TWI507550B - Copper - zinc - tin - based copper alloy - Google Patents
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Description
本發明係關於一種適用於電池連接引板材料等要求反覆彎曲性之用途的銅合金條。The present invention relates to a copper alloy strip suitable for use in applications such as battery connecting tab materials that require reversible bending.
於視訊攝影機等攜帶用電子機器中使用有鎳鎘電池或鋰電池等充電式電池。又，受到近年來降低環境負荷趨勢之影響，電動汽車或油電混合車之需求亦增加，車載用鋰離子二次電池之開發亦不斷推進。為了確保必需之電容，該等充電式電池係將複數個單體構造之電池以複數個相互接近之狀態電連接來使用。用於連接電池之金屬零件被稱為集電引板或引板，多數情況下，為了實現確實之連接，藉由利用由電阻引起之發熱的電阻焊接來與電池之電極熔接(專利文獻1)。A rechargeable battery such as a nickel-cadmium battery or a lithium battery is used in a portable electronic device such as a video camera. In addition, the demand for electric vehicles or hybrid vehicles has also increased due to the trend of reducing environmental load in recent years, and the development of lithium-ion secondary batteries for vehicles has been continuously promoted. In order to ensure the necessary capacitance, the rechargeable battery is used by electrically connecting a plurality of cells of a single structure in a state in which a plurality of cells are in close proximity to each other. A metal part for connecting a battery is called a current collecting tab or a lead plate. In many cases, in order to achieve a reliable connection, the electrode of the battery is welded by resistance welding using heat generated by a resistor (Patent Document 1). .
為了將電極焊接有引板之複數個電池緊密地收納於盒體內，而對引板實施嚴格之彎曲加工。因此，對使用於引板之材料要求與電極之良好的焊接性及反覆彎曲性。In order to closely store a plurality of batteries in which the electrodes are welded with the lead plates, the lead plates are subjected to strict bending processing. Therefore, the material used for the tab is required to have good weldability and reversibility of the electrode.
於使用串聯型電阻焊接機連接構成電極之不鏽鋼板或軟鋼板與引板時，若引板之導電率過高，則會有過大之電流流至引板而導致熔損。因此，於以往之引板一直使用鎳或導電率相對較低之銅合金等。When a stainless steel plate or a mild steel plate and a lead plate constituting an electrode are connected by a series resistance welding machine, if the conductivity of the lead plate is too high, an excessive current flows to the lead plate to cause melt loss. Therefore, nickel or a copper alloy having a relatively low conductivity has been used in the conventional lead plates.
[專利文獻1]日本特許公開2004-134197[Patent Document 1] Japanese Patent Publication No. 2004-134197
然而，受到近年來鎳價格上漲之影響，出現了為了降低成本而將引板材料由鎳變為銅合金的趨勢。作為適合用作引板材料之銅合金，可舉銅-鎳-錫系合金，但銅-鎳-錫系合金之焊接性及反覆彎曲性並不充分，而期待該等特性之改善。However, due to the recent increase in nickel prices, there has been a tendency to change the lead material from nickel to copper alloy in order to reduce costs. A copper-nickel-tin alloy which is suitable as a material for a tab material is used, but the weldability and the reversibility bendability of the copper-nickel-tin alloy are not sufficient, and improvement of these characteristics is expected.
因此，本發明之目的在於提供一種具有良好反覆彎曲性與耐疲勞特性的銅-鋅-錫系銅合金條。Accordingly, it is an object of the present invention to provide a copper-zinc-tin-based copper alloy strip having good reversibility of bending and fatigue resistance.
本案發明人發現，藉由減少{220}面之比例，進而增加{200}面及{311}面之比例，可兼具良好之反覆彎曲性與強度。The inventor of the present invention found that by reducing the ratio of {220} faces and increasing the ratio of {200} faces and {311} faces, both of them have good reversibility of bending and strength.
本發明之銅-鋅-錫系銅合金條含有2.0~12.0質量%之鋅、0.1~1.0質量%之錫，剩餘部分由銅及不可避免之雜質構成，於將來自表面之{200}面的X射線繞射強度設為I{200}，來自{311}面的X射線繞射強度設為I{311}，來自{220}面的X射線繞射強度設為I{220}，且將純銅粉末標準試樣之來自(200)、(220)、(311)面之X射線繞射強度分別設為I0 {200}、I0 {220}、I0 {311}時，滿足2.5≦[I{220}/I0 {220}]≦3.5、2.2≦[I{200}/I0 {200}+I{311}/I0 {311}]且1.5≦I{311}/I{200}。The copper-zinc-tin-based copper alloy strip of the present invention contains 2.0 to 12.0% by mass of zinc and 0.1 to 1.0% by mass of tin, and the balance is composed of copper and unavoidable impurities, which will be from the {200} plane of the surface. The X-ray diffraction intensity is set to I{200}, the X-ray diffraction intensity from the {311} plane is set to I{311}, and the X-ray diffraction intensity from the {220} plane is set to I{220}, and When the X-ray diffraction intensities from the (200), (220), and (311) planes of the pure copper powder standard sample are set to I 0 {200}, I 0 {220}, and I 0 {311}, respectively, 2.5 ≦ is satisfied. [I{220}/I 0 {220}]≦3.5, 2.2≦[I{200}/I 0 {200}+I{311}/I 0 {311}] and 1.5≦I{311}/I{ 200}.
並且較佳為含有合計為0.005~0.8質量%之選自Ni、Mg、Fe、P、Mn及Cr之群中之一種以上。Further, it is preferably one or more selected from the group consisting of Ni, Mg, Fe, P, Mn, and Cr in a total amount of 0.005 to 0.8% by mass.
較佳為藉由切割法求出之結晶粒徑為15μm以下。The crystal grain size determined by the dicing method is preferably 15 μm or less.
較佳於表面具有回焊鍍錫層。Preferably, the surface has a reflow tin plating layer.
根據本發明，可獲得具有良好之反覆彎曲性與耐疲勞特性的銅-鋅-錫系銅合金條。According to the present invention, a copper-zinc-tin-based copper alloy strip having excellent reversibility of bending and fatigue resistance can be obtained.
10‧‧‧引板片10‧‧‧ lead plate
20‧‧‧單體電池20‧‧‧ single battery
20a‧‧‧電極20a‧‧‧electrode
30‧‧‧電路基板30‧‧‧ circuit board
32‧‧‧焊錫32‧‧‧Solder
40‧‧‧連接器40‧‧‧Connector
50‧‧‧盒體50‧‧‧ box
X‧‧‧方向X‧‧‧ direction
Y‧‧‧方向Y‧‧‧ direction
圖1係表示將使用有本發明之合金條之引板片與單體電池電極電阻焊接後之狀態之圖。Fig. 1 is a view showing a state in which a tab piece using the alloy strip of the present invention is resistance-welded to a single cell electrode.
圖2係表示耐聯合國試驗(疲勞試驗)之方法之圖。Figure 2 is a diagram showing the method of resistance to the United Nations test (fatigue test).
以下，對本發明之實施形態之銅-鋅-錫系銅合金條進行說明。再者，於本發明中，所謂%，只要未特別說明，則表示質量%。Hereinafter, a copper-zinc-tin-based copper alloy strip according to an embodiment of the present invention will be described. In the present invention, the term "%" means mass% unless otherwise specified.
如圖1所示，本發明之銅合金條被切割成例如短條狀之引板片10，藉由電阻焊接而與單體電池20之電極20a連接(熔接)。於圖1中，各單體電池20之極性不同之電極彼此藉由引板片10電連接，且係串聯地連接。As shown in Fig. 1, the copper alloy strip of the present invention is cut into, for example, a strip-shaped tab piece 10, which is joined (fused) to the electrode 20a of the unit cell 20 by resistance welding. In FIG. 1, the electrodes of the respective cells 20 having different polarities are electrically connected to each other by the tab piece 10, and are connected in series.
首先，對銅合金條之組成之限定理由進行說明。First, the reason for limiting the composition of the copper alloy strip will be described.
將Zn含量設為2.0~12.0質量%，較佳為設為2.0~9.0質量%。若Zn未達2.0%，則作為引板所需之強度會變得不充分，並且導電率變得過高而於焊接時引板發生熔損，或者電流變得不易流至電極側之不鏽鋼板或軟鋼板，故而使焊接性劣化。若Zn超過12.0%，則於焊接時Zn會氣化而使材料脆化，從而使焊接性劣化，不僅如此，亦會使導電率降低，而不易達成電池之高性能化。The Zn content is 2.0 to 12.0% by mass, preferably 2.0 to 9.0% by mass. If the Zn is less than 2.0%, the strength required as a guide plate may become insufficient, and the electrical conductivity may become too high, and the lead plate may be melted during welding, or the electric current may not easily flow to the stainless steel plate on the electrode side. Or a soft steel plate, which deteriorates weldability. When Zn exceeds 12.0%, Zn vaporizes during welding to embrittle the material, thereby deteriorating the weldability, and also lowers the electrical conductivity, which makes it difficult to achieve high performance of the battery.
將Sn含量設為0.1~1.0質量%，較佳設為0.1~0.5質量%。若Sn未達 0.1%，則無法獲得充分之強度。若Sn超過1.0%，則導電率會下降。The Sn content is set to 0.1 to 1.0% by mass, preferably 0.1 to 0.5% by mass. If Sn is not up to At 0.1%, sufficient strength cannot be obtained. If Sn exceeds 1.0%, the electrical conductivity will decrease.
為了改善合金之強度、耐熱性、耐應力緩和性等，上述合金條中可進而含有合計為0.005~0.8質量%之選自Ni、Mg、Fe、P、Mn及Cr之群中之一種以上。若該等元素之總量未達0.005%，則無法獲得所欲之特性，若總量超過0.8%，則雖然可獲得所欲之特性，但導電性或彎曲加工性會下降。In order to improve the strength, the heat resistance, the stress relaxation resistance, and the like of the alloy, the alloy strip may further contain one or more selected from the group consisting of Ni, Mg, Fe, P, Mn, and Cr in a total amount of 0.005 to 0.8% by mass. If the total amount of these elements is less than 0.005%, the desired characteristics cannot be obtained. If the total amount exceeds 0.8%, the desired properties can be obtained, but the electrical conductivity or bending workability is lowered.
其次，對銅合金條之織構之規定進行說明。本發明人等對在各種條件下製造銅-鋅-錫系銅合金條時之各結晶面的積體度與反覆彎曲性之關係進行了調查、分析，結果獲得了以下見解。Next, the specification of the texture of the copper alloy strip will be described. The inventors of the present invention investigated and analyzed the relationship between the degree of integration of the crystal faces of the copper-zinc-tin-based copper alloy strips under various conditions and the reversibility of the bending property, and as a result, obtained the following findings.
首先，銅-鋅-錫系銅合金條通常係於熱軋及面削後，反覆進行多次(通常為2次左右)冷軋與退火，最後進行精軋來製造，但反覆彎曲性於最後之退火完成時最良好，隨著精冷軋之加工度之增加，反覆彎曲性會下降。另一方面，銅合金條之強度隨著精冷軋之加工度之增加而提高。First, the copper-zinc-tin-based copper alloy strip is usually subjected to hot rolling and surface-cutting, and is repeatedly subjected to cold rolling and annealing a plurality of times (usually about 2 times), and finally finished by finish rolling, but the bending property is repeated at the end. The annealing is the best at completion, and as the degree of processing of the finish cold rolling increases, the over-bending property is lowered. On the other hand, the strength of the copper alloy strip increases as the degree of processing of the finish cold rolling increases.
因此，為了兼具良好之反覆彎曲性與強度，必需使精冷軋之加工度不過高。而且，由於隨著精軋加工度之增加，I(220)會增加，且I(200)與I(311)會減少，故而如下所述般，減少{220}面之比例，並且增加{200}面及{311}面之比例。將精軋之加工度設為15~50%即可。Therefore, in order to have good reversibility of bending and strength, it is necessary to make the degree of processing of the finish cold rolling not too high. Moreover, as the degree of finish rolling increases, I(220) increases, and I(200) and I(311) decrease, so as follows, the ratio of {220} faces is reduced, and {200 is increased. The ratio of the face and the {311} face. The finishing degree of the finish rolling can be set to 15 to 50%.
又，若提高退火時之升溫速度，則與{200}面相比，作為整粒之{311}面會更多地成長，而使合金條內之應變變少，藉此提高反覆彎曲性及耐疲勞特性。Further, when the temperature increase rate at the time of annealing is increased, the {311} surface as the whole grain grows more than the {200} surface, and the strain in the alloy strip is reduced, thereby improving the reversibility and resistance. Fatigue properties.
再者，關於銅-鋅-錫系銅合金條之強度(拉伸強度)，又，若如上所述般控制織構，且於下述耐聯合國試驗中合格，則只要為320MPa以上之拉伸強度，便不存在問題。尤其是，若為400MPa以上則較佳。In addition, as for the strength (tensile strength) of the copper-zinc-tin-based copper alloy strip, if the texture is controlled as described above and it is qualified in the following UN resistance test, it is stretched at 320 MPa or more. Strength, there is no problem. In particular, it is preferably 400 MPa or more.
亦即，以如下方式控制織構：於將來自表面之{200}面的X射線繞射強度設為I{200}，來自{311}面的X射線繞射強度設為I{311}，來自{220}面的X射線繞射強度設為I{220}，且將純銅粉末標準試樣之來自(200)、(220)、(311)面之X射線繞射強度分別設為I0 {200}、I0 {220}、I0 {311}時，本發明之銅-鋅-錫系銅合金條滿足2.5≦[I{220}/I0 {220}]≦3.5、2.2≦[I{200}/I0 {200}+I{311}/I0 {311}]，且1.5≦I{311}/I{200}。That is, the texture is controlled in such a manner that the X-ray diffraction intensity from the {200} plane of the surface is set to I{200}, and the X-ray diffraction intensity from the {311} plane is set to I{311}, The X-ray diffraction intensity from the {220} plane is set to I{220}, and the X-ray diffraction intensities from the (200), (220), and (311) planes of the pure copper powder standard sample are set to I 0 respectively. When {200}, I 0 {220}, I 0 {311}, the copper-zinc-tin-based copper alloy strip of the present invention satisfies 2.5 ≦ [I{220}/I 0 {220}] ≦ 3.5, 2.2 ≦ [ I{200}/I 0 {200}+I{311}/I 0 {311}], and 1.5≦I{311}/I{200}.
於[I{220}/I0 {220}]未達2.5之情形時，精冷軋之加工度不充分，而使銅合金條之強度下降。於[I{220}/I0 {220}]超過3.5之情形時，精冷軋之加工度變得過高，而使反覆彎曲性下降。In [I {220} / I 0 {220}] When the case of less than 2.5, the working ratio of finish cold-rolling is not sufficient, so that the copper alloy strip strength. When [I{220}/I 0 {220}] exceeds 3.5, the degree of finishing of the finish cold rolling becomes too high, and the creep resistance is lowered.
於[I{200}/I0 {200}+I{311}/I0 {311}]未達2.2之情形時，精冷軋之加工度變得過高，而使反覆彎曲性下降。再者，[I{200}/I0 {200}+I{311}/I0 {311}]之上限例如於製造上，4.0左右為上限。When [I{200}/I 0 {200}+I{311}/I 0 {311}] is not in the case of 2.2, the degree of processing of the finish cold rolling becomes too high, and the repeated bending property is lowered. Furthermore, the upper limit of [I{200}/I 0 {200}+I{311}/I 0 {311}] is, for example, manufactured, and the upper limit is about 4.0.
又，如上所述，為了製造銅-鋅-錫系銅合金條，而於熱軋及面削後，反覆進行多次冷軋與退火，但若提高退火時之升溫速度，則與{200}面相比，作為整粒之{311}面會更多地成長，而使合金條內之應變變少，從而進一步提高反覆彎曲性及耐疲勞特性。而且，若1.5≦I{311}/I{200}，則織構中之{311}面之比例變得足夠多，故而較佳。再者，為了使1.5≦I{311}/I{200}，將退火時之升溫速度設為例如20℃/sec以上即可。再者，以往退火時之升溫速度通常為5~15℃/sec。Further, as described above, in order to produce a copper-zinc-tin-based copper alloy strip, after hot rolling and surface shaving, multiple cold rolling and annealing are repeated, but if the temperature rise rate during annealing is increased, {200} Compared with the surface, the {311} surface as the whole grain grows more, and the strain in the alloy strip is less, thereby further improving the reversibility of bending and fatigue resistance. Further, if 1.5 ≦ I {311} / I {200}, the ratio of the {311} plane in the texture becomes sufficient, which is preferable. In addition, in order to make 1.5≦I{311}/I{200}, the temperature increase rate at the time of annealing may be 20 ° C / sec or more. Further, the rate of temperature rise in the conventional annealing is usually 5 to 15 ° C / sec.
本發明之銅-鋅-錫系銅合金條之厚度並無特別限制，若為0.4mm以下，則在用於電池引板用途等之情形時可實現輕量化，並且進一步提高反覆彎曲性，故而較佳。The thickness of the copper-zinc-tin-based copper alloy strip of the present invention is not particularly limited, and when it is 0.4 mm or less, weight reduction can be achieved in the case of use for a battery tab or the like, and the overturning flexibility is further improved. Preferably.
又，亦可於本發明之銅-鋅-錫系銅合金條之單面或兩面設置厚度5 μm以下之回焊鍍錫層。回焊鍍錫層可藉由下述回焊處理而形成，即，於銅-鋅-錫系銅合金條之表面實施公知之電鍍錫，或者於0.1~1.0μm之基底鍍銅上實施上述電鍍錫後，保持為錫之熔融溫度以上。即便進行厚度5μm以下之回焊處理，上述銅合金條之織構之積體度(I{220}等)及反覆彎曲性亦不會變化。Further, a thickness of 5 may be provided on one or both sides of the copper-zinc-tin-based copper alloy strip of the present invention. Reflow soldering tin layer below μm. The reflow tin plating layer can be formed by the following reflow treatment, that is, performing known electroplating tin on the surface of the copper-zinc-tin-based copper alloy strip, or performing the above electroplating on the base copper plating of 0.1 to 1.0 μm. After tin, it remains above the melting temperature of tin. Even if the reflow process is performed with a thickness of 5 μm or less, the texture (I{220}, etc.) and the reversibility of the texture of the copper alloy strip are not changed.
本發明之銅-鋅-錫系銅合金條通常可於熱軋及面削後，反覆進行多次(通常為2次左右)冷軋與退火，最後進行精軋來製造。反覆彎曲性於最後之退火完成時最良好，隨著精冷軋之加工度之增加，反覆彎曲性會下降。The copper-zinc-tin-based copper alloy strip of the present invention can be produced by repeatedly performing cold rolling and annealing a plurality of times (usually about twice), followed by finish rolling, after hot rolling and surface grinding. The reversal bending property is the best at the completion of the final annealing, and as the degree of processing of the finish cold rolling increases, the reversibility of the bending property is lowered.
進而，如上所述，為了使1.5≦I{311}/I{200}，將退火時之升溫速度設為20℃/sec以上即可。退火時之升溫速度之上限並無特別指定，例如為35℃/sec左右。Further, as described above, in order to make 1.5 ≦I{311}/I{200}, the temperature increase rate at the time of annealing may be 20 ° C/sec or more. The upper limit of the temperature increase rate during annealing is not particularly specified, and is, for example, about 35 ° C / sec.
再者，較佳將熱軋結束時之溫度設為例如600~750℃。Further, it is preferred to set the temperature at the end of hot rolling to, for example, 600 to 750 °C.
又，較佳將於熱軋後進行之上述退火時之材料之最高到達溫度設為900℃以下。若退火時之材料之最高到達溫度超過900℃，則存在如下情形：藉由切割法求出之結晶粒徑超過15μm，I{311}/I{200}未達1.5，而使反覆彎曲性劣化。Further, it is preferable that the maximum temperature of the material at the time of the annealing performed after the hot rolling is 900 ° C or lower. If the maximum temperature of the material at the time of annealing exceeds 900 ° C, there is a case where the crystal grain size determined by the dicing method exceeds 15 μm, and I{311}/I{200} does not reach 1.5, and the repeated bending property is deteriorated. .
以如下方式製作各實施例及比較例之試樣。Samples of the respective examples and comparative examples were prepared in the following manner.
以電解銅為原料，使用大氣熔解爐熔製表1所示之組成之銅合金，而鑄造成鑄錠。於600~750℃對該鑄錠進行熱軋直至板厚為10mm後，進行面削，再反覆進行複數次冷軋與退火，最後進行精軋，實施例16係將精軋後之板厚設為0.4mm，除此以外係將精軋後之板厚設為0.15mm而製得試樣。又，退火時之爐溫係設為650~1000℃，退火時間係設為15~110 sec。於減緩退火時之升溫速度之情形時降低爐溫，延長退火時間。相反地，於加快退火時之升溫速度之情形時，使爐溫升高，縮短退火時間。又，於將試樣投入爐內時，使K熱電偶與試樣接觸，測定退火時之材料之最高到達溫度。The electrolytic copper was used as a raw material, and the copper alloy having the composition shown in Table 1 was melted using an atmospheric melting furnace, and cast into an ingot. The ingot is hot rolled at 600 to 750 ° C until the thickness is 10 mm, then face-cut, and then repeated cold rolling and annealing, and finally finish rolling, and Example 16 is to set the thickness of the plate after finish rolling. The sample was prepared by setting the thickness of the rolled sheet to 0.15 mm in addition to 0.4 mm. Moreover, the furnace temperature during annealing is set to 650 to 1000 ° C, and the annealing time is set to 15 to 110. Sec. When the temperature increase rate during annealing is slowed down, the furnace temperature is lowered and the annealing time is prolonged. Conversely, when the temperature increase rate at the time of annealing is accelerated, the furnace temperature is raised to shorten the annealing time. Further, when the sample was placed in the furnace, the K thermocouple was brought into contact with the sample, and the maximum temperature of the material at the time of annealing was measured.
將冷軋之總加工度設為98%，將精軋之加工度、退火時之升溫速度設為如表1所示般。The total degree of cold rolling was set to 98%, and the degree of finishing rolling and the rate of temperature increase during annealing were as shown in Table 1.
進而，對於實施例17，利用以下方法對所獲得之試樣之兩面依序實施前處理、基底鍍銅(厚度0.5μm)、及鍍錫(厚度1.5μm)，繼而對鍍錫層實施回焊處理。Further, in Example 17, the pretreatment of the both sides of the obtained sample, the base copper plating (thickness 0.5 μm), and the tin plating (thickness 1.5 μm) were sequentially performed by the following method, and then the tin plating layer was reflowed. deal with.
前處理：藉由10質量%硫酸-1質量%過氧化氫溶液對試樣進行酸洗，而去除表面氧化膜。於鹼性水溶液中將試樣作為陰極進行電解脫脂(電流密度：7.5A/dm2 ，脫脂劑：氫氧化鈉10g/L、碳酸鈉30g/L、偏矽酸鈉7g/L，剩餘部分為水，溫度：80℃，時間60秒)。其次，使用10質量%之硫酸水溶液進行酸洗。Pretreatment: The sample was pickled by a 10% by mass sulfuric acid-1 mass% hydrogen peroxide solution to remove the surface oxide film. The sample was used as a cathode in an alkaline aqueous solution for electrolytic degreasing (current density: 7.5 A/dm 2 , degreaser: sodium hydroxide 10 g/L, sodium carbonate 30 g/L, sodium metasilicate 5 g/L, and the remainder was Water, temperature: 80 ° C, time 60 seconds). Next, pickling was carried out using a 10% by mass aqueous sulfuric acid solution.
鍍銅：浴組成：硫酸60g/L、硫酸銅200g/L、剩餘部分水，鍍浴溫度：25℃，電流密度：5.0A/dm2 Copper plating: bath composition: sulfuric acid 60g / L, copper sulfate 200g / L, the remaining part of water, plating bath temperature: 25 ° C, current density: 5.0A / dm 2
鍍錫：浴組成：硫酸亞錫40g/L、硫酸60g/L、甲酚磺酸40g/L、明膠2g/L、β-萘酚1g/L、剩餘部分水，鍍浴溫度：20℃，電流密度：1.5A/dm2 Tin plating: bath composition: stannous sulfate 40g / L, sulfuric acid 60g / L, cresol sulfonic acid 40g / L, gelatin 2g / L, β-naphthol 1g / L, the remaining part of water, plating bath temperature: 20 ° C, current density: 1.5A / dm 2
鍍銅厚度及鍍錫厚度之測定：根據鍍敷電解時間(於電解時間為2分鐘之情形時，回焊處理前之銅層之厚度為0.8μm，錫層之厚度為約1μm)進行調整。The thickness of the copper plating and the thickness of the tin plating were adjusted according to the plating electrolysis time (when the electrolysis time was 2 minutes, the thickness of the copper layer before the reflow treatment was 0.8 μm, and the thickness of the tin layer was about 1 μm).
回焊處理：將鍍錫後之試樣***至將溫度調整為400℃、環境氣體調整為氮氣(氧為1vol%以下)之加熱爐中5~30秒，然後進行水冷。Reflow treatment: The sample after tin plating is inserted into a heating furnace adjusted to a temperature of 400 ° C and an atmosphere gas adjusted to nitrogen (oxygen is 1 vol % or less) for 5 to 30 seconds, followed by water cooling.
分別測定所獲得之試樣表面之{200}、{311}、{220}面的X射線繞射強度I。測定係使用RIGAKU製造之RINT2500，X射線照射條件係使用鈷管，並設為管電壓25KV、管電流20mA。以同樣之方式分別測定純銅粉末標準試樣之{200}、{311}、{220}面之X射線繞射強度I0 。The X-ray diffraction intensity I of the {200}, {311}, and {220} planes of the obtained sample surface was measured, respectively. For the measurement, RINT 2500 manufactured by RIGAKU was used, and a cobalt tube was used for the X-ray irradiation conditions, and the tube voltage was 25 KV and the tube current was 20 mA. The X-ray diffraction intensity I 0 of the {200}, {311}, and {220} faces of the pure copper powder standard sample was measured in the same manner.
藉由JIS-H0501所規定之切割法求出軋壓平行剖面之結晶粒徑。The crystal grain size of the parallel cross section of the rolling was determined by the cutting method prescribed in JIS-H0501.
利用拉伸試驗機，根據JIS-Z2241，分別測定與軋壓方向平行之方向上的拉伸強度(TS)。將對於與軋壓方向平行之方向分別測定之拉伸強度的平均值示於表1。The tensile strength (TS) in the direction parallel to the rolling direction was measured by a tensile tester in accordance with JIS-Z2241. The average value of the tensile strengths measured in the direction parallel to the rolling direction is shown in Table 1.
利用圖2所示之方法進行耐聯合國試驗，而評價耐疲勞特性。耐聯合國試驗係疲勞試驗之一種，如圖2所示，係將單體電池20以3行(串聯)×2段(並聯)配置，於將試樣(引板片)10焊接於電極20a後，將最外側之引板片10焊接32於電路基板30。電路基板30連接於連接器40，且整體收容於盒體50。繼而，使盒體50於X方向(單體電池20之串聯連接方向)、Y方向(單體電池20之並聯連接方向)、及Z方向(垂直於X-Y方向之方向)上分別以振幅：0.8mm、頻率：7.0~200Hz、掃描時間：7.5min×12循環(合計90min)進行振動。振動方向僅設為X、Y、Z之各方向中之一者，而非於複數個方向上同時振動，頻率與時間成比例，使頻率於上述範圍內增減。The fatigue resistance was evaluated by using the method shown in Fig. 2 to carry out the UN resistance test. One type of fatigue test of the United Nations test system, as shown in Fig. 2, the unit cells 20 are arranged in 3 rows (series) × 2 segments (parallel), after the sample (leaf sheet) 10 is welded to the electrode 20a. The outermost lead sheet 10 is soldered 32 to the circuit board 30. The circuit board 30 is connected to the connector 40 and is housed in the casing 50 as a whole. Then, the case 50 is set to have an amplitude of 0.8 in the X direction (the series connection direction of the unit cells 20), the Y direction (the parallel connection direction of the unit cells 20), and the Z direction (the direction perpendicular to the XY directions). Mm, frequency: 7.0~200Hz, scanning time: 7.5min × 12 cycles (total 90min) for vibration. The vibration direction is only set to one of the directions of X, Y, and Z, and is not simultaneously vibrated in a plurality of directions, and the frequency is proportional to time, so that the frequency is increased or decreased within the above range.
以此方式進行試驗，並根據以下基準進行評價。若評價為○，則較佳。The test was conducted in this manner and evaluated according to the following criteria. If the evaluation is ○, it is preferable.
○：於試驗後引板無斷裂或龜裂○: no cracking or cracking of the guide plate after the test
×：於試驗後引板有斷裂或龜裂×: The plate has cracks or cracks after the test.
以使長邊方向與軋壓方向平行之方式製作4個厚度0.15mm、寬度10mm、長度40mm之試片，將與試片之長邊方向成直角之方向作為彎曲軸，進行180°彎曲後，將其彎回。將此作為1次，並反覆進行彎曲直至試樣斷裂，求出4個試樣之平均斷裂(反覆彎曲)次數。根據以下基準進行評價。若評價為◎~△，則於實際使用上不存在問題。Four test pieces having a thickness of 0.15 mm, a width of 10 mm, and a length of 40 mm were produced so that the longitudinal direction was parallel to the rolling direction, and the direction perpendicular to the longitudinal direction of the test piece was used as a bending axis, and after bending at 180°, Bend it back. This was taken once, and the bending was repeated until the sample was broken, and the number of average fractures (repetitive bending) of the four samples was determined. Evaluation was performed based on the following criteria. If the evaluation is ◎~△, there is no problem in actual use.
◎：反覆彎曲次數超過3次◎: Repeated bending times more than 3 times
○：反覆彎曲次數為2次以上但未達3次○: The number of times of repeated bending is 2 or more but not 3 times
△：反覆彎曲次數為2次△: The number of times of repeated bending is 2 times
×：反覆彎曲次數未達2次×: The number of repeated bendings is less than 2 times
將所獲得之結果示於表1。The results obtained are shown in Table 1.
由表1明確可知，於滿足2.5≦[I{220}/I0 {220}]≦3.5、2.2≦[I{200}/I0 {200}+I{311}/I0 {311}]且1.5≦I{311}/I{200}之各實施例之情形時，耐疲勞特性及反覆彎曲性均優異。As is clear from Table 1, it satisfies 2.5≦[I{220}/I 0 {220}]≦3.5, 2.2≦[I{200}/I 0 {200}+I{311}/I 0 {311}] In the case of each of the examples of 1.5≦I{311}/I{200}, both the fatigue resistance and the overflexibility were excellent.
另一方面，於精冷軋之加工度超過50%之比較例1、5、6之情形時，[I{200}/I0 {200}+I{311}/I0 {311}]未達2.2，反覆彎曲性下降。On the other hand, in the case of Comparative Examples 1, 5, and 6 in which the degree of processing of the finish cold rolling exceeds 50%, [I{200}/I 0 {200}+I{311}/I 0 {311}] Up to 2.2, the repeated bending is reduced.
於退火時之升溫速度未達20℃/sec之比較例2、3之情形時，I{311}/I{200}未達1.5，耐疲勞特性下降。In the case of Comparative Examples 2 and 3 at which the temperature increase rate at the time of annealing was less than 20 ° C/sec, I{311}/I{200} did not reach 1.5, and the fatigue resistance was lowered.
於未進行精冷軋之比較例4之情形、及精冷軋之加工度未達15%之比較例7之情形時，[I{220}/I0 {220}]未達2.5，耐疲勞特性劣化。In the case of Comparative Example 4 in which no finish cold rolling was performed, and in the case of Comparative Example 7 in which the degree of finish cold rolling was less than 15%, [I{220}/I 0 {220}] was less than 2.5, and fatigue resistance was obtained. Characteristics are degraded.
於退火時之升溫速度未達20℃/sec、且精冷軋之加工度未達15%之比較例8之情形時，I{311}/I{200}未達1.5，並且[I{220}/I0 {220}]未達2.5，耐疲勞特性及反覆彎曲性之兩者皆不佳。When the temperature rise rate at the time of annealing is less than 20 ° C / sec, and the degree of processing of the finish cold rolling is less than 15%, I {311} / I {200} is less than 1.5, and [I {220 }/I 0 {220}] Less than 2.5, both fatigue resistance and repeated bending are not good.
於退火時之材料之最高到達溫度超過900℃之比較例9之情形時，精軋後之結晶粒徑超過15μm而粗大化，且I{311}/I{200}未達1.5，反覆彎曲性不佳。In the case of Comparative Example 9 in which the maximum temperature of the material at the time of annealing exceeds 900 ° C, the crystal grain size after finish rolling is more than 15 μm and coarsened, and I{311}/I{200} is less than 1.5, and the bending property is repeated. Not good.
10‧‧‧引板片10‧‧‧ lead plate
20‧‧‧單體電池20‧‧‧ single battery
20a‧‧‧電極20a‧‧‧electrode
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