ｓｉ：
Ｓｉは酸素との親和性が高いために表面にＳｉＯ２を形成し、Ｃｒ２Ｏ３と 共に溶融する鉛フリーはんだであるＳｎ−Ａｇ合金が直接金属と接して反応してしまうことを阻害する効果があるが、Ｓｉを０．２％未満含有しても所望の効果が得られず、一方、３．５％を越えて含有すると、合金の脆化が顕在化し、板などへの形状付与が困難となるので好ましくない。したがって、Ｓｉの含有量を０．２〜３．５％に定めた。一層好ましい範囲は０．５〜２．０％である。
Ａｌ：
Ａｌは酸素との親和性が高いために表面にＡｌ２Ｏ３を形成し、Ｃｒ２Ｏ３と共に溶融する鉛フリーはんだである溶融Ｓｎ−Ａｇ合金が直接金属と接して反応してしまうことを阻害する効果があるので含有させるが、Ａｌを０．０５％未満含有しても所望の効果が得られず、一方、０．４％を越えて含有すると、逆に侵食を加速してしまい好ましくない。したがって、Ａｌの含有量を０．０５〜０．４％に定めた。一層好ましい範囲は０．０５〜０．２％である。
Ｍｎ：
Ｍｎは、母相の結晶構造であるオーステナイト構造を安定化させることにより、脆化を抑制し、その結果、形状付与を容易にする作用があるが、Ｍｎが０．０２％未満含有しても所望の効果が得られず、一方、２．０％を超えて含有すると鉛フリーはんだとの濡れ性を高め、溶融鉛フリーハンダとの反応を促進することとなり、損傷を加速するので好ましくない。したがって、Ｍｎの含有量を０．０２〜２．０％とした。一層好ましくは、０．１〜１．０％である。
Next, the reason for limitation of each element in the alloy composition of the Fe-based alloy and the lead-free soldering device member excellent in erosion resistance to the molten lead-free solder of the present invention will be described in detail.
Co:
Co is added to the Fe-based alloy because it improves the wear resistance and at the same time suppresses the thermodynamic reaction to the molten Sn, thereby suppressing the damage caused by the molten lead-free solder. However, if the Co content is less than 15%, especially the OLE_LINK3 reactivity inhibitory effect with Sn is not sufficient OLE_LINK3, while if it exceeds 48%, the reactivity inhibitory effect is saturated. Economically unfavorable. Therefore, Co contained in the lead-free soldering device member made of the Fe-based alloy and the Fe-based alloy of the present invention is set to 15 to 48%. More preferably, it is 20 to 45%.
Cr:
Cr is concentrated on the surface to form a thin and dense passive film mainly composed of Cr 2 O 3 , so that the molten Sn—Ag solder, which is a lead-free solder that melts, is directly bonded to the soldering device member. Although there is an effect of inhibiting the reaction in contact, if Cr is contained in less than 13%, the desired effect cannot be obtained, while if it exceeds 28%, the precipitation of Cr-alpha phase is promoted. As a result, processing becomes difficult. Therefore, Cr contained in the lead-free soldering device member made of the Fe-based alloy of the present invention is set to 13 to 28%. More preferably, it is 15 to 25%.
Si:
Since Si has a high affinity with oxygen, it forms SiO 2 on the surface and inhibits the Sn—Ag alloy, which is a lead-free solder that melts together with Cr 2 O 3 , from contacting and reacting directly with the metal. Although there is an effect, the desired effect cannot be obtained even if Si is contained in an amount of less than 0.2%. On the other hand, if the content exceeds 3.5%, embrittlement of the alloy becomes obvious, and shapes are imparted to a plate or the like. Is not preferable because it becomes difficult. Therefore, the Si content is set to 0.2 to 3.5%. A more preferable range is 0.5 to 2.0%.
Al:
Since Al has a high affinity with oxygen, Al 2 O 3 is formed on the surface, and a molten Sn—Ag alloy, which is a lead-free solder that melts together with Cr 2 O 3 , reacts in direct contact with the metal. Although it is contained because it has an inhibiting effect, the desired effect cannot be obtained even if Al is contained in an amount of less than 0.05%. On the other hand, if it exceeds 0.4%, erosion is accelerated, which is preferable. Absent. Therefore, the Al content is set to 0.05 to 0.4%. A more preferable range is 0.05 to 0.2%.
Mn:
Mn stabilizes the austenite structure, which is the crystal structure of the parent phase, thereby suppressing embrittlement and, as a result, has an effect of facilitating shape formation, but even if Mn is contained in an amount of less than 0.02% On the other hand, if the content exceeds 2.0%, the wettability with the lead-free solder is increased, the reaction with the molten lead-free solder is promoted, and damage is accelerated, which is not preferable. Therefore, the content of Mn is set to 0.02 to 2.0%. More preferably, it is 0.1 to 1.0%.
Ｎ：
Nは、母相の結晶構造であるオーステナイト構造を安定化させることにより、脆化を抑制し、その結果、形状付与を容易にする作用があるが、Ｎが０．０１％未満含有しても所望の効果が得られず、一方、０．３％を超えて含有すると脆化して加工性を損なうこととなるので好ましくない。したがって、Nの含有量を０．０１〜０．３％とした。一層好ましくは、０．１〜０．３％である。
Ｃ：
Ｃは同時に含有するＣｒと共に硬化相であるクロム炭化物を形成し、これを微細に分散させることで溶融鉛フリーはんだに対する耐摩耗性を著しく向上させる作用があるが、Ｃは０．０２％未満を含有しても所望の効果が得られず、一方、０．５％を越えて含有すると、合金が脆化し、板などへの形状付与が困難となるので好まし くない。したがって、Ｃの含有量を０．０２〜０．５％に定めた。一層好ましい範囲は０．０４〜０．３％である。
ＷおよびＭｏ：
ＷおよびＭｏは、共に耐摩耗性を向上させることにより、溶融鉛フリーはんだによる損傷を抑制する効果があるので必要に応じて添加されるが、ＷおよびＭｏの内の１種または２種以上を合計で１％未満含有しても所望の効果が得られず、一方、ＷおよびＭｏの内の１種または２種以上を合計で１０％を越えて含有すると加工性が劣化する。したがって、ＷおよびＭｏの含有量は、ＷおよびＭｏの内の１種または２種以上を合計で１〜１０％になるように定めた。好ましくは、３〜８％である。
ＮｂおよびＴａ：
ＮｂおよびＴａは、同時に含有するCと共にＮｂＣやＴａＣ等の炭化物を形成し、これを微細に分散させることで溶融鉛フリーはんだに対する耐摩耗性を著しく向上させる作用があるので必要に応じて添加されるが、ＮｂおよびＴａの内の１種または２種以上を合計で０．１％未満含有しても所望の効果が得られず、一方、ＮｂおよびＴａの内の１種または２種以上を合計で３％を越えて含有すると加工性が劣化する。したがって、ＮｂおよびＴａの含有量は、ＮｂおよびＴａの内の１種または２種以上を合計で０．１〜３％になるように定めた。好ましくは、０．２〜１％である。
Ｙおよび希土類元素：
これら成分は、微量に添加することにより、溶融鉛フリーはんだ中で形成されるＦｅ基合金の表面皮膜の密着性を向上させることにより鉛フリーはんだに対する 耐侵食性を向上させる効果があるところから、必要に応じて添加される。しかし、Ｙおよび希土類元素の内の１種または２種以上を合計で０．００１％未満含有しても所望の効果が得られず、一方、０．３％を越 えて含有すると、逆に表面皮膜は剥離し易くなり、有害となるので好ましくない。したがって、Ｙおよび希土類元素の含有量はＹおよび希土類元素の内の１種または２種以上を合計で０．００１〜０．３％に定めた。一層好ましい範囲は０．０５〜０．１２％である。
不可避不純物：
不可避不純物としてはＰやＳなどが挙げられるが、これら不純物は、高温加工などの合金製造時における割れや溶接部における高温割れの原因となる。したがって、できるだけ低減することが望ましい。また、Ｎｉは３％未満、Ｚｒ、Ｍｇ、ＣａおよびＴｉはそれぞれ０．０５％未満の含有であれば本発明のＦｅ基合金の特性を大きく損ねることが無いので、その範囲での含有は許容される。
N:
N stabilizes the austenite structure, which is the crystal structure of the parent phase, thereby suppressing embrittlement and, as a result, has an effect of facilitating shape formation. On the other hand, the desired effect cannot be obtained. On the other hand, if it exceeds 0.3%, embrittlement occurs and workability is impaired. Therefore, the N content is set to 0.01 to 0.3%. More preferably, it is 0.1 to 0.3%.
C:
C forms a chromium carbide as a hardened phase together with Cr contained at the same time, and finely disperses this to significantly improve the wear resistance against molten lead-free solder, but C is less than 0.02%. Even if contained, the desired effect cannot be obtained. On the other hand, if it exceeds 0.5%, the alloy becomes brittle and it is difficult to impart a shape to a plate or the like. Therefore, the content of C is set to 0.02 to 0.5%. A more preferable range is 0.04 to 0.3%.
W and Mo:
Both W and Mo are added as necessary because they have the effect of suppressing damage caused by molten lead-free solder by improving wear resistance, but one or more of W and Mo are added. If the total content is less than 1%, the desired effect cannot be obtained. On the other hand, if one or more of W and Mo are included in excess of 10%, the workability deteriorates. Therefore, the content of W and Mo is determined so that one or more of W and Mo are 1 to 10% in total. Preferably, it is 3 to 8%.
Nb and Ta:
Nb and Ta form carbides such as NbC and TaC together with C that is contained at the same time, and finely disperse them to significantly improve the wear resistance against molten lead-free solder. However, even if one or more of Nb and Ta are contained in a total amount of less than 0.1%, the desired effect cannot be obtained, while one or more of Nb and Ta are obtained. If the total content exceeds 3%, workability deteriorates. Therefore, the content of Nb and Ta was determined so that one or more of Nb and Ta was 0.1 to 3% in total. Preferably, it is 0.2 to 1%.
Y and rare earth elements:
Because these components are added in trace amounts, they have the effect of improving the corrosion resistance of lead-free solder by improving the adhesion of the surface film of Fe-based alloy formed in molten lead-free solder. It is added as necessary. However, even if one or more of Y and rare earth elements are contained in a total amount of less than 0.001%, a desired effect cannot be obtained. The film is not preferable because it easily peels off and becomes harmful. Therefore, the content of Y and rare earth elements is set to 0.001 to 0.3% in total for one or more of Y and rare earth elements. A more preferable range is 0.05 to 0.12%.
Inevitable impurities:
Inevitable impurities include P and S, but these impurities cause cracks during alloy production such as high-temperature processing and hot cracks in welds. Therefore, it is desirable to reduce as much as possible. Further, if the Ni content is less than 3% and the Zr, Mg, Ca and Ti contents are each less than 0.05%, the characteristics of the Fe-based alloy of the present invention will not be greatly impaired. Is done.
この発明のＦｅ基合金からなる鉛フリーはんだ付け装置部材は、鉛フリーはんだに対する耐侵食性が優れており、したがって、この部材で作製した鉛フリーはんだ付け装置は長期間損傷することなく使用することができ、電子・電気産業上優れた効果をもたらすものである。 The lead-free soldering device member made of the Fe-based alloy of the present invention has excellent erosion resistance against lead-free solder. Therefore, the lead-free soldering device made of this member should be used without being damaged for a long time. It has excellent effects on the electronics and electrical industries.
通常の高周波溶解炉を用いて溶解し鋳造して表１〜７に示される成分組成を有するＦｅ基合金からなる厚さ：４０ｍｍ、重さ：約５ｋｇを有するインゴットを作製した。このインゴットを１２３０℃で１０時間均質化熱処理を施し、１０００〜１２３０℃の範囲内に保持しながら、１回の熱間圧延で１ｍｍの厚さを減少させつつ最終的に厚さ：３ｍｍの薄板とし、ついで１２００℃で３０分間保持し水焼入れすることにより固溶化処理を施し、表面をバフ研磨することにより本発明鉛フリーはんだ付け装置部材（以下、本発明部材という）１〜８２および比較鉛フリーはんだ付け装置部材（以下、比較部材という）１〜１９からなる薄板を作製した。 An ingot having a thickness of 40 mm and a weight of about 5 kg made of an Fe-based alloy having the composition shown in Tables 1 to 7 was prepared by melting and casting using a normal high-frequency melting furnace. The ingot was subjected to a homogenization heat treatment at 1230 ° C. for 10 hours and held within a range of 1000 to 1230 ° C., and the thickness was reduced to 1 mm by one hot rolling and finally a thin plate having a thickness of 3 mm. Then, it is held at 1200 ° C. for 30 minutes and subjected to solid solution treatment by water quenching, and the surface of the lead-free soldering apparatus member (hereinafter referred to as the member of the present invention) 1 to 82 and comparative lead by buffing the surface. Thin plates made of free soldering device members (hereinafter referred to as comparative members) 1 to 19 were produced.
さらに、ＳＵＳ３０４からなる厚さ：３ｍｍの従来鉛フリーはんだ付け装置部材（以下、従来部材という）を用意した。 Furthermore, a conventional lead-free soldering device member (hereinafter referred to as a conventional member) having a thickness of 3 mm made of SUS304 was prepared.
さらに、鉛フリーはんだの基本組成として知られているＳｎ−３．０％Ａｇ−０．１％Ｎｉの組成の鉛フリーはんだを用意した。 Furthermore, a lead-free solder having a composition of Sn-3.0% Ag-0.1% Ni, which is known as a basic composition of lead-free solder, was prepared.
前記本発明部材１〜８２、比較部材１〜１９および従来部材からなる薄板をそれぞれ縦：３０ｍｍ、横：２０ｍｍ、厚さ：３ｍｍの寸法に切断して試験片を作製し、これら試験片の表面を研磨し、最終的に耐水エメリー紙＃４００仕上げの表面研摩したのち、これらをアセトン中超音波振動状態に５分間保持し脱脂した。
さらに、Ｓｎ−３．０％Ａｇ−０．１％Ｎｉの組成の鉛フリーはんだを４３５℃に加熱しこの温度に保持することにより溶融鉛フリーはんだを作製した。この溶融鉛フリーはんだを撹拌翼により対流させ、この対流している溶融鉛フリーはんだに前記試験片を浸漬し、１０００時間保持した。１０００時間保持後、試験片を取出し、試験片の断面を光学顕微鏡により観察し、最大侵食深さを測定し、その結果を表８〜９に示し、溶融鉛フリーはんだに対する耐侵食性を評価した。
The specimens 1 to 82, the comparative members 1 to 19 and the conventional members were cut into the dimensions of 30 mm in length, 20 mm in width, and 3 mm in thickness to prepare test pieces, and the surfaces of these test pieces After polishing the surface and finally polishing the surface of water-resistant emery paper # 400, they were degreased by being kept in an ultrasonic vibration state in acetone for 5 minutes.
Further, a lead-free solder having a composition of Sn-3.0% Ag-0.1% Ni was heated to 435 ° C. and maintained at this temperature to produce a molten lead-free solder. The molten lead-free solder was convected by a stirring blade, and the test piece was immersed in the convected molten lead-free solder and held for 1000 hours. After holding for 1000 hours, the test piece was taken out, the cross section of the test piece was observed with an optical microscope, the maximum erosion depth was measured, the results are shown in Tables 8 to 9, and the erosion resistance against molten lead-free solder was evaluated. .
表１〜９に示された結果から、本発明部材１〜８２の試験片の最大侵食深さは、従来部材であるＳＵＳ３０４ステンレス鋼の試験片の最大侵食深さに比べて小さくいところから、本発明部材１〜８２は、従来部材に比べて鉛フリーはんだに対する耐侵食性に優れていることが分かる。 From the results shown in Tables 1 to 9, the maximum erosion depth of the test pieces of the present invention members 1 to 82 is smaller than the maximum erosion depth of the test piece of SUS304 stainless steel which is a conventional member. It turns out that this invention members 1-82 are excellent in the corrosion resistance with respect to lead-free solder compared with the conventional member.
しかし、この発明から外れた比較部材１〜１９の試験片は耐侵食性が劣っていたり、さらに板に加工する途中で割れが発生するものがあったりして好ましくない特性が有ることが分かる。 However, it can be seen that the test pieces of the comparative members 1 to 19 that deviate from the present invention have unfavorable characteristics because they are inferior in erosion resistance, or some cracks are generated during processing into a plate.
Claims (15)
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005220329A JP4857641B2 (en) | 2005-07-29 | 2005-07-29 | Lead-free soldering equipment made of Fe-based alloy with excellent corrosion resistance against molten lead-free solder |
| PCT/JP2006/313886 WO2007007797A1 (en) | 2005-07-13 | 2006-07-12 | Cobalt- or iron-base alloy excellent in the resistance to corrosion from molten lead-free solder and members of lead-free soldering apparatus which are made of the alloy |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005220329A JP4857641B2 (en) | 2005-07-29 | 2005-07-29 | Lead-free soldering equipment made of Fe-based alloy with excellent corrosion resistance against molten lead-free solder |
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| Publication Number | Publication Date |
|---|---|
| JP2007031809A JP2007031809A (en) | 2007-02-08 |
| JP4857641B2 true JP4857641B2 (en) | 2012-01-18 |
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| JPS62235459A (en) * | 1986-04-03 | 1987-10-15 | Nippon Kokan Kk <Nkk> | Steel having resistance to high-temperature sulfidization |
| JP2956130B2 (en) * | 1990-05-24 | 1999-10-04 | 大同特殊鋼株式会社 | Nozzle for zinc die casting |
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