TWI345502B - - Google Patents
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- TWI345502B TWI345502B TW094102918A TW94102918A TWI345502B TW I345502 B TWI345502 B TW I345502B TW 094102918 A TW094102918 A TW 094102918A TW 94102918 A TW94102918 A TW 94102918A TW I345502 B TWI345502 B TW I345502B
- Authority
- TW
- Taiwan
- Prior art keywords
- mass
- alloy
- solder
- less
- solder alloy
- Prior art date
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- 229910000679 solder Inorganic materials 0.000 claims description 103
- 229910045601 alloy Inorganic materials 0.000 claims description 93
- 239000000956 alloy Substances 0.000 claims description 93
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 88
- 229910052742 iron Inorganic materials 0.000 claims description 34
- 238000002844 melting Methods 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 17
- 230000007797 corrosion Effects 0.000 claims description 16
- 238000005260 corrosion Methods 0.000 claims description 16
- 239000011347 resin Substances 0.000 claims description 13
- 229920005989 resin Polymers 0.000 claims description 13
- 239000000843 powder Substances 0.000 claims description 11
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 229910052770 Uranium Inorganic materials 0.000 claims description 2
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 claims 1
- 238000003466 welding Methods 0.000 description 28
- 238000005476 soldering Methods 0.000 description 25
- 230000008018 melting Effects 0.000 description 21
- 229910017944 Ag—Cu Inorganic materials 0.000 description 18
- 238000000034 method Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 7
- 230000004907 flux Effects 0.000 description 7
- 238000007747 plating Methods 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
- 230000008439 repair process Effects 0.000 description 6
- 229910020816 Sn Pb Inorganic materials 0.000 description 4
- 229910020836 Sn-Ag Inorganic materials 0.000 description 4
- 229910020922 Sn-Pb Inorganic materials 0.000 description 4
- 229910020988 Sn—Ag Inorganic materials 0.000 description 4
- 229910008783 Sn—Pb Inorganic materials 0.000 description 4
- 229910002056 binary alloy Inorganic materials 0.000 description 4
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 3
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- 238000009736 wetting Methods 0.000 description 3
- 229910000640 Fe alloy Inorganic materials 0.000 description 2
- 229910020220 Pb—Sn Inorganic materials 0.000 description 2
- 229910020994 Sn-Zn Inorganic materials 0.000 description 2
- 229910009069 Sn—Zn Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 230000005496 eutectics Effects 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 229910001020 Au alloy Inorganic materials 0.000 description 1
- 229910020630 Co Ni Inorganic materials 0.000 description 1
- 229910000531 Co alloy Inorganic materials 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 229910005382 FeSn Inorganic materials 0.000 description 1
- 229910017112 Fe—C Inorganic materials 0.000 description 1
- -1 Sn-3Ag-〇 Substances 0.000 description 1
- 229910020888 Sn-Cu Inorganic materials 0.000 description 1
- 229910019204 Sn—Cu Inorganic materials 0.000 description 1
- 229910018956 Sn—In Inorganic materials 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- 238000002679 ablation Methods 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000003353 gold alloy Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- DNYWZCXLKNTFFI-UHFFFAOYSA-N uranium Chemical compound [U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U] DNYWZCXLKNTFFI-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
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- E—FIXED CONSTRUCTIONS
- E05—LOCKS; KEYS; WINDOW OR DOOR FITTINGS; SAFES
- E05C—BOLTS OR FASTENING DEVICES FOR WINGS, SPECIALLY FOR DOORS OR WINDOWS
- E05C17/00—Devices for holding wings open; Devices for limiting opening of wings or for holding wings open by a movable member extending between frame and wing; Braking devices, stops or buffers, combined therewith
- E05C17/02—Devices for holding wings open; Devices for limiting opening of wings or for holding wings open by a movable member extending between frame and wing; Braking devices, stops or buffers, combined therewith by mechanical means
- E05C17/44—Devices for holding wings open; Devices for limiting opening of wings or for holding wings open by a movable member extending between frame and wing; Braking devices, stops or buffers, combined therewith by mechanical means with a device carried on the wing for frictional or like engagement with a fixed flat surface, e.g. for holding wings open or closed by retractable feet
-
- E—FIXED CONSTRUCTIONS
- E05—LOCKS; KEYS; WINDOW OR DOOR FITTINGS; SAFES
- E05B—LOCKS; ACCESSORIES THEREFOR; HANDCUFFS
- E05B9/00—Lock casings or latch-mechanism casings ; Fastening locks or fasteners or parts thereof to the wing
- E05B9/08—Fastening locks or fasteners or parts thereof, e.g. the casings of latch-bolt locks or cylinder locks to the wing
-
- E—FIXED CONSTRUCTIONS
- E05—LOCKS; KEYS; WINDOW OR DOOR FITTINGS; SAFES
- E05C—BOLTS OR FASTENING DEVICES FOR WINGS, SPECIALLY FOR DOORS OR WINDOWS
- E05C17/00—Devices for holding wings open; Devices for limiting opening of wings or for holding wings open by a movable member extending between frame and wing; Braking devices, stops or buffers, combined therewith
- E05C17/02—Devices for holding wings open; Devices for limiting opening of wings or for holding wings open by a movable member extending between frame and wing; Braking devices, stops or buffers, combined therewith by mechanical means
- E05C17/44—Devices for holding wings open; Devices for limiting opening of wings or for holding wings open by a movable member extending between frame and wing; Braking devices, stops or buffers, combined therewith by mechanical means with a device carried on the wing for frictional or like engagement with a fixed flat surface, e.g. for holding wings open or closed by retractable feet
- E05C17/446—Devices for holding wings open; Devices for limiting opening of wings or for holding wings open by a movable member extending between frame and wing; Braking devices, stops or buffers, combined therewith by mechanical means with a device carried on the wing for frictional or like engagement with a fixed flat surface, e.g. for holding wings open or closed by retractable feet of the retractable sliding feet type
-
- E—FIXED CONSTRUCTIONS
- E05—LOCKS; KEYS; WINDOW OR DOOR FITTINGS; SAFES
- E05Y—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES E05D AND E05F, RELATING TO CONSTRUCTION ELEMENTS, ELECTRIC CONTROL, POWER SUPPLY, POWER SIGNAL OR TRANSMISSION, USER INTERFACES, MOUNTING OR COUPLING, DETAILS, ACCESSORIES, AUXILIARY OPERATIONS NOT OTHERWISE PROVIDED FOR, APPLICATION THEREOF
- E05Y2201/00—Constructional elements; Accessories therefor
- E05Y2201/60—Suspension or transmission members; Accessories therefor
- E05Y2201/622—Suspension or transmission members elements
- E05Y2201/676—Transmission of human force
- E05Y2201/68—Handles, cranks
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Electric Connection Of Electric Components To Printed Circuits (AREA)
- Coating With Molten Metal (AREA)
Description
1345502 ft年β月丨柯修(更)正替換頁 九、發明說明 — 【發明所屬之技術領域】 本發明係有關被覆Fe或Fe系合金構件之防止鐵熔蝕 用焊料合金與防止鐵熔蝕之方法。本發明係特別有關藉由 手焊對於印刷基板進行焊接時所使用之焊接用機器構件的 防止鐵熔蝕用之焊料合金與防止鐵熔蝕之方法。 【先前技術】 先行技術中，印刷基板之焊接時係使用Pb-Sn合金。 此P b - S η合金其共晶組成（P b- 6 3 S η )之熔點爲1 8 3 °C，可 以較低溫進行焊接。因此，對於不耐熱電子零件之熱影響 不大，且焊接性優異，因此，具有很少出現未焊接或脫落 等焊接不良的優點。惟，Pb-Sn合金含有對人體有害之Pb 成份，因此，最近電子機器之焊接使用不含Pb之所謂的 「無鉛焊料」。 無鉛焊料係指以Sn爲主成份者，目前所使用之無鉛 焊料合金除了 Sn-3.5Ag (熔點：221°C) 、Sn-0.7Cu (熔 點：227 °C ) 、Sn-_9Zn (熔點：199。(：） 、Sn-58Bi (熔點 :139°C)等二元合金外’尙有在此等中適度添加Ag、Cu 、Zn、 Bi、 In、 Sb、 Ni、 Cr、 Co、 Fe、 Μη、 P、 Ge、 Ga 等第三元素者。 本發明所謂的「……合金」係指至少含有該成份之合 金者’如上述之二元合金係指該二元合金本身與該二元合 金中再添加一種以上之第三元素的合金者。例如Sn-Zn系 -5- 1345502 f御"月丨相修沒)正替^ _______j 係指Sn_Zn合金本身及該Sn_Zn中再添加—種以上之前述 第三元素之合金者，Sn-Ag系係指Sn-Ag合金本身及Sn-Ag中再添加一種以上之上述第三元素之合金者。 目前’ Sn-Ag-Cu系無鉛焊料合金之主流係Sn-3Ag-〇」Cu、Sn-3_5Ag-0_75Cu等之Sn-Ag-Cu系無鉛焊料合金 者° Sn-Ag-Cu系無鉛焊料合金可適用於手焊（manual soldering)、流動焊接（fiow s〇ldering)、迴焊（reflow soldering )等各種工法’焊接強度之信賴性及焊接性優異 〇 實際使用之其他無鉛焊料合金，其中低成本之流動焊 接用焊料合金例如Sn-0.7Cu無鉛焊料合金等之Sn-Cu系 合金、及低熔融溫度之迴焊用金合例如Sn-Zn系焊料合金 及Sn-In系焊料合金等，但是由整體觀之，僅爲極微的比 例。 手焊係指以手動作業之焊接，利用焊接鏝（S〇ldering iron，Soldering trowel)進行焊接。手焊係針對流動焊接 、迴焊之修正或其後安裝的零件進行焊接。焊接鏝係於內 藏加熱器之焊接鏝本體之前端裝設鏝尖之構造。 鏝尖之主材料係使用導熱性良好之Cu及Cu合金等， 其進行焊接之前端部份爲了防止因Sn造成Cu之熔蝕，因 此，進行鍍Fe、鍍Ni外再鍍Fe來被覆。 惟，用於手焊之焊料合金由先行技術之Sn-Pb系焊料 合金改爲目前使用之Sn-Ag-Cu系無鉛焊料合金，其鏝尖 之耗損快速，焊接鏝之鏝尖壽命變成約1/3。 13455021345502 ft β 丨 丨 修 修 修 修 修 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 九 九 九 九 九 九 九 九 九 九 九 九 九 九 九 九 九 九The method. The present invention relates to a solder alloy for preventing iron corrosion and a method for preventing iron corrosion by a welding machine member used for welding a printed circuit board by hand welding. [Prior Art] In the prior art, a Pb-Sn alloy is used for soldering of a printed substrate. The P b - S η alloy has a eutectic composition (P b - 6 3 S η ) having a melting point of 183 ° C and can be welded at a relatively low temperature. Therefore, the heat resistance of the heat-resistant electronic component is not large, and the weldability is excellent. Therefore, there is little advantage of poor soldering such as soldering or peeling. However, Pb-Sn alloy contains Pb which is harmful to human body. Therefore, recently, the welding of electronic equipment uses a so-called "lead-free solder" which does not contain Pb. Lead-free solder refers to the main component of Sn. The lead-free solder alloy currently used is Sn-3.5Ag (melting point: 221 °C), Sn-0.7Cu (melting point: 227 °C), Sn-_9Zn (melting point: 199). (:), Sn-58Bi (melting point: 139 °C) and other binary alloys, 尙 have moderately added Ag, Cu, Zn, Bi, In, Sb, Ni, Cr, Co, Fe, Μη The third element such as P, Ge, Ga, etc. The term "... alloy" as used in the present invention means an alloy containing at least the component. 'The above binary alloy means the binary alloy itself and the binary alloy. Adding more than one alloy of the third element. For example, Sn-Zn system-5- 1345502 f Royal "月丨相修修)正^ _______j means that the Sn_Zn alloy itself and the Sn_Zn are added in more than one kind In the alloy of the third element, the Sn-Ag system refers to an alloy in which one or more of the above-described third elements are further added to the Sn-Ag alloy itself and the Sn-Ag. At present, Sn-Ag-Cu lead-free solder alloys such as Sn-Ag-Cu lead-free solder alloys are the mainstay of Sn-Ag-Cu lead-free solder alloys, such as Sn-3Ag-〇, Cu, Sn-3_5Ag-0_75Cu, etc. Suitable for manual soldering, flow welding (fiow s), reflow soldering, etc. 'The reliability of soldering strength and solderability are excellent. Other lead-free solder alloys actually used, of which low cost a solder alloy for flow soldering, such as a Sn-Cu alloy such as a Sn-0.7Cu lead-free solder alloy, and a gold alloy for reflow soldering at a low melting temperature, for example, a Sn-Zn solder alloy and a Sn-In solder alloy, but the whole The view is only a very small proportion. Hand soldering refers to welding by hand welding using a welding 镘 (S〇ldering iron, Soldering trowel). Hand soldering is used for welding of flow soldering, reflow soldering or post-installed parts. The welding raft is attached to the front end of the welding raft body of the built-in heater. The main material of the tip is made of Cu or a Cu alloy having good thermal conductivity, and the end portion before welding is used to prevent Cu from being eroded by Sn. Therefore, it is coated with Fe and Ni plating and then coated with Fe. However, the solder alloy used for hand soldering is changed from the prior art Sn-Pb solder alloy to the Sn-Ag-Cu lead-free solder alloy currently used, and the tip loss is fast, and the tip life of the solder bump becomes about 1 /3. 1345502
卜、月丨k修⑧正替換買I 先行技術中，抑制使用無鉛焊料時之鏝尖之Fe被覆 層之侵蝕的手段，提案使用添加〇.〇1質量％〜〇.2質量％之 焊料合金者（專利文獻1)。惟，無鉛焊料合金中添加Fe 雖具相同焊接時間之抑制Fe被覆層的侵蝕效果，但是明 顯阻礙焊料之潤濕性，因而延長焊接時間，結果Fe被覆 層受侵蝕。 [專利文獻1]特開2003-62688號 【發明內容】 【發明欲解決的課題】 本發明之課題係以提供一種使用被覆Fe或Fe系合金 的構件，以Sn爲主成份之Sn-Ag-Cu系之無鉛焊料合金進 行焊接時，防止被覆Fe或Fe系合金之焊接用機器構件之 鐵熔蝕之焊料合金及防止F e熔鈾的方法。 φ 【解決課題的手段】 如上述，Fe被熔蝕之現象明顯的原因係因置換成無鉛 焊料，容易溶解Fe之焊料中之Sn含有率變高，焊料本身 之潤濕性不良，焊接鏝之焊接時間約2倍，由先行技術之 Sn-Pb系焊料合金之熔融溫度（約1 83°C )至Sn-Ag-Cu系 無鉛焊料合金之熔融溫度（約220°C )，其中焊料之熔融 溫度約上昇40°C，因此，鏝尖之使用溫度亦由Sn-Pb系焊 料合金之使用溫度之3 5 0 °C~420°C上昇至Sn-Ag-Cu系無 鉛焊料合金之使用溫度之380°C~450°C等’結果促進與Fe ^345502 年卜月ι狗修(£)正替换〜 之反應，被覆層易被侵蝕。 本發明人等藉由使用於Sn-Ag-Cu系無鉛焊料合金中 添加微量Co的焊料，發現Co分散於Sn-Ag-Cu系無鉛焊 料合金中，防止Fe之溶解，因此，不易產生焊接鏝之鏝 尖的Fe熔蝕，進而完成本發明。 本發明之防止鐵熔蝕用焊料合金係由Ag : 0.3質量％ 以上’ 4.0質量％以下、Cu : 0· 1質量％以上，1.0質量％以 下、Co : 0.001質量％以上，〇.5質量％以下，剩餘部份實 質上由Sn所成之合成組成的焊料合金。 爲了提昇焊料合金之耐疲勞性，於該焊料合金組成中 亦可含有0.01質量％以上，0.1質量％以下之Ni。 本發明係使用被覆Fe或Fe系合金之焊接用構件，以 Sn爲主成份之Sn-Ag-Cu系無鉛焊料合金進行焊接時，使 用含有0.001質量％以上，0.5質量％以下之Co之Sn-Ag-Cu系無鉛焊料合金後進行焊接爲特徵之防止被覆Fe或Fe 系合金之焊接用機器構件的鐵熔蝕的方法。 藉由本發明防止鐵熔蝕之易產生鐵熔蝕之焊接用機器 構件例如用於手焊之焊接鏝之鏝尖，用於焊接機器人之焊 接鏝之鏝尖，及用於修補裝置之焊接鏝之鏝尖等。 此種構件係於如上述以鍍Fe，或鍍Ni後再鍍Fe來被 覆。又，Fe鍍敷時亦包含Fe-C合金類之Fe系合金鍍敷。 【發明效果】 藉由使用在本發明之Sn-Ag-Cu系無鉛焊料合金中添 -8- 1345502In the technique of suppressing the erosion of the Fe coating of the tip of the lead-free solder, it is proposed to use a solder alloy containing 〇.〇1% by mass to 〇.2% by mass. (Patent Document 1). However, the addition of Fe to the lead-free solder alloy suppresses the etching effect of the Fe coating layer with the same soldering time, but significantly hinders the wettability of the solder, thereby prolonging the soldering time, and as a result, the Fe coating is eroded. [Problem to be Solved by the Invention] The object of the present invention is to provide a member using a Fe or Fe-based alloy, Sn-Ag-based with Sn as a main component. When a Cu-based lead-free solder alloy is welded, a solder alloy for preventing iron corrosion of a welding machine member coated with Fe or a Fe-based alloy and a method for preventing fused uranium by F e are prevented. φ [Means for Solving the Problem] As described above, the reason why Fe is etched is obvious because it is replaced by lead-free solder, and the Sn content in the solder which is easy to dissolve Fe is high, and the wettability of the solder itself is poor. The soldering time is about 2 times, the melting temperature of the Sn-Pb solder alloy of the prior art (about 1 83 ° C) to the melting temperature of the Sn-Ag-Cu lead-free solder alloy (about 220 ° C), in which the solder is melted. The temperature rises by about 40 ° C. Therefore, the use temperature of the tip is also raised from the temperature of 300 ° C to 420 ° C of the Sn-Pb solder alloy to the use temperature of the Sn-Ag-Cu lead-free solder alloy. The results of 380 ° C ~ 450 ° C and other results promote the reaction with Fe ^ 345502 years ι 狗 dog repair (£) is replaced by ~, the coating is easily eroded. The present inventors discovered that Co is dispersed in a Sn-Ag-Cu-based lead-free solder alloy by using a solder containing a small amount of Co in a Sn-Ag-Cu-based lead-free solder alloy to prevent dissolution of Fe, and thus it is difficult to produce soldering defects. The tip of the Fe is etched to complete the present invention. The solder alloy for preventing iron corrosion according to the present invention is composed of Ag: 0.3% by mass or more and 4.0% by mass or less, Cu: 0.1% by mass or more, 1.0% by mass or less, and Co: 0.001% by mass or more, 〇.5% by mass Hereinafter, the remaining portion is a solder alloy composed of a synthetic composition of Sn. In order to improve the fatigue resistance of the solder alloy, Ni may be contained in an amount of 0.01% by mass or more and 0.1% by mass or less in the solder alloy composition. In the present invention, when a welding member coated with Fe or a Fe-based alloy is used, and a Sn-Ag-Cu-based lead-free solder alloy containing Sn as a main component is used for welding, Sn containing 0.001% by mass or more and 0.5% by mass or less of Co is used. A method of preventing iron corrosion of a welding machine member for coating a Fe or Fe-based alloy characterized by welding a lead-free solder alloy of Ag-Cu. The welding machine member for preventing iron corrosion which is easy to generate iron corrosion by the present invention, for example, the tip of the welding boring for hand welding, the tip of the welding boring for the welding robot, and the welding boring for the repairing device镘 等 and so on. Such a member is coated with Fe as described above or by plating with Ni. Further, in the case of Fe plating, Fe-C alloy-based Fe-based alloy plating is also included. [Effect of the Invention] By using the Sn-Ag-Cu-based lead-free solder alloy of the present invention, -8 - 1345502
Pf5年卜月ί 曰修(¾正替換頁 -W —— 加Co : 0·001質量％以上，0.5質量％以下，較佳爲Co : 0·01質量％以上，0.1質量％以下之焊料合金，相較於以往 之Sn-Pb系焊料合金，即使使用焊料之Fe熔蝕快速之Sn-Ag-Cu系無鉛焊料合金，用於手焊之焊接鏝的鏝尖保護膜 之Fe被覆層的熔蝕較少，鏝尖壽命約延長爲3倍。 【實施方式】 φ (發明實施之最佳形態） 其中，有關本發明之焊料合金的防止Fe熔蝕機構雖 並未明確，惟，可推測如下述。 亦即，「Fe熔蝕」係指與焊料接觸之構件等所含有之 Fe份耗損於焊料中的現象，通常，Fe份會熔解於熔融焊 料中的現象。 如此，於使用無鉛焊料合金之焊接中，產生Fe溶飩 之原因係Sn與Fe進行反應（相互擴散）合金化後，此乃 φ 是變成容易熔解於熔融焊料中之Sn的緣故。Sn之含量愈 多，Fe熔餓愈明顯》 於不銹鋼也同樣產生此現象，產生不銹鋼之熔蝕。不 銹鋼亦爲Fe系合金之一種，因此，本說明書中亦包含此 情形，稱爲Fe熔蝕》 由此可知，欲防止無鉛焊料合金所呈現之Fe熔飩時 ，只要限制可溶解Fe量及其速度者即可。 該溶解量與速度係依焊料組成與溫度而異。因此，欲 抑制Fe熔解於焊料中之Sn之速度時，如先行技術所示， -9- 1345502Pf5年年月 曰 曰 修 (3⁄4正换页-W ——Co alloy: Co. 0.001 mass% or more, 0.5 mass% or less, preferably Co: 0.001 mass% or more, 0.1 mass% or less of the solder alloy Compared with the conventional Sn-Pb-based solder alloy, even if a Fe-Ag-Cu-based lead-free solder alloy which is quickly etched by Fe is used, the Fe coating of the tip protective film for hand soldering is melted. The etch is less, and the life of the tip is about three times longer. [Embodiment] φ (Best Mode for Carrying Out the Invention) Among them, the mechanism for preventing Fe corrosion of the solder alloy of the present invention is not clear, but it is presumed as follows In other words, "Fe ablation" refers to a phenomenon in which Fe contained in a member that is in contact with solder is depleted in solder, and generally, Fe is melted in molten solder. Thus, a lead-free solder alloy is used. In the welding, the reason why Fe is dissolved is caused by the reaction of Sn and Fe (interdiffusion) alloying, and this is because φ is Sn which is easily melted in the molten solder. The more the content of Sn, the more the Fe melts. Obviously, this phenomenon also occurs in stainless steel, resulting in no Corrosion of stainless steel. Stainless steel is also a kind of Fe alloy. Therefore, this case is also included in this specification, which is called Fe corrosion. It can be seen that when it is to prevent the Fe melting of the lead-free solder alloy, it is only necessary to limit The amount of dissolved Fe and its velocity can be either. The amount and speed of dissolution vary depending on the composition of the solder and the temperature. Therefore, when suppressing the rate of melting of Sn in the solder, as shown in the prior art, -9- 1345502
-- I ff年卜月< M修(※正替起 — - 」 可預先添加Fe於Sn中即可抑制。惟，熔融狀態下，熔解 之Fe於凝固後對於Sn幾乎不會固溶，即使微量之Fe溶 解時’凝固時會析出FeSn化合物（結晶析出），會造成 液相線溫度上昇。-- I ff year and month < M repair (※ is replaced by - - " can be suppressed by adding Fe in the Sn in advance. However, in the molten state, the melted Fe hardly dissolves on Sn after solidification. Even if a small amount of Fe is dissolved, the FeSn compound (crystal precipitation) precipitates during solidification, which causes the liquidus temperature to rise.
Fe由周期表觀之係屬第8族之金屬，屬於相同的第8 族之Co及Ni，屬於第6族之Cr等稱爲過渡金屬，具相 似性質。大部份之過渡金屬與Fe相同，不會固溶於Sn中 ，以化合物形態析出，而造成液相線溫度上昇，惟，Ni或 Co具有製作共晶組成，使熔融溫度降低的性質。本發明 人等著眼於此點。Fe is a metal belonging to Group 8 from the periodic table, belonging to the same Group 8 Co and Ni, and Cr belonging to Group 6 is called a transition metal and has similar properties. Most of the transition metals are the same as Fe, do not dissolve in the Sn, precipitate in the form of a compound, and cause the liquidus temperature to rise. However, Ni or Co has a property of making a eutectic composition and lowering the melting temperature. The inventors of the present invention have focused on this point.
Ni、Co添加於Sn-Ag-Cu系無鉛焊料合金時，此等於 熔融時會熔於Sn中。特別是Co，於Sn-Ag-Cu系無鉛焊 料合金中，Co即使微量熔解時，Fe、Ni、Cr等同種過渡 金屬也無法再溶解，證明Fe系合金構件或被覆Fe或Fe 系合金之構件之熔蝕被抑制。實驗結果，Ni的情形也具相 同效果，惟，Ni添加於，Sn-Ag-Cu系合金時，伴隨液相 線溫度之上昇，可容許量有其限度，未能添加大量的Ni。 另外，Co之添加，相較於Ni，即使微量有有效果，此外 ，即使與Ni同等的量，也未發現液相線溫度之上昇。When Ni and Co are added to a Sn-Ag-Cu-based lead-free solder alloy, this is equivalent to melting in Sn when molten. In particular, in Co-free Sn-Ag-Cu-based lead-free solder alloys, Fe, Ni, and Cr equivalent transition metals cannot be redissolved even when Co is slightly melted, and Fe-based alloy members or members coated with Fe or Fe-based alloys are proved. The erosion is suppressed. As a result of the experiment, the same effect was obtained in the case of Ni. However, when Ni was added to the Sn-Ag-Cu alloy, the allowable amount of the liquidus temperature was increased, and a large amount of Ni could not be added. Further, the addition of Co was not as effective as that of Ni, and the liquidus temperature was not increased even in the same amount as Ni.
Sn-Ag-Cu系無鉛焊料合金中之最佳之Co的添加量係 依Sn之含量而定，Sn約95 %以上時，以0.001質量％以 上，0.5質量％以下爲佳，更佳爲0.01質量％以上，〇.1質 量%以下。 當Co量爲少於0.01質量％，特別是少於o.ool質量％ -10- 1345502 昨Λ月丨?日修(k)正替换頁 | 1 ——- 時，則無被覆Fe或Fe系合金之機器構件的ϊ?ε熔鈾抑制 效果’反之’ Co量多於0.1質量％，特別是多於〇_5質量 %會引起液相線溫度之上昇，恐造成作業性不良之虞。 依據本發明時，特別可實現適於手焊之焊料合金組成 ，因此，本發明之焊料合金之潤濕性特佳。 後述表1顯示Sn-Ag_Cu系無鉛焊料合金之熔融溫度 與弧面狀沾錫（meniscograph)法之歸零（zero cross)時 間。適於手焊之無鉛焊料合金之組成係歸零時間爲3秒以 內之焊料。 其中，針對Sn之Ag的添加可明顯提昇焊料合金之潤 濕性。對於Sn基劑之無鉛焊料之Ag的添加係藉由0.3質 量％以上，效果顯現，特別是添加3.0質量％以上時，更提 昇焊料合金之潤濕性。添加4.0質量％以上之Ag時，會提 高焊料合金之熔融溫度，因此，務必提昇焊接鏝之設定溫 度，Fe熔蝕變大。 又，對於Sn基劑之無鉛焊料之Cu之微量添加’不僅 提昇焊料合金之強度，同時亦降低焊料合金之熔融溫度’ 潤濕性亦提昇。The optimum amount of Co added in the Sn-Ag-Cu-based lead-free solder alloy is determined by the content of Sn. When Sn is about 95% or more, it is preferably 0.001% by mass or more and 0.5% by mass or less, more preferably 0.01%. % by mass or more, 〇.1% by mass or less. When the amount of Co is less than 0.01% by mass, especially less than o.ool% by mass -10- 1345502 Yesterday 丨? 日修(k) is replacing page | 1 ——-, then there is no coating of Fe or Fe The ϊ ε 熔 抑制 抑制 抑制 抑制 ' ' ' ' ' ' 合金 合金 Co Co Co Co Co Co Co Co Co Co Co Co Co Co Co Co Co Co Co Co Co Co Co Co Co Co Co Co Co Co Co According to the present invention, a solder alloy composition suitable for hand soldering can be particularly realized, and therefore, the solder alloy of the present invention is particularly excellent in wettability. Table 1 below shows the melting temperature of the Sn-Ag_Cu-based lead-free solder alloy and the zero cross time of the mencigraph method. The composition of the lead-free solder alloy suitable for hand soldering is solder with a return time of less than 3 seconds. Among them, the addition of Ag to Sn can significantly improve the wettability of the solder alloy. When the addition of Ag to the lead-free solder of the Sn base is 0.3% by mass or more, the effect is exhibited, and particularly when 3.0% by mass or more is added, the wettability of the solder alloy is further improved. When 4.0% by mass or more of Ag is added, the melting temperature of the solder alloy is increased. Therefore, it is necessary to increase the set temperature of the solder joint and the Fe is increased. Further, the micro-addition of Cu to the lead-free solder of the Sn base not only increases the strength of the solder alloy, but also lowers the melting temperature of the solder alloy, and the wettability is also improved.
Cu之添加係添加0 · 1質量％以上，較佳爲添加〇 . 5質 量％以上，所期待之效果顯現，超過1 ·〇質量％時’會提高 焊料合金之溶融溫度，因此，務必提昇焊鏝之設定溫度’ 且Fe熔蝕變大。 適於手焊之Sn_Ag-Cu系無鉛焊料合金係Ag: 〇·3質 量％以上，4.0質量％以下、Cn : 0· 1質量％以上，1 ·〇質量 -11 - 1345502 修(¼)正替换 %以下’剩餘部份爲Sn之組成較佳，其中最理想之Sn-Ag-Cu系無鉛焊料合金的組成爲Ag: 3.0質量％以上，未 達4·0質量％、Cu : 0.1質量％以上，未達1.0質量％，剩 餘部份爲S η。 依據本發明，藉由添加0.0 0 1質量％以上，〇 · 5質量％ 以下，較佳爲0.01質量％以上，0.1質量％以下之Co於此 等無鉛焊料合金中，可減少焊接鏝之鏝尖對Fe或Fe系合 金之鍍敷的鐵熔蝕者。 用於被覆Fe或Fe系合金之焊接用構件之防止鐵熔蝕 方法之本發明的焊料合金組成係由 Ag : 0.3質量％以上， 4.0質量％以下、Cu : 0.1質量％以上，1.0質量％以下、Co :0.001質量％以上，0.5質量％以下，剩餘部份實質上爲 Sn所成之合金組成的焊料合金。較佳爲該焊料合金係以 Ag : 3.0質量％以上，4.0質量％以下、Cu : 0.1質量％以上 ，1 .〇質量％以下、Co : 0.01質量％以上，0.1質量％以下 ，剩餘部份實質上爲Sn所成之合金組成的焊料合金。 依據本發明時，藉由添加微量Ni於被覆Fe或Fe系 合金之焊接用構件之防止鐵熔蝕方法所使用之焊料合金組 成，可改善焊料合金之耐疲勞性。所添加之Ni係Ni若少 於0.01質量％時，無改善耐疲勞性的效果，該Ni量若高 於1質量％時’ Ni會析出’焊料合金之熔點會上昇至接 近3 00 t，因此，務必提昇焊接鏝之設定溫度，使得鐵熔 蝕變大。 本發明之焊料合金可爲任意形態者，惟爲防止鐵熔蝕 -12- 1345502 P件卜月，徊修泛頁 之前提下’大多用於流動焊接或迴焊之修正或其後安裝零 件之焊接，因此大多作爲所謂的樹脂粉芯焊料（Resin flux cored solders)使用。 其中樹脂粉芯焊料係預先將3%左右之助焊劑（flux) 存在於線狀成型之焊料中心部者，可同時進行焊料合金之 供給與焊劑之添加，已爲公知之焊料合金之一的使用形態 。當然，此時之助焊劑亦爲公知者，例如有松脂系或鹵系 ，目前以松脂系爲佳。另外，用於樹脂粉芯焊料之助焊劑 組成已於JIS規定，本發明亦採用該規定者即可，並特別 限定。 以下，藉由實施例具體說明本發明之作用效果。 (實施例） 製作表1所示之各焊料合金組成之樹脂粉芯焊料，焊 接印刷基板之焊墊（Land) ’檢查鏝尖之可使用次數。其焊料 合金組成、其熔融溫度、潤濕均衡法之歸零時間及鏝尖可 使用次數之結果同樣整理於表1。 -13- 1345502 ,ρ^ι^Φ修(¾正替換克| 表 焊料組成 Sn Ag Cu Co Ni 其他 溶融溫度(r) 歸零 時間 使用 次數 固相 線 液相 線 (sec) 實施 例 1 剩餘部份 1 0.5 0.01 - 217 227 2.3 2180 2 剩餘部份 0.3 0.5 0.01 0.01 218 228 2.5 2330 3 剩餘部份 3 0.5 0.01 - 217 220 1.5 2877 4 剩餘部份 3 0.5 0.1 0.01 218 221 1.6 2746 5 剩餘部份 3.5 1 0.01 - 217 233 1.5 2843 6 剩餘部份 3.9 0.5 0.01 - 217 229 1.3 3201 7 剩餘部份 3.9 1 0.1 - 218 231 1.4 2981 8 剩餘部份 3.9 1 0.1 0.1 218 233 1.4 2874 比較 例 1 剩餘部份 0.5 - - 227 231 4.0 780 2 剩餘部份 - 0.7 - - Fe0.05 227 230 3.6 1463 3 剩餘部份 0.3 0.5 - - 217 228 2.6 985 4 剩餘部份 0.1 0.7 - - 217 228 3.1 820 5 剩餘部份 3.5 1 1 217 270 3.2 1830 6 剩餘部份 - - - Pb37 183 183 0.8 3506 7 剩餘部份 3.0 0.5 - 0.25 218 320 1.9 1980 取得此等結果之試驗條件如下。 (1 )鏝尖之使用次數 焊墊形狀：圓形 焊墊尺寸：直徑〇.8mm 焊鏝溫度：焊料合金之熔融溫度+160°C 鏝尖材質構造：母材 Cu 基底 鍍Ni (厚度50μπ〇 表面 鍍Fe (厚度30μιη ) 樹脂粉芯焊料 樹脂粉芯焊料徑：直徑〇.5mm -14 - 1345502 替换頁 卸，？日修(更)正替‘ 助焊劑等級：AA(JIS Z 3283) 助焊劑含量：3質量％ (2 )熔融溫度（JIS Z 3 198-1 ) 測定方法：差式掃描熱量測定法（DSC) 昇溫速度：5°C/分鐘載體氣體：Air (3 )藉由潤濕均衡法之潤濕性測定（JIS Z 3198-4 )The addition of Cu is added in an amount of 0.1% by mass or more, preferably 5% by mass or more, and the desired effect is exhibited. When the amount exceeds 1% by mass, the melting temperature of the solder alloy is increased. Therefore, it is necessary to increase the soldering temperature. The set temperature of 镘 is 'and the Fe is enlarged. Sn_Ag-Cu-based lead-free solder alloy for hand welding Ag: 〇·3 mass% or more, 4.0 mass% or less, Cn: 0·1 mass% or more, 1 ·〇 quality -11 - 1345502 repair (1⁄4) replacement % or less of the remaining portion is preferably Sn, and the composition of the most preferable Sn-Ag-Cu-based lead-free solder alloy is Ag: 3.0% by mass or more, less than 4.0% by mass, and Cu: 0.1% by mass or more. , less than 1.0% by mass, and the remainder is S η. According to the present invention, by adding 0.001% by mass or more, 〇·5 mass% or less, preferably 0.01% by mass or more, 0.1% by mass or less of Co in such a lead-free solder alloy, the tip of the solder can be reduced. An iron etcher for the plating of Fe or Fe alloys. The solder alloy composition of the present invention for preventing iron corrosion of a member for welding a Fe or Fe-based alloy is made of Ag: 0.3% by mass or more, 4.0% by mass or less, Cu: 0.1% by mass or more, and 1.0% by mass or less. Co: 0.001 mass% or more and 0.5 mass% or less, and the remainder is substantially a solder alloy composed of an alloy of Sn. Preferably, the solder alloy has Ag: 3.0% by mass or more, 4.0% by mass or less, Cu: 0.1% by mass or more, 1.% by mass or less, and Co: 0.01% by mass or more and 0.1% by mass or less, and the remaining part is substantially A solder alloy composed of an alloy of Sn. According to the present invention, the fatigue resistance of the solder alloy can be improved by adding a trace amount of Ni to the solder alloy composition for preventing the iron etching method of the member for welding of the Fe or Fe-based alloy. When the amount of the Ni-based Ni to be added is less than 0.01% by mass, the effect of improving the fatigue resistance is not obtained. When the amount of Ni is more than 1% by mass, 'Ni is precipitated', and the melting point of the solder alloy rises to nearly 300 t. It is necessary to increase the set temperature of the soldering iron to make the iron corrosion larger. The solder alloy of the present invention can be of any form, but to prevent iron corrosion -12 - 1345502 P piece of the month, before the repair of the general page, the "mostly used for flow welding or reflow correction or post-installation parts" Soldering is therefore mostly used as so-called Resin flux cored solders. Among them, the resin powder core solder has a flux of about 3% in advance in the center portion of the wire-formed solder, and the supply of the solder alloy and the addition of the flux can be simultaneously performed, which is one of the well-known solder alloys. form. Of course, fluxes are also known at this time, such as rosin or halogen, and rosin is preferred. Further, the flux composition for the resin powder core solder is specified in JIS, and the present invention is also applicable to the specification, and is particularly limited. Hereinafter, the effects of the present invention will be specifically described by way of examples. (Example) A resin powder core solder of each solder alloy composition shown in Table 1 was prepared, and a solder pad (Land) of a printed circuit board was soldered to check the number of times the tip was used. The results of the solder alloy composition, the melting temperature, the zeroing time of the wetting equalization method, and the number of times the tips can be used are also summarized in Table 1. -13- 1345502 , ρ^ι^Φ repair (3⁄4 positive replacement gram | table solder composition Sn Ag Cu Co Ni other melting temperature (r) return to zero time usage number solidus liquidus (sec) Example 1 Remaining part Parts 1 0.5 0.01 - 217 227 2.3 2180 2 Remaining part 0.3 0.5 0.01 0.01 218 228 2.5 2330 3 Remaining part 3 0.5 0.01 - 217 220 1.5 2877 4 Remaining part 3 0.5 0.1 0.01 218 221 1.6 2746 5 Remaining part 3.5 1 0.01 - 217 233 1.5 2843 6 Remaining part 3.9 0.5 0.01 - 217 229 1.3 3201 7 Remaining part 3.9 1 0.1 - 218 231 1.4 2981 8 Remaining part 3.9 1 0.1 0.1 218 233 1.4 2874 Comparative example 1 Remaining part 0.5 - - 227 231 4.0 780 2 Remaining part - 0.7 - - Fe0.05 227 230 3.6 1463 3 Remaining part 0.3 0.5 - - 217 228 2.6 985 4 Remaining part 0.1 0.7 - - 217 228 3.1 820 5 Remaining part 3.5 1 1 217 270 3.2 1830 6 Remaining part - - - Pb37 183 183 0.8 3506 7 Remaining part 3.0 0.5 - 0.25 218 320 1.9 1980 The test conditions for obtaining these results are as follows: (1) The number of times the tip is used : Round pad size: Diameter 〇.8mm Soldering temperature: melting temperature of solder alloy +160°C 镘 Tip material structure: base material Cu base plating Ni (thickness 50μπ〇 surface plating Fe (thickness 30μιη) resin powder core solder resin powder core solder diameter: diameter 〇.5mm -14 - 1345502 Replacement page unloading, daily repair (more) replacement ' Flux grade: AA (JIS Z 3283) Flux content: 3 mass% (2) Melting temperature (JIS Z 3 198-1) Measurement method: differential scanning calorimetry (DSC) Heating rate: 5 ° C / min Carrier gas: Air (3) Wetting property measurement by wetting equalization method (JIS Z 3198-4 )
浸漬深度：2mm 浸漬速度：5mm/秒 浸漬時間：1 0秒 焊料溫度：250°C 使用助焊劑：ww松香之25% IPA溶液 含有0.001質量％以上、0.5質量％以下之Co的本發 明之焊料合金，鏝尖可使用次數接近3000次’而不含Co 之比較例之樹脂粉芯焊料之使用次數爲1 000次以下’使 用前述專利文獻1所揭示之焊料合金之樹脂粉芯焊料亦僅 可使用1 5 00次而已。 -15-Immersion depth: 2 mm Immersion speed: 5 mm/sec. Immersion time: 10 seconds Solder temperature: 250 ° C Flux: 25% of ww rosin The IPA solution contains 0.001% by mass or more and 0.5% by mass or less of Co of the present invention. In the case of the alloy, the number of times the resin tip core can be used is close to 3,000 times, and the number of times of use of the resin powder core solder of the comparative example containing no Co is 1,000 or less. The resin powder core solder using the solder alloy disclosed in the above Patent Document 1 can only be used. Use 1 500 times. -15-
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| CN102091882A (en) * | 2011-01-12 | 2011-06-15 | 北京工业大学 | Lead-free solder containing Sn, Ag, Cu and Co |
| WO2019035197A1 (en) * | 2017-08-17 | 2019-02-21 | 千住金属工業株式会社 | Solder alloy for preventing fe erosion, flux cored solder, wire solder, flux cored wire solder, flux-coated solder and solder joint |
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| JP3599101B2 (en) * | 2000-12-11 | 2004-12-08 | 株式会社トッパンＮｅｃサーキットソリューションズ | Solder, surface treatment method of printed wiring board using the same, and mounting method of electronic component using the same |
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