TW201837194A - Lead-free solder alloy and solder joint - Google Patents
Lead-free solder alloy and solder joint Download PDFInfo
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- TW201837194A TW201837194A TW107111241A TW107111241A TW201837194A TW 201837194 A TW201837194 A TW 201837194A TW 107111241 A TW107111241 A TW 107111241A TW 107111241 A TW107111241 A TW 107111241A TW 201837194 A TW201837194 A TW 201837194A
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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
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C13/00—Alloys based on tin
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Abstract
Description
本發明係關於一種與至少於表面層含有Al的基板的焊接時可使用的Sn-Ag-Cu系無鉛焊料合金。 The present invention relates to a Sn-Ag-Cu based lead-free solder alloy that can be used for soldering to a substrate containing Al at least in its surface layer.
由於Al相較於其他金屬,具有高熱導率,較少發生熱應力,經常可用於電子機器等的散熱構件。此外,近年作為Al特性的比重小或強度受到矚目,作為賦予馬達等的輕量化的素材受到研究。 Compared with other metals, Al has high thermal conductivity and less thermal stress, and is often used as a heat sink for electronic equipment. In addition, in recent years, attention has been paid to a small specific gravity or strength as an Al characteristic, and studies have been made on materials that are lightweight for motors and the like.
但是,如上述,Al用於散熱構件或馬達的線圈等時,雖然使用焊料的接合相當平常,但有無法獲得充分的接合強度及可靠性的問題點存在。 However, as described above, when Al is used for a heat radiating member or a coil of a motor, although bonding using solder is quite common, there are problems in that sufficient bonding strength and reliability cannot be obtained.
作為Al用焊料,分別於專利文獻1中揭示Sn-(3~40%)Zn-(1~10%)Ag-(0.5~4%)Cu組成的焊料合金,專利文獻2中揭示Sn-(0.5~7%)Mg-(1.5~20%)Zn-(0.5~15%)Ag組成的焊料合金。 As a solder for Al, Patent Literature 1 discloses a solder alloy composed of Sn- (3 ~ 40%) Zn- (1 ~ 10%) Ag- (0.5 ~ 4%) Cu, and Patent Literature 2 discloses Sn- ( 0.5 ~ 7%) solder alloy consisting of Mg- (1.5 ~ 20%) Zn- (0.5 ~ 15%) Ag.
此外,分別於專利文獻3中揭示Sn-(10~15%)Zn-(0.1~1.5%)Cu-(0.0001~0.1%)Al-(0.0001~0.03%)Si-(0.0001~0.02%)Ti-(0.0001~0.01%)B組成的焊料合金,專利文獻4中揭示Sn-(10%以下)Ag-(15%以下)Al組成的Al構件直接接合用焊料合金。 In addition, Patent Literature 3 discloses Sn- (10 ~ 15%) Zn- (0.1 ~ 1.5%) Cu- (0.0001 ~ 0.1%) Al- (0.0001 ~ 0.03%) Si- (0.0001 ~ 0.02%) Ti -(0.0001 to 0.01%) B solder alloy, Patent Literature 4 discloses a solder alloy for direct bonding of Al members composed of Sn- (10% or less) Ag- (15% or less) Al.
然後,專利文獻5中揭示作為Al材料彼此或Al材料與異質材料的接合相關的接合方法,使用由選自Cu、Ag、In、Bi、Co、Ti群組的金屬元素與剩餘部分Sn而成的Sn系焊料的接合。 Then, Patent Document 5 discloses a joining method for joining Al materials to each other or Al materials and heterogeneous materials, using a metal element selected from the group consisting of Cu, Ag, In, Bi, Co, and Ti and the remaining portion of Sn. Sn-based solder joints.
專利文獻1:日本特開昭50-50250號公報。 Patent Document 1: Japanese Patent Application Laid-Open No. 50-50250.
專利文獻2:日本特開昭50-56347號公報。 Patent Document 2: Japanese Patent Application Laid-Open No. 50-56347.
專利文獻3:日本特開2006-167800號公報。 Patent Document 3: Japanese Patent Application Laid-Open No. 2006-167800.
專利文獻4:日本特開2008-142729號公報。 Patent Document 4: Japanese Patent Application Laid-Open No. 2008-142729.
專利文獻5:日本特開2011-167714號公報。 Patent Document 5: Japanese Patent Application Laid-Open No. 2011-167714.
另一方面,已知作為無鉛焊料合金被廣泛使用的Sn-Ag-Cu系焊料合金不適合用於Al構件的接合。詳言之,已知使用Sn-Ag-Cu系焊料合金,進行Al構件彼此的接合時,或是Al構件與異種金屬構件接合時,由於形成於Al構件表面的氧化膜,或是電解腐蝕(伽凡尼腐蝕,galvanic corrosion)等問題發生,無法獲得充分的接合強度。 On the other hand, it is known that a Sn-Ag-Cu based solder alloy widely used as a lead-free solder alloy is not suitable for joining Al members. In detail, it is known that when an Sn member is used to bond Al members to each other, or when an Al member is bonded to a dissimilar metal member, an oxide film formed on the surface of the Al member or electrolytic corrosion is used ( Galvanic corrosion and other problems occur, and sufficient joint strength cannot be obtained.
再者,相關的軟焊接合使用在海水之類的鹽水等環境時,有上述電解腐蝕迅速進行,在短時間Sn-Ag-Cu系焊料合金與Al構件剝離的問題。 Furthermore, when the related soft soldering is used in an environment such as salt water such as seawater, the above-mentioned electrolytic corrosion proceeds rapidly, and there is a problem that the Sn-Ag-Cu-based solder alloy and the Al member are separated in a short time.
然而,專利文獻1~5中,並未揭示有關於Sn-Ag-Cu系焊料合金。此外,對於使用Sn-Ag-Cu系焊料合金接合Al構件 的軟焊接合,關於在鹽水環境的耐腐蝕性及接合可靠性的提升未有助益。 However, Patent Documents 1 to 5 do not disclose Sn-Ag-Cu based solder alloys. In addition, soft soldering of Al members using Sn-Ag-Cu based solder alloys has not contributed to the improvement of corrosion resistance and joint reliability in salt water environments.
本發明係鑑於相關的事實而完成者,作為其目的,係提供一種即使在鹽水環境,對於與Al構件的接合可維持良好的耐腐蝕性及高接合可靠性的Sn-Ag-Cu系無鉛焊料合金及軟焊接合。 The present invention was made in view of the related facts, and as its object, it is to provide a Sn-Ag-Cu based lead-free solder capable of maintaining good corrosion resistance and high bonding reliability for bonding to an Al member even in a salt water environment. Alloy and soft welding.
本發明相關的無鉛焊料合金係與至少於表面層含有Al的被接合構件的焊接時可使用的Sn-Ag-Cu系無鉛焊料合金中,其特徵在於:包含:Ni以及與Al的標準電極電位的差為0.7V以下的助劑。 The Sn-Ag-Cu-based lead-free solder alloy which can be used for soldering to a joined member containing Al at least in its surface layer according to the present invention is characterized in that it includes: Ni and a standard electrode potential with Al The difference is 0.7V or less.
本發明相關的無鉛焊料合金,其特徵在於:上述助劑為選自Mn、Ti、Mg、Zr當中至少一者。 The lead-free solder alloy according to the present invention is characterized in that the auxiliary agent is at least one selected from the group consisting of Mn, Ti, Mg, and Zr.
本發明相關的無鉛焊料合金,其特徵在於:Mn的添加量超過0至0.01質量%。 The lead-free solder alloy according to the present invention is characterized in that the added amount of Mn exceeds 0 to 0.01% by mass.
本發明相關的無鉛焊料合金,其特徵在於:包含:3.00重量%的Ag,5.00重量%的Cu,0.05重量%的Ni。 The lead-free solder alloy according to the present invention is characterized by comprising: 3.00 wt% Ag, 5.00 wt% Cu, and 0.05 wt% Ni.
本發明相關的軟焊接合係添加有Ni的Sn-Ag-Cu系無鉛焊料合金,與至少於表面層含有Al的被接合構件之軟焊接合,其特徵在於:上述無鉛焊料合金包含與Al的標準電極電位的差為0.7V以下的助劑,上述助劑分佈於接合部位。 The Sn-Ag-Cu lead-free solder alloy to which Ni is added in the soft soldering system according to the present invention is soft-welded to a member to be joined containing Al at least in its surface layer, wherein the lead-free solder alloy includes Al and Al Auxiliaries with a standard electrode potential difference of 0.7 V or less, which are distributed at the joints.
根據本發明,提供一種即使於鹽水環境,對於與Al構件的接合可維持良好耐腐蝕性及高接合可靠性的 Sn-Ag-Cu系無鉛焊料合金及軟焊接合。 According to the present invention, there is provided a Sn-Ag-Cu-based lead-free solder alloy and a solder joint capable of maintaining good corrosion resistance and high joint reliability for joining to an Al member even in a salt water environment.
1,1a,1b‧‧‧試驗片 1,1a, 1b ‧‧‧test piece
2‧‧‧焊料合金箔 2‧‧‧solder alloy foil
100‧‧‧軟焊接合 100‧‧‧soft welding
第1圖係表示本實施形態相關的軟焊接合的試驗試樣中使用的試驗片的側視圖。 FIG. 1 is a side view showing a test piece used in a test sample for solder welding according to this embodiment.
第2圖係表示本實施形態相關的軟焊接合的試驗試樣的一例的示意圖。 FIG. 2 is a schematic diagram showing an example of a test sample for soft soldering according to this embodiment.
第3圖係表示表2的腐蝕試驗結果的條形圖。 FIG. 3 is a bar graph showing the results of the corrosion test in Table 2.
第4圖係表示表6的最大應力的測定結果的條形圖。 FIG. 4 is a bar graph showing the measurement results of the maximum stress in Table 6.
第5圖係表示表7的最大應力的比例的條形圖。 FIG. 5 is a bar graph showing the ratio of the maximum stress in Table 7. FIG.
第6圖係表示比較例1的最大應力,與實施例2~5及比較例2~5試驗試樣的最大應力的差,相對於與Al的標準電極電位的差(V)作圖而成的圖表。 FIG. 6 is a graph showing the maximum stress of Comparative Example 1, and the difference between the maximum stress of the test samples of Examples 2 to 5 and Comparative Examples 2 to 5, plotted against the standard electrode potential difference (V) from Al. Chart.
以下,針對本發明實施形態相關的Sn-Ag-Cu系無鉛焊料合金及軟焊接合,依據圖示詳細說明。 Hereinafter, the Sn-Ag-Cu based lead-free solder alloy and the solder joint according to the embodiment of the present invention will be described in detail with reference to the drawings.
本實施形態相關的Sn-Ag-Cu系無鉛焊料合金係可使用在與含有Al的被接合構件的焊接時。本文中,含有Al的被接合構件包括:例如純鋁部材或具有Al塗層的表面的構件,或是,至少於表面層包含Al的構件。 The Sn-Ag-Cu-based lead-free solder alloy system according to this embodiment can be used when soldering to a member to be joined containing Al. Herein, the bonded member containing Al includes, for example, a member made of pure aluminum or a surface having an Al coating layer, or a member containing Al at least in the surface layer.
以下,於至少一側的純鋁(Al)板進行Sn-Ag-Cu系無鉛焊料合金的焊接的情形為例進行說明。本實施形態相關的Sn-Ag-Cu系無鉛焊料合金除了含有Sn、Ag、Cu之外,更包含Ni及助劑。以下,以添加有Mn作為助劑的情形為例進行說明。 Hereinafter, a case where the Sn-Ag-Cu based lead-free solder alloy is soldered on at least one pure aluminum (Al) plate will be described as an example. The Sn-Ag-Cu-based lead-free solder alloy according to this embodiment contains, in addition to Sn, Ag, and Cu, Ni and an auxiliary agent. Hereinafter, a case where Mn is added as an assistant will be described as an example.
表1係表示本實施形態相關的Sn-Ag-Cu系焊料合金(實施例1)的組成的表。此外,表1中一併表示比較例1及比較例2。 Table 1 is a table showing the composition of a Sn-Ag-Cu based solder alloy (Example 1) according to this embodiment. In addition, Table 1 shows Comparative Example 1 and Comparative Example 2 together.
如表1所示,本實施形態相關的Sn-Ag-Cu系焊料合金(以下,稱為實施例1)係包含:Cu、Ag、Ni分別為5重量%、3重量%、0.05重量%,更包含0.003重量%的Mn,剩餘部分為Sn,實施例1中焊接溫度為320℃。 As shown in Table 1, the Sn-Ag-Cu-based solder alloy (hereinafter, referred to as Example 1) related to this embodiment contains Cu, Ag, and Ni at 5 wt%, 3 wt%, and 0.05 wt%, respectively. It further contained 0.003% by weight of Mn, and the remainder was Sn. The soldering temperature in Example 1 was 320 ° C.
此外,比較例1包含:Cu、Ag、Ni分別為5重量%、3重量%、0.05重量%,剩餘部分為Sn。比較例2包含:Cu、Ag分別為0.5重量%、3重量%,剩餘部分為Sn。比較例1、2中焊接溫度分別為320℃、245℃。 In addition, Comparative Example 1 contains Cu, Ag, and Ni at 5 wt%, 3 wt%, and 0.05 wt%, respectively, and the remainder is Sn. Comparative Example 2 contains Cu and Ag at 0.5% by weight and 3% by weight, respectively, and the remainder is Sn. In Comparative Examples 1 and 2, the soldering temperatures were 320 ° C and 245 ° C, respectively.
使用上述實施例1、比較例1及比較例2作成軟焊接合的試驗試樣。試驗試樣藉由使用實施例1、比較例1及比較例2,將Al試驗片彼此接合而作成。以下,詳細說明。 The above-mentioned Example 1, Comparative Example 1 and Comparative Example 2 were used to prepare test samples for soldering. The test samples were prepared by joining Al test pieces to each other using Example 1, Comparative Example 1, and Comparative Example 2. The details are described below.
第1圖係表示軟焊接合的試驗試樣中使用的試驗片的側視圖,第2圖係表示軟焊接合的試驗試樣的一例的示意圖。試驗片1具有25×5×1mm的短條狀。 FIG. 1 is a side view showing a test piece used in a test sample for soldering, and FIG. 2 is a schematic diagram showing an example of a test sample for soldering. The test piece 1 has a short strip shape of 25 × 5 × 1 mm.
首先,如第1圖所示於試驗片1的端部塗佈助焊劑約0.01g。上述助焊劑係Nihon superior公司製的No.1261。接著,於試驗片1的端部,寬度6mm的約正方形的焊接範圍(第1圖中,以斜線陰影表示)上進行實施例1、比較例1或比較例2的焊接,形成此等合金的鍍覆層。準備一對此類試驗片。 First, as shown in FIG. 1, about 0.01 g of a flux was applied to the end of the test piece 1. The above-mentioned flux is No. 1261 made by Nihon superior. Next, at the end of the test piece 1, a welding range of approximately square with a width of 6 mm (shown by hatching in the first figure) was performed in Example 1, Comparative Example 1, or Comparative Example 2 to form these alloys. Plating. Prepare a pair of such test pieces.
藉由將如以上所準備的Al的試驗片彼此焊接,作成試驗試樣的軟焊接合100。亦即,於實施例1、比較例1、2的任一者,試驗試樣的軟焊接合100皆為一側的試驗片1a及另一側的試驗片1b皆由Al的試驗片所製作。 The test pieces of Al prepared as described above were welded to each other to prepare a solder joint 100 of a test sample. That is, in any of Example 1, Comparative Examples 1, and 2, the solder joint 100 of the test sample is made of one test piece 1a and the other test piece 1b is made of an Al test piece. .
於試驗試樣的軟焊接合100的製作中,如第2圖所示,將Al的試驗片1a、1b的上述焊接範圍對向貼合,於該等之間夾著6×5×0.4mm的焊料合金箔2,加熱焊料合金箔2及其周圍,將試驗片1a、1b接合。此時,焊接溫度如表1所記載,試驗片1a、1b互相平行。之後,所作成的軟焊接合100冷卻至室溫,獲得如第2圖所示的試驗試樣的軟焊接合100。 In the production of the soft solder joint 100 of the test specimen, as shown in FIG. 2, the above-mentioned welding ranges of the Al test pieces 1 a and 1 b were opposed to each other, and 6 × 5 × 0.4 mm was sandwiched between them. The solder alloy foil 2 is heated, the solder alloy foil 2 and its surroundings are heated, and the test pieces 1a and 1b are joined. At this time, the welding temperature is as described in Table 1, and the test pieces 1a and 1b are parallel to each other. Then, the prepared solder joint 100 was cooled to room temperature, and the solder joint 100 of the test sample shown in FIG. 2 was obtained.
實施例1的試驗試樣中,試驗片1a、1b係藉由實施例1而接合,比較例1的試驗試樣中,試驗片1a、1b係藉由比較例1而接合,比較例2的試驗試樣中,試驗片1a、1b係藉由比較例2而接合。 Among the test samples of Example 1, the test pieces 1a and 1b were joined by Example 1. Among the test samples of Comparative Example 1, the test pieces 1a and 1b were joined by Comparative Example 1. In the test sample, the test pieces 1a and 1b were joined by Comparative Example 2.
據此,使用實施例1及比較例1、2的試驗試樣的軟焊接合100進行腐蝕試驗。相關的腐蝕試驗係將各試驗試樣完全浸漬於3%的NaCl水溶液中,放置在室溫。此時,試驗試樣以彼此不接觸的方式靜置。浸漬開始起24小時的時候將試驗試樣取出,確認是否能正常地接合。 Accordingly, the corrosion test was performed using the solder joint 100 of the test samples of Example 1 and Comparative Examples 1 and 2. The relevant corrosion test is that each test sample is completely immersed in a 3% NaCl aqueous solution and left at room temperature. At this time, the test specimens were left to stand without contacting each other. 24 hours after the start of immersion, the test sample was taken out, and it was confirmed whether it joined normally.
相關的確認係藉由於試驗試樣的軟焊接合100的一端起約5mm的位置P1以樹脂製焊鉗的前端擠壓、固定,於另一端起約5mm的位置P2以樹脂製焊鉗的前端按壓3次而進行。此時,按壓試驗試樣的軟焊接合100的強度係試驗試樣變形,未發生強制性剝離程度的強度。正常接合的試驗試樣再度浸漬於NaCl水溶液內,未能正常接合,亦即,發生剝離的試樣從容器取出。 The relevant confirmation is that the position of P1, which is about 5 mm from one end of the soft solder joint 100 of the test sample, is squeezed and fixed by the tip of the resin welding tongs, and the position of P2, which is about 5 mm from the other end, is the front of the resin welding tongs. Press 3 times. At this time, the strength of the solder joint 100 that pressed the test sample was a strength in which the test sample was deformed and no forced peeling occurred. The normally joined test specimens were immersed again in the NaCl aqueous solution and failed to join normally, that is, the peeled specimens were taken out of the container.
相關的腐蝕試驗結果表示於表2。表2中腐蝕試驗結果係顯示於試驗片1b的接合部位發生剝離。第3圖係表示表2的腐蝕試驗結果的條形圖。亦即,表2及第3圖係試驗片1a、1b皆為Al的試驗片的情形時,在試驗片1b的腐蝕試驗結果。 The relevant corrosion test results are shown in Table 2. The results of the corrosion test in Table 2 show that peeling occurred at the joints of the test piece 1b. FIG. 3 is a bar graph showing the results of the corrosion test in Table 2. That is, when the test pieces 1a and 1b in Table 2 and FIG. 3 are Al test pieces, the results of the corrosion test on the test piece 1b are shown.
相關的腐蝕試驗係於實施例1、比較例1、2中分別各進行3次。表2中係表示浸漬開始起至確認剝離發生的日數(以下,稱為接合日數)。此外,腐蝕試驗結果依升序表示。 The relevant corrosion tests were performed three times in each of Example 1, Comparative Examples 1, and 2. Table 2 shows the number of days from the start of immersion until the occurrence of peeling (hereinafter referred to as the number of bonding days). In addition, the corrosion test results are shown in ascending order.
由表2及第3圖可知,比較例2的平均接合日數為12日,比較例1的平均接合日數為36日,實施例1的平均接合日數為108日。亦即,比較接合日數時,依比較例2、比較例1、實施例1的順序越來越長。比較例1的接合日數相較於比較例2的接合日數長3倍,又實施例1的接合日數相較於比較例1的接合日數長3倍。 As can be seen from Tables 2 and 3, the average number of joint days in Comparative Example 2 was 12 days, the average number of joint days in Comparative Example 1 was 36 days, and the average number of joint days in Example 1 was 108 days. That is, when comparing the number of joining days, the order of Comparative Example 2, Comparative Example 1, and Example 1 becomes longer and longer. The number of joining days in Comparative Example 1 was three times longer than that of Comparative Example 2, and the number of joining days in Example 1 was three times longer than that of Comparative Example 1.
由上述,實施例1中,試驗片1b為Al時,亦即,為含有Al的被接合構件的情形時,相較於比較例1、2,耐腐蝕性、接合可靠性更佳。 From the above, in Example 1, when the test piece 1b is Al, that is, when it is a member to be joined containing Al, the corrosion resistance and joint reliability are better than those of Comparative Examples 1 and 2.
誠如上述,實施例1即使置於鹽水的使用環境中的情況時,可維持優良的耐腐蝕性及高接合可靠性。此種結果係推測作為助劑所添加的Mn之影響。以下,詳細說明。 As described above, Example 1 can maintain excellent corrosion resistance and high joint reliability even when it is placed in a use environment of salt water. This result is presumed to be the effect of Mn added as an auxiliary. The details are described below.
電解腐蝕係標準電極電位的差越大越容易進行。亦即,含有Al的被接合構件的情形,與Al的標準電極電位的差越大,焊料合金在接合部位的電解腐蝕越嚴重,在鹽水中則電解腐蝕的速度更加速。 The larger the difference between the standard electrode potentials of the electrolytic corrosion system, the easier it becomes. That is, in the case of a member to be joined containing Al, the larger the difference between the standard electrode potential of Al and Al, the more severe the electrolytic corrosion of the solder alloy at the joint, and the faster the rate of electrolytic corrosion in salt water.
另一方面,實施例1中添加的Mn的標準電極電位為-1.18V,此外Al的標準電極電位為-1.68。Mn及Al之間標準電極電位的差(以下,稱為Mn的電位差)為0.5V,相對而言較小。實施例1中,推測此類Mn分佈於軟焊接合100的接合界面附近(接合部位)。推測例如在形成於接合部位的Cu-Al系或Cu-Ag系的類金屬化合物中含有Mn。因此,實施例1中,在接合部位,使含有Al的被接合構件與焊料合金的標準電極電位的差降低。推測在接合部位的腐蝕藉此受到抑制。 On the other hand, the standard electrode potential of Mn added in Example 1 was -1.18 V, and the standard electrode potential of Al was -1.68. The difference in standard electrode potential between Mn and Al (hereinafter referred to as the potential difference of Mn) is 0.5 V, which is relatively small. In Example 1, it is estimated that such Mn is distributed near the joint interface (joint portion) of the solder joint 100. It is estimated that, for example, Mn is contained in a Cu-Al-based or Cu-Ag-based metalloid compound formed at a joint. Therefore, in Example 1, the difference in the standard electrode potential between the member to be joined containing Al and the solder alloy was reduced at the joining portion. It is presumed that corrosion at the joints is thereby suppressed.
於上述,雖然以添加有作為抑制電解腐蝕的助劑的Mn的情況為例加以說明,但本發明不限定於此等。只要與Al的標準電極電位的差為Mn的電位差(0.5V)以下的助劑即可。例如,由於Ti及Zr的標準電極電位分別為-1.63V及-1.55,與Al的標準電極電位的差分別為0.05V及0.13V,Mn的電位差比0.5V更小。因此,作為助劑,亦可使用Ti或Zr。 As mentioned above, although the case where Mn was added as an auxiliary agent which suppresses electrolytic corrosion is demonstrated as an example, this invention is not limited to these. It is sufficient if the difference between the standard electrode potential of Al and the potential difference (0.5 V) of Mn or less is sufficient. For example, since the standard electrode potentials of Ti and Zr are -1.63V and -1.55, respectively, and the standard electrode potentials of Al are 0.05V and 0.13V, respectively, the potential difference of Mn is smaller than 0.5V. Therefore, Ti or Zr can also be used as an auxiliary agent.
此外,本發明不限於以上所記載者。作為Mn以外的助劑,亦可使用與Al的標準電極電位的差跟Mn的電位差(0.5V)相同程度者。例如,Mg的情形時,標準電極電位為-2.36,與Al的標準電極電位的差為0.68V,與Mn的電位差0.5V相同程度。因此,作為助劑,亦可使用Mg。 The present invention is not limited to those described above. As the auxiliary agent other than Mn, a difference between the standard electrode potential of Al and the potential difference (0.5 V) of Mn may be used. For example, in the case of Mg, the standard electrode potential is -2.36, the difference between the standard electrode potential and Al is 0.68V, and the potential difference between Mn and 0.5V is about the same. Therefore, Mg can also be used as an adjuvant.
承上述,作為抑制電解腐蝕的助劑,使用與Al的標準電極電位的差為0.7V以下者即可。亦即,作為相關的助劑,Mn、Mg、Ti、Zr當中的任一者皆可。此外不限於此,使用Mn、Mg、Ti、Zr當中的二者以上皆可。 Based on the above, as the auxiliary agent for suppressing electrolytic corrosion, it is sufficient to use a difference between the standard electrode potential of Al and 0.7 V or less. That is, as a related auxiliary agent, any of Mn, Mg, Ti, and Zr may be used. In addition, it is not limited to this, and two or more of Mn, Mg, Ti, and Zr may be used.
於上述,雖然舉本實施形態相關的Sn-Ag-Cu系焊料合金含有0.003重量%的Mn的情形為例進行說明,但本發明不限於此等。Mn為0~0.01重量%的範圍內,本實施形態相關的Sn-Ag-Cu系焊料合金達到上述效果。 As described above, the case where the Sn-Ag-Cu-based solder alloy according to this embodiment contains 0.003% by weight of Mn is described as an example, but the present invention is not limited to these. The Mn is in the range of 0 to 0.01% by weight, and the Sn-Ag-Cu-based solder alloy according to this embodiment achieves the above-mentioned effects.
如上述,由於要確認使用Mn、Mg、Ti、Zr當中任一者作為助劑時,以及作為助劑添加0~0.01重量%Mn時,能否達到抑制電解腐蝕的效果,對於使用Mg、Ti、Zr作為助劑時,以及添加0~0.01重量%Mn作為助劑時,亦進行試驗。 As described above, it is necessary to confirm whether the effect of suppressing electrolytic corrosion can be achieved when using any of Mn, Mg, Ti, and Zr as an auxiliary agent and when 0 to 0.01% by weight of Mn is added as an auxiliary agent. When Zr is used as an adjuvant, and when 0 to 0.01% by weight Mn is added as an adjuvant, tests are also performed.
添加作為助劑Mg、Ti、Zr或0~0.01重量%的Mn, 進行使用試驗試樣的軟焊接合100的試驗。詳言之,將試驗試樣的軟焊接合100浸漬於鹽水中預定時間後,測定相關的軟焊接合100的抗張強度,觀察隨著於鹽水中的浸漬時間接合強度的變化。 Mg, Ti, Zr, or 0 to 0.01% by weight of Mn was added as an auxiliary agent, and a test of solder joint 100 using a test sample was performed. Specifically, after the solder joint 100 of the test sample is immersed in the salt water for a predetermined time, the tensile strength of the solder joint 100 is measured, and the change in the joint strength with the immersion time in the salt water is observed.
表3係表示上述抗張強度的測定中使用的試驗試樣的軟焊接合100(Sn-Ag-Cu系焊料合金)的組成的表。此外,表3所記載的比較例1及比較例2係與上述相同者。再者,表3中追加了用以比較的比較例3~5。 Table 3 is a table | surface which shows the composition of the solder joint 100 (Sn-Ag-Cu-type solder alloy) of the test sample used for the said tensile strength measurement. The comparative examples 1 and 2 described in Table 3 are the same as those described above. In addition, Comparative Examples 3 to 5 are added to Table 3 for comparison.
如表3所示,作為助劑,本實施形態相關的軟焊接合100(表3的實施例2~5)分別包含Mn、Mg、Ti、Zr。另一方面,新的比較例3~5分別包含Zn、Na、Fe作為助劑。 As shown in Table 3, the soft solder joints 100 (Examples 2 to 5 in Table 3) related to the present embodiment each contain Mn, Mg, Ti, and Zr as auxiliary agents. On the other hand, the new comparative examples 3 to 5 each contain Zn, Na, and Fe as auxiliary agents.
本實施形態相關的軟焊接合100當中,實施例2包 含Ag、Cu、Ni分別為3重量%、5重量%、0.05重量%,更包含0.009重量%的Ti,剩餘部分為Sn。實施例3包含Ag、Cu及Ni與實施例2同量,更包含0.008重量%的Zr,剩餘部分為Sn。實施例4包含Ag、Cu及Ni與實施例2同量,更包含0.010重量%的Mn,剩餘部分為Sn。實施例5包含Ag、Cu及Ni與實施例2同量,更包含0.004重量%的Mg,剩餘部分為Sn。實施例2~5中焊接溫度皆為320℃。 Among the solder joints 100 according to this embodiment, Example 2 contains 3% by weight, 5% by weight, 0.05% by weight of Ni, 0.05% by weight of Ti, 0.009% by weight of Ti, and the remaining portion is Sn. Example 3 contains the same amounts of Ag, Cu, and Ni as in Example 2, and further contains 0.008% by weight of Zr, and the remaining portion is Sn. Example 4 contains the same amounts of Ag, Cu, and Ni as in Example 2, and further contains 0.010% by weight of Mn, and the remaining portion is Sn. Example 5 contains Ag, Cu, and Ni in the same amount as in Example 2, and further contains 0.004% by weight of Mg, and the remaining portion is Sn. In Examples 2 to 5, the welding temperature was 320 ° C.
此外,比較例3係Ag、Cu及Ni與實施例2同量,更包含0.012重量%的Zn,剩餘部分為Sn。比較例4係Ag、Cu及Ni與實施例2同量,更包含0.008重量%的Na,剩餘部分為Sn。比較例5係Ag、Cu及Ni與實施例2同量,更包含0.010重量%的Fe,剩餘部分為Sn。 In addition, Comparative Example 3 was the same amount of Ag, Cu, and Ni as in Example 2, and further contained 0.012% by weight of Zn, and the remainder was Sn. Comparative Example 4 is the same amount of Ag, Cu, and Ni as in Example 2, and further contains 0.008% by weight of Na, and the remainder is Sn. Comparative Example 5 is the same amount of Ag, Cu, and Ni as in Example 2, and further contains 0.010% by weight of Fe, and the remainder is Sn.
比較例3~5中焊接溫度皆為320℃。且,關於比較例1~2已於先前說明,故省略說明。 In Comparative Examples 3 to 5, the soldering temperature was 320 ° C. Since Comparative Examples 1 to 2 have been described previously, descriptions thereof are omitted.
表4係表示實施例2~5及比較例2~5中所添加的助劑的標準電極電位(V)以及助劑的標準電極電位(V)與Al的標準電極電位的差(V)。亦即,與Al的標準電極電位的差(V)係從Al的標準電極電位扣除助劑的標準電極電位的值。表4中與Al的標準電極電位的差(V)以絕對值表示。且,比較例2中,作為助劑視為添加有Sn者,記載助劑的標準電極電位(V)及Al的標準電極電位的差(V)。 Table 4 shows the standard electrode potential (V) of the additives added in Examples 2 to 5 and Comparative Examples 2 to 5 and the difference (V) between the standard electrode potential (V) of the additives and the standard electrode potential of Al. That is, the difference (V) from the standard electrode potential of Al is a value obtained by subtracting the standard electrode potential of the additive from the standard electrode potential of Al. The difference (V) from the standard electrode potential of Al in Table 4 is expressed as an absolute value. In addition, in Comparative Example 2, it is considered that Sn is added as an auxiliary, and the difference (V) between the standard electrode potential (V) of the auxiliary and the standard electrode potential of Al is described.
[表4]
作為助劑,分別添加Mn、Mg、Ti、Zr、Zn、Na、Fe時(實施例2~5、比較例3~4),此等各成分(元素)的添加量,固定為使各元素放出的電子量成為等量的方式。此等係由於電解腐蝕係因異種金屬元素(助劑)間的電子授受所引起的反應現象,關於腐蝕抑制效果,為了比較評估各元素的添加效果,因此判斷必須校準與反應的授受相關的電子量。 When Mn, Mg, Ti, Zr, Zn, Na, and Fe are added as additives (Examples 2 to 5, Comparative Examples 3 to 4), the amounts of these components (elements) are fixed so that each element The amount of emitted electrons becomes equal. These are due to the phenomenon of electrolytic corrosion caused by the electron transfer between different metal elements (auxiliaries). Regarding the corrosion inhibition effect, in order to compare and evaluate the addition effect of each element, it is necessary to calibrate the electrons related to the transfer of the reaction the amount.
具體而言,以Mn的添加量為0.010重量%的情形作為基準,使各元素於離子化時的放出電子量成為等量的方式,從各元素的離子化價數及原子量,基於以下的算式算出。表5表示各元素的離子化價數、原子量及經計算的添加量(表5中,計算添加量)。 Specifically, based on the case where the amount of Mn added is 0.010% by weight, the amount of electrons emitted by each element at the time of ionization is made equal, and the ionization valence and atomic weight of each element are based on the following formula Figure it out. Table 5 shows the ionization valence, atomic weight, and calculated addition amount of each element (in Table 5, the addition amount is calculated).
添加量=Mn的添加量×(Mn的價數/元素的價數)×(元素的原子量/Mn的原子量)。 Addition amount = addition amount of Mn × (valence of Mn / valence of element) × (atomic weight of element / atomic weight of Mn).
使用表3所記載的實施例2~5及比較例1~5的焊料合金,作成軟焊接合的試驗試樣。試驗試樣與第2圖所示者相同形狀。此外,關於第2圖所示的試驗試樣的製作已於先前說明,故省略詳細說明。 The solder alloys of Examples 2 to 5 and Comparative Examples 1 to 5 described in Table 3 were used to prepare test samples for soldering. The test sample has the same shape as that shown in FIG. 2. In addition, the production of the test sample shown in FIG. 2 has already been described previously, so detailed description is omitted.
在對於據此所作成的實施例2~5及比較例1~5的試驗試樣進行抗張強度的測定之前,將此等試驗試樣浸漬於鹽水中預定時間。詳言之,將實施例2~5及比較例1~5相關的試驗試樣完全地浸漬於鹽水(3%的NaCl水溶液)中,放置於室溫。此時,試驗試樣以彼此不接觸的方式靜置。在浸漬開始起的經過時間為72小時,168小時,336小時的時候將試驗試樣取出,測定抗張強度。鹽水每一週進行更換。 Before the test specimens of Examples 2 to 5 and Comparative Examples 1 to 5 thus prepared were measured for tensile strength, these test specimens were immersed in saline for a predetermined time. Specifically, the test samples related to Examples 2 to 5 and Comparative Examples 1 to 5 were completely immersed in brine (3% aqueous NaCl solution) and left at room temperature. At this time, the test specimens were left to stand without contacting each other. When the elapsed time from the start of immersion was 72 hours, 168 hours, and 336 hours, the test sample was taken out and the tensile strength was measured. The saline is changed every week.
抗張強度的測定使用島津製作所製測試機AG-IS10kN進行。詳言之,浸漬於鹽水之後的實施例2~5及比較例1~5的試驗試樣,以室溫(20℃~25℃)、10mm/分的條件,拉伸各試驗試樣至斷裂為止,測定試驗試樣的抗張強度。抗張 強度的測定對於各試驗試樣各進行5次。 The tensile strength was measured using a tester AG-IS10kN manufactured by Shimadzu Corporation. Specifically, the test samples of Examples 2 to 5 and Comparative Examples 1 to 5 after being immersed in salt water were stretched to break at a temperature of 10 mm / min at room temperature (20 ° C to 25 ° C). Until then, the tensile strength of the test specimen was measured. The measurement of tensile strength was performed 5 times for each test sample.
抗張強度(最大應力)的測定結果如表6所示。表6中,「0小時」意指鹽水的浸漬處理前。此外,表6中「0」的值表示在試驗試樣的軟焊接合中,焊料合金(焊料合金箔2)與試驗片1a、1b之間發生剝離。此外,第4圖表示表6的最大應力的測定結果的條形圖。第4圖中,縱軸表示最大應力值,橫軸表示實施例2~5及比較例1~5。 Table 6 shows the measurement results of the tensile strength (maximum stress). In Table 6, "0 hours" means before the salt water immersion treatment. In addition, the value of "0" in Table 6 indicates that peeling occurred between the solder alloy (solder alloy foil 2) and the test pieces 1a and 1b during the soft soldering of the test sample. FIG. 4 is a bar graph showing the measurement results of the maximum stress in Table 6. In FIG. 4, the vertical axis represents the maximum stress value, and the horizontal axis represents Examples 2 to 5 and Comparative Examples 1 to 5.
表7係以上述浸漬處理前(0小時)作為基準,表示實施例2~5及比較例1~5的試驗試樣的最大應力的測定結果者。亦即,表7中,在實施例2~5及比較例1~5各自於預定時間的浸漬處理後的最大應力以相對於在0小時的最大應力的比例(百分率)表示。此外,第5圖係表示表7的最大應力的比例的條形圖。 第5圖中,縱軸表示相對於浸漬處理前應力值的比例,橫軸表示實施例2~5及比較例1~5。 Table 7 shows the measurement results of the maximum stress of the test samples of Examples 2 to 5 and Comparative Examples 1 to 5 based on the pre-dip treatment (0 hours) as a reference. That is, in Table 7, the maximum stress after the immersion treatment in each of Examples 2 to 5 and Comparative Examples 1 to 5 at a predetermined time is expressed as a ratio (percentage) to the maximum stress at 0 hours. FIG. 5 is a bar graph showing the ratio of the maximum stress in Table 7. In Fig. 5, the vertical axis represents the ratio to the stress value before the immersion treatment, and the horizontal axis represents Examples 2 to 5 and Comparative Examples 1 to 5.
從第4圖~第5圖及表6~表7可知,實施例2~5及比較例1~5的試驗試樣的任一者,浸漬處理的時間隨著72小時、168小時、336小時越長,最大應力越降低。亦即,判斷隨著浸漬處理的時間越長腐蝕變嚴重,最大應力降低。 As can be seen from Fig. 4 to Fig. 5 and Tables 6 to 7, the immersion treatment time of any of the test samples of Examples 2 to 5 and Comparative Examples 1 to 5 increased with 72 hours, 168 hours, and 336 hours. The longer the maximum stress decreases. That is, it is judged that as the time of the dipping treatment becomes longer, the corrosion becomes more serious, and the maximum stress decreases.
但是,於72小時、168小時及336小時的浸漬處理後,實施例2~5相關的試驗試樣的軟焊接合100的最大應力顯示高於比較例1~5相關的試驗試樣的最大應力的值。 However, after the immersion treatment at 72 hours, 168 hours, and 336 hours, the maximum stress of the solder joint 100 of the test samples related to Examples 2 to 5 was higher than the maximum stress of the test samples related to Comparative Examples 1 to 5. Value.
實施例2~5中,可知72小時的浸漬處理後的最大應力皆為299N以上,168小時的浸漬處理後的最大應力皆為158N以上,336小時的浸漬處理後的最大應力皆為54N以上。 In Examples 2 to 5, the maximum stress after the 72-hour immersion treatment was 299 N or more, the maximum stress after the 168-hour immersion treatment was 158 N or more, and the maximum stress after the 336-hour immersion treatment was 54 N or more.
如此一來,已知於浸漬處理後,由於實施例2~5相關的試驗試樣的軟焊接合100的最大應力高於比較例1~5相關的試驗試樣的最大應力,實施例2~5相關的試驗試樣的軟焊接合100相較於比較例1~5相關的試驗試樣,耐腐蝕性佳。 In this way, it is known that after the dipping treatment, the maximum stress of the solder joint 100 of the test specimens related to Examples 2 to 5 is higher than the maximum stress of the test specimens related to Comparative Examples 1 to 5. Compared with the test samples related to Comparative Examples 1 to 5, the solder joint 100 of the test sample related to 5 has better corrosion resistance.
第6圖係比較例1的最大應力與實施例2~5及比較例2~5的試驗試樣的最大應力的差,相對於與Al的標準電極電位的差(V)作圖而成的圖表。第6圖中,縱軸表示與比較例1的最大應力差,橫軸表示與Al的標準電極電位的差(V)。 FIG. 6 is a graph in which the difference between the maximum stress of Comparative Example 1 and the maximum stress of the test samples of Examples 2 to 5 and Comparative Examples 2 to 5 is plotted against the standard electrode potential difference (V) from Al. chart. In FIG. 6, the vertical axis represents the maximum stress difference from Comparative Example 1, and the horizontal axis represents the difference (V) from the standard electrode potential of Al.
由第6圖可知,以與Al的標準電極電位的差(V)為0.70時為界區分最大應力。與Al的標準電極電位的差(V)比0.70更低者,與比較例1的最大應力差大於0,與Al的標準電極電位的差(V)比0.70更大者,與比較例1的最大應力差小於0。與Al的標準電極電位的差(V)比0.70更低者相當於實施例2~5相關的試驗試樣的軟焊接合100,與Al的標準電極電位的差(V)比0.70更大者相當於比較例2~5。 As can be seen from Fig. 6, the maximum stress is distinguished when the difference (V) from the standard electrode potential of Al is 0.70. The standard electrode potential difference (V) from Al is lower than 0.70, the maximum stress difference from Comparative Example 1 is greater than 0, and the standard electrode potential difference (V) from Al is larger than 0.70, compared to The maximum stress difference is less than 0. The standard electrode potential difference (V) lower than 0.70 corresponds to the solder joint 100 of the test samples related to Examples 2 to 5, and the standard electrode potential difference (V) to Al is larger than 0.70. This corresponds to Comparative Examples 2 to 5.
亦即,於實施例2~5相關的試驗試樣的軟焊接合100中,浸漬處理後的最大應力(抗張強度)較比較例1更高,於比較例2~5相關的試驗試樣中,浸漬處理後的最大應力(抗張強度)較比較例1更低。換言之,實施例2~5相關的試驗試樣的軟焊接合100的任一者於浸漬處理後顯示較比較例1~5更高的最大應力(抗張強度)。 That is, in the soft-welded joint 100 of the test samples related to Examples 2 to 5, the maximum stress (tensile strength) after the dipping treatment was higher than that of Comparative Example 1, and the test samples related to Comparative Examples 2 to 5 However, the maximum stress (tensile strength) after the immersion treatment was lower than that of Comparative Example 1. In other words, any one of the solder joints 100 of the test samples related to Examples 2 to 5 showed a higher maximum stress (tensile strength) than that of Comparative Examples 1 to 5 after the dipping treatment.
由以上可確認由於使用與Al的標準電極電位的差為0.7V以下的Mn、Mg、Ti、Zr作為助劑,於軟焊接合100(焊料合金)中可抑制電解腐蝕。 From the above, it was confirmed that the use of Mn, Mg, Ti, and Zr having a difference between the standard electrode potential of Al and 0.7 V or less as an auxiliary suppresses electrolytic corrosion in the solder joint 100 (solder alloy).
詳言之,藉由使用含有超過0至0.010重量%的Mn作為助劑的無鉛焊料合金,於本實施例的軟焊接合100中達到抑制電解腐蝕的效果。 In detail, by using a lead-free solder alloy containing more than 0 to 0.010% by weight of Mn as an auxiliary agent, the effect of suppressing electrolytic corrosion is achieved in the solder joint 100 of this embodiment.
且,Mn為具有容易被氧化的性質的元素,於焊料(合金)表面形成氧化物即所謂的銹渣時,成為使焊接性或作業性低下的原因。此外,於Sn添加有Mn時,亦有所謂的焊料合金的熔點上昇的問題。像這種Mn的添加,亦有使焊料合金本身的性能或焊接作業性低下的觀點,不希望添加超過0.010重量%的Mn。 In addition, Mn is an element having a property of being easily oxidized, and when an oxide, that is, a so-called slag, is formed on the surface of a solder (alloy), it causes a decrease in solderability or workability. In addition, when Mn is added to Sn, there is also a problem that the melting point of a so-called solder alloy rises. Such addition of Mn also has the viewpoint of lowering the performance of the solder alloy itself or soldering workability, and it is not desirable to add more than 0.010% by weight of Mn.
此外,如上述,藉由使用含有超過0至0.009重量%的Ti作為助劑的無鉛焊料合金,本實施例的軟焊接合100亦達到抑制電解腐蝕的效果。 In addition, as described above, by using a lead-free solder alloy containing more than 0 to 0.009% by weight of Ti as an auxiliary agent, the solder joint 100 of this embodiment also achieves the effect of suppressing electrolytic corrosion.
再者,藉由使用含有超過0至0.004重量%的Mg作為助劑的無鉛焊料合金,本實施例的軟焊接合100亦達到抑制電解腐蝕的效果。然後,藉由使用含有超過0至0.008重量%的Zr作為助劑的無鉛焊料合金,本實施例的軟焊接合100亦達到抑制電解腐蝕的效果。 Furthermore, by using a lead-free solder alloy containing more than 0 to 0.004% by weight of Mg as an auxiliary agent, the solder joint 100 of this embodiment also achieves the effect of suppressing electrolytic corrosion. Then, by using a lead-free solder alloy containing more than 0 to 0.008% by weight of Zr as an auxiliary agent, the solder joint 100 of this embodiment also achieves the effect of suppressing electrolytic corrosion.
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TWI820277B (en) * | 2018-12-27 | 2023-11-01 | 美商阿爾發金屬化工公司 | Lead-free solder compositions |
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