JP3687996B2 - Brazing material for platinum and platinum alloys - Google Patents
Brazing material for platinum and platinum alloys Download PDFInfo
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Description
【0001】
【産業上の利用分野】
開示技術は、白金、及び、白金合金製の時計バンド,指輪,ネックレース等の装身具、及び、各種機械器具の構造材料等の接合に用いられるろう材の技術分野に属する。
【0002】
【従来の技術】
周知の如く、白金、及び、白金合金製の時計バンド,指輪,ネックレース等の装身具、及び、各種機械器具,装置類の構造材料は、その審美的観点、或いは、利用目的、更には構造的要因等により複数種の素材自体を相互に接合する態様が多い。
【0003】
また、この接合を行う方法には、従来より、所謂ろう材を用いるろう付手段が一般的である。より具体的には、高周波誘導加熱によるろう付、或いは、電気炉加熱によるろう付手段が広く用いられている。さらに、用いられるろう材の融点は、作業性等の観点から母材金属と100℃以上の融点差があることが好ましいとされている。
【0004】
そして、かかる接合に用いられるろう材の材質、特に、白金、及び、白金合金の母材の接合用としては、一般に金合金、或いは、パラジウム合金が用いられている。
【0005】
これらに用いられているろう材としての金合金は、比較的低融点を有することから、ろう付の作業性が比較的良好である。ところが、亜鉛,カドミウム等が多量に含まれているために、ろう付の作業時にこれらの添加元素と母材の白金,白金合金とが反応し、ろう付の境界部に脆い拡散層が形成されて製品の機械的強度が弱くなるという欠点がある。また、母材の白金との濡れ性も悪く、接合性に乏しい難点がある。更には、ろう付部の表面粗さが大きいという不具合がある。加えて、ろう付後に必要とされる酸洗処理によりろう材が変色する不都合さがあり、そのうえ、母材である白金、及び、白金合金と色調的に異なる点があり、したがって、審美的にはなじみが悪いというマイナス点があった。
【0006】
また、他のろう材であるパラジウム合金はニッケル,銅,銀等を含む合金であるが、母材の白金,白金合金との濡れ性が不良で接合性に乏しい難点がある。更には、ろう付部の表面粗さが大きい不具合がある。そのうえ、上述ろう材の金合金同様に母材である白金、及び、白金合金と色調的に異和感を伴う審美上なじみが悪というマイナス点があった。
【0007】
さらに、これらのろう材は当業者に周知の如く白金、及び、白金合金用ろう材とはいうものの、白金を全く含有しないろう材であり、母材の白金,白金合金と同白金品位のろう材の現出が広く産業界より強く要望されていた。
【0008】
【発明が解決しようとする課題】
この出願の発明の目的は上述従来技術に基づく母材の白金,白金合金に対するろう材の問題点を解決すべき技術的課題とし、ろう付作業性が良く、また、母材の白金,白金合金との濡れ性が良く、接合性に優れ、したがって、充分な機械的強度を有し、しかも、ろう付部の表面粗さが小さく、加えて、ろう付後必要となる酸洗処理作業にあっても変色することがなく、更には色調的に、及び、白金品位的にも母材の白金、及び、白金合金と同様でなじみ性が良いようにして金属製品製造産業における接合技術利用分野に益する優れた白金、及び、白金合金用ろう材を提供せんとするものである。
【0009】
【課題を解決するための手段】
上述目的に沿い先述特許請求の範囲を要旨とするこの出願の発明の構成は、前述課題を解決するために、重量配合比でアンチモン4%以上〜18.5%未満であって、残部白金と不純物より成るろう材が母材の白金、及び、白金合金との濡れ性が良く、また、接合性に優れ、充分な機械的強度を有し、しかも、ろう付部の表面粗さが小さく、更に色調的にも母材の白金、及び、白金合金と同様でなじみ性が良く、加えて、ろう付後に必要な酸洗処理作業でも変色することがなく、そのうえ、上述基合金に対し重量配合比がインジウム0.05〜5.0%,スズ0.05〜5.0%,ガリウム0.05〜5.0%,ゲルマニウム0.05〜5.0%の少くとも一種を添加することにより、融点の低下,ろう付作業性の向上,母材白金、及び、白金合金との濡れ性改善,接合強度向上,表面粗さ低減等の機能,効果を助長改善することが出来るようにした技術的手段を講じたものである。
【0010】
【発明の背景】
次に、この出願の発明の定性的,定量的背景を述べる。
【0011】
〔アンチモン〕
アンチモンについて重量比を4%以上〜18.5%未満とした背景は以下の通りである。
アンチモンの重量比が4%未満であると、融点が高く、理想的なろう付温度である母材金属の白金,白金合金との融点差100℃以上を確保出来ず、ろう付作業が困難であるばかりか、母材の白金,白金合金との濡れ性が低下し、良好な接合性が損われることが実験により確認された。
一方、アンチモンの重量比が18.5%以上になると、高品位白金合金との融点差が大きくなり接合強度が低下すると共に、表面粗さが大きくなることが実験により確認された。
そこで、アンチモンについては、重量比を4%以上〜18.5%未満を最適範囲とした。
【0012】
〔インジウム,スズ,ガリウム,ゲルマニウム〕
また、重量配合比でインジウムについては0.05〜5.0%,スズについては0.05〜5.0%,ガリウムについては0.05〜5.0%,ゲルマニウムについては0.05〜5.0%の少くとも一種を添加することとした技術的根拠は、それらの少くとも一種を添加することにより融点を低下し、ろう付作業性を向上し、また、母材の白金、及び、白金合金との濡れ性を改善し、更に、接合強度を向上し、加えて、ろう付部表面粗さを低減するそれぞれの機能,効果を助長改善する作用があることを実験により確認したことによるものである。
【0013】
また、インジウム,スズ,ガリウム,ゲルマニウムのそれぞれについて添加重量範囲を限定した理由は、以下の通りである。
【0014】
インジウムについては0.05%以下では充分な効果が確認されず、一方、5.0%を超えると、母材の白金,白金合金との濡れ性が低下し、ろう付接合強度が低下することが実験的に確認され、したがって、その重量配合比で0.05〜5.0%を最適範囲と決定したものである。
【0015】
また、スズについては0.05%以下では効果が期待出来ず、一方、5.0%を超えると接合強度の低下が生じるばかりか、ろう付部の表面粗さが大きくなり、更に色調的に白金、及び、白金合金と異なることが確認され、したがって、スズについては0.05〜5.0%を最適範囲として限定したものである。
【0016】
また、ガリウムについては、他の添加元素と同様0.05%以下の添加では実験により効果が認められず、一方、5.0%を超えると母材としての白金,白金合金との濡れ性が低下し、ろう付接合強度が低下するのみならず、ろう付部の表面粗さが大きくなることが実験により確認され、そのため、ガリウムについては0.05〜5.0%を最適範囲と限定したものである。
【0017】
最後に、ゲルマニウムについては0.05%以下では期待する効果が確認出来ず、一方、5%を超えると、ガリウム同様、母材の白金,白金合金との濡れ性が低下し、ろう付接合強度の低下が生じることが確認され、したがって、当該ゲルマニウムについては0.05〜5.0%を最適範囲として限定的に決定したものである。
【0018】
【実施例】
次に、この出願の発明の実施例を従来品についての従来例と対比し示すと次の表1の通りである。
【0019】
【表1】
【0020】
なお、各々の試料は各素材を周知の高周波加熱溶解炉にて溶解して直径2mm,長さ50mmの所定形状のろう材を作製した。
【0021】
一方、このようにして作製されたろう材をこれまた周知の処理方法により微粉化し、粉末ろう材を作製した。
【0022】
それぞれ作製されたろう材は、次のろう付試験方法により試験し、表2に示す結果を得た。
【0023】
【表2】
【0024】
(1) ろう材の広がり試験
縦横30mm,厚さ1mmの白金母材を使用し、JIS Z 3191の硬ろうの広がり試験方法に準じた方法により試験し、ろうの広がり状態、及び、表面粗れを観察した。試験結果は、表2の「ろう広がり試験結果」の欄に記載した通りである。
この試験において、ろうの広がり状態を確認したところ、実施例1〜22及び従来例24については、ろう広がり状態に問題がないことが確認され、「良好」なろう広がり状態であると評価した。一方、従来例23及び25については、実施例1〜22及び従来例24と比較してろう広がり状態が悪かったため、「不良」なろう広がり状態であると評価した。
また、実施例1〜22及び従来例23〜25について、ろう付部の表面粗さを相対評価したところ、実施例1〜22については外観に表面荒れはほとんど確認されなかった。一方、従来例23〜25については、実施例1〜22と比較して大きな表面荒れが発生していることが確認された。
【0025】
(2) ろう付強度試験
白金母材を使用し、JIS Z 3192ろう付継手の引張り、及び、せん断試験方法に準じた方法により試験片を作製し、JIS Z 2241に準じた引張り試験方法を用いて試験した。試験結果は、表2の「ろう付強度試験結果」の欄に記載した通りである。
【0026】
(3) 変色試験
上述(1)のろう材の広がり試験片を、50℃の10%希塩酸溶液中に全浸漬して変色度合いを目視により観察した。観察は、同じ成分の処理前試料(酸洗処理していない同成分の試験片)と対比することにより行われ、結果は表2の「変色試験結果」の欄に記載し た通りである。
この試験により、実施例1〜22は、ろう付後必要となる酸洗処理作業を経ても変色することがないことが確認された。一方、従来例23〜25については、酸洗処理していない試験片と対比したところ明らかな色の変化が見られ、酸洗処理作業によって変色することが確認された。
【0027】
(4) ろう材色調の評価
上述(3)の試験後の試験片について、母材金属である白金,白金合金に対する色調的観点からの調和性を目視により評価した。評価結果は、表2の「ろう材色調」の欄に記載した通りである。
この評価により、酸洗処理によって変色しなかった実施例1〜22は、母材金属である白金,白金合金と同等の白金品位(色調的観点からの調和性)を有することが確認された。一方、酸洗処理によって変色した従来例23及び24については、それぞれ銀色,金色であったため、母材金属である白金,白金合金と色調的に異なることが明らかになった。また、酸洗処理によって変色した従来例25については、実施例1〜22に比して光沢が少なく且つ白濁していたため、母材金属である白金,白金合金と色調的に異なることが明らかになった。
【0028】
【発明の効果】
以上、この出願の発明によれば、基本的に重量配合比でアンチモン4%以上〜18.5%未満であって、残部白金と不純物より成るろう材としたことによりろう付作業性が良く、また、母材の白金,白金合金との濡れ性が良く、接合性に優れ、したがって、充分な機械的強度を有し、しかも、ろう付部の表面粗さが小さく、加えて、ろう付後必要となる酸洗処理作業でも変色することがなく、更には母材の白金、及び、白金合金と同様な白金品位で、また、上述合金を基合金としたものに対し重量配合比がインジウム0.05〜5.0%,スズ0.05〜5.0%,ガリウム0.05〜5.0%,ゲルマニウム0.05〜5.0%の少くとも一種を添加することにより、上記融点の低下,ろう付作業性の向上,母材の白金,白金合金との濡れ性改善,接合強度向上,表面粗さ低減等の機能,効果を助長改善することが出来るという優れた効果が奏される。[0001]
[Industrial application fields]
The disclosed technology belongs to the technical field of brazing materials used for joining jewelry such as platinum and platinum alloy watch bands, rings, necklaces, and structural materials of various machine tools.
[0002]
[Prior art]
As is well known, platinum, and platinum alloy watch band, ring, jewelry such as neck race, and various machinery, construction material of the device class, the aesthetic point of view, or purpose, and more structural There are many modes in which a plurality of types of materials themselves are joined together due to factors or the like.
[0003]
Further, the method of performing this bonding, conventionally brazed means using a so-called brazing material Ru general der. More specifically, brazing by high frequency induction heating, or brazing means are widely used by electric furnace heating. Furthermore, it is said that the melting point of the brazing material used preferably has a melting point difference of 100 ° C. or more from the base metal from the viewpoint of workability and the like.
[0004]
The material of the brazing material used for such bonding, particularly, platinum, and, as a for bonding the base material of platinum alloy, generally gold alloy, or palladium alloy.
[0005]
Since the gold alloys used as these brazing materials have a relatively low melting point, the workability of brazing is relatively good. However, because of the large amount of zinc, cadmium, etc., these additive elements react with the base material platinum and platinum alloys during the brazing operation, and a brittle diffusion layer is formed at the brazing boundary. There is a disadvantage that the mechanical strength of the product becomes weak . In addition, the wettability of the platinum of the base material or worse, poor difficulties there Ru in bonding property. Furthermore, a problem that a large surface roughness of the brazed portion there Ru. In addition, there is an inconvenience that the brazing material is discolored by the pickling treatment required after brazing, and furthermore, there is a point that is different in color tone from platinum and platinum alloy as a base material, and therefore aesthetically. There was a negative point that familiarity was bad.
[0006]
Further, the palladium alloy is another braze nickel, copper, an alloy containing silver, etc., platinum base material, wettability difficulties there Ru poor bondability poor of platinum alloy. Furthermore, defect there Ru surface roughness of the brazed portion is large. In addition, there is a negative point that platinum, which is a base material as well as the gold alloy of the brazing material described above, and aesthetic compatibility with the platinum alloy, which is unnatural in color tone, is bad.
[0007]
Furthermore, although these brazing materials are platinum and brazing alloys for platinum alloys as is well known to those skilled in the art, they are brazing materials that do not contain platinum at all, and are of the same quality as platinum and platinum alloys of the base material. The appearance of the material was widely requested by the industry.
[0008]
[Problems to be solved by the invention]
The object of the invention of this application is to solve the problem of the brazing material for the base metal platinum and platinum alloy based on the above-mentioned prior art, and the brazing workability is good, and the base material platinum and platinum alloy It has good wettability and excellent bondability, therefore it has sufficient mechanical strength, and the surface roughness of the brazing part is small. Even if it is not discolored, and in terms of color tone and platinum quality, it is similar to platinum and platinum alloys of the base material, and is compatible with the bonding technology application field in the metal product manufacturing industry. It is intended to provide an excellent platinum and brazing material for platinum alloys that will benefit.
[0009]
[Means for Solving the Problems]
In order to solve the above-mentioned problems, the composition of the invention of the present application, which is summarized in the scope of the above claims along with the above-mentioned object, is 4% or more to less than 18.5% antimony by weight, and the balance platinum and The brazing material made of impurities has good wettability with the base material platinum and platinum alloy, has excellent bonding properties, has sufficient mechanical strength, and has a small surface roughness of the brazing part, Furthermore, in terms of color, it is similar to the base material platinum and platinum alloy and has good compatibility. In addition, it does not change color even in the pickling process required after brazing, and it is blended by weight with the above base alloy. By adding at least one of the ratios indium 0.05-5.0%, tin 0.05-5.0%, gallium 0.05-5.0%, germanium 0.05-5.0% , Lowering of melting point, improvement of brazing workability, base material platinum and white Improving wettability between the alloy, the bonding strength improves, the surface roughness reducing such features, in which took technical means to be able to improve promoting effect.
[0010]
BACKGROUND OF THE INVENTION
Next, the qualitative and quantitative background of the invention of this application will be described .
[0011]
[Antimony]
The background of the antimony having a weight ratio of 4% to less than 18.5% is as follows.
If the weight ratio of antimony is less than 4%, the melting point is high, and it is difficult to braze because the melting point difference between the base metal platinum and the platinum alloy, which is an ideal brazing temperature, cannot exceed 100 ° C. In addition, it has been confirmed by experiments that the wettability with platinum and platinum alloys of the base material is lowered and the good bondability is impaired.
On the other hand, when the weight ratio of antimony is 18.5% or more, it has been confirmed by experiments that the melting point difference from the high-grade platinum alloy is increased, the bonding strength is lowered, and the surface roughness is increased .
Therefore , for antimony, the optimum range is a weight ratio of 4% to less than 18.5%.
[0012]
[Indium, tin, gallium, germanium]
Moreover, 0.05 to 5.0% for indium, 0.05 to 5.0% for tin, 0.05 to 5.0% for gallium, and 0.05 to 5 for germanium. The technical reason for adding at least one of 0.0% is to lower the melting point by adding at least one of them, improve the workability of brazing, and platinum and By confirming through experiments that the wettability with platinum alloy is improved, the bonding strength is improved, and in addition, the functions and effects of reducing the surface roughness of the brazed part are promoted and improved. Is.
[0013]
Moreover, the reason for limiting the addition weight range for each of indium, tin, gallium, and germanium is as follows.
[0014]
For indium, if 0.05% or less, a sufficient effect is not confirmed. On the other hand, if it exceeds 5.0%, the wettability with platinum or platinum alloy of the base material is lowered, and the brazing joint strength is lowered. Therefore, 0.05 to 5.0% is determined as the optimum range in the weight blending ratio.
[0015]
In addition, with respect to tin, if 0.05% or less, the effect cannot be expected. On the other hand, if it exceeds 5.0%, not only the bonding strength is lowered, but also the surface roughness of the brazed portion is increased, and the color tone is further improved. It is confirmed that it is different from platinum and platinum alloys. Therefore, for tin, 0.05 to 5.0% is limited as the optimum range.
[0016]
For gallium, as with other additive elements, if 0.05% or less is added, no effect is observed by experiment. On the other hand, if it exceeds 5.0%, wettability with platinum or a platinum alloy as a base material is not observed. It is confirmed by experiment that not only the brazing joint strength is lowered but also the surface roughness of the brazing portion is increased, and thus 0.05 to 5.0% is limited to the optimum range for gallium. Is.
[0017]
Lastly, for germanium, the expected effect cannot be confirmed at 0.05% or less. On the other hand, when it exceeds 5%, the wettability with platinum and platinum alloys of the base material is lowered, as with gallium, and the brazing joint strength Therefore, it is confirmed that 0.05 to 5.0% is limited as the optimum range for the germanium.
[0018]
【Example】
Next, the embodiment of the invention of this application is shown in Table 1 below in comparison with the conventional example of the conventional product.
[0019]
[Table 1]
[0020]
Each sample was prepared by melting each material in a known high-frequency heating melting furnace to produce a brazing material having a predetermined shape with a diameter of 2 mm and a length of 50 mm.
[0021]
On the other hand, the brazing material thus produced was pulverized by a known processing method to produce a powder brazing material.
[0022]
Each brazing material produced was tested by the following brazing test method, and the results shown in Table 2 were obtained.
[0023]
[Table 2]
[0024]
(1) Brazing material spread test Using a platinum base material of 30 mm in length and width and 1 mm in thickness, tested according to the method of JIS Z 3191 hard solder spreading test, and the spreading state of the wax and surface roughness Was observed. The test results are as described in the column of “Waist spread test results” in Table 2.
In this test, when the wax spread state was confirmed, it was confirmed that Examples 1 to 22 and Conventional Example 24 had no problem in the wax spread state, and were evaluated as “good” wax spread states. On the other hand, the conventional examples 23 and 25 were evaluated as being “bad” in the wax spreading state because the wax spreading state was worse than those in the examples 1 to 22 and the conventional example 24.
Moreover, when the surface roughness of the brazing part was relatively evaluated for Examples 1 to 22 and Conventional Examples 23 to 25, the surface roughness of Examples 1 to 22 was hardly confirmed. On the other hand, as for Conventional Examples 23 to 25, it was confirmed that a larger surface roughness was generated as compared with Examples 1 to 22.
[0025]
(2) Brazing strength test Using a platinum base material, a test piece was prepared by a method according to the tensile and shear test methods of JIS Z 3192 brazed joint, and a tensile test method according to JIS Z 2241 was used. And tested. The test results are as described in the “brazing strength test results” column of Table 2.
[0026]
(3) Discoloration test The spread specimen of the brazing material described in (1) above was fully immersed in a 10% dilute hydrochloric acid solution at 50 ° C., and the degree of discoloration was visually observed. The observation is performed by comparing with a sample before treatment of the same component (a test piece of the same component not subjected to pickling treatment), and the result is as described in the column of “discoloration test result” in Table 2 .
By this test, it was confirmed that Examples 1-22 did not discolor even if it passed through the pickling process required after brazing. On the other hand, about the conventional examples 23-25, when the contrast with the test piece which has not been pickled, the clear color change was seen, and it was confirmed that it changes color by the pickling process.
[0027]
(4) Evaluation of brazing material color tone
About the test piece after the test of the above-mentioned (3), the harmony from the viewpoint of color tone with respect to platinum and platinum alloy as the base metal was visually evaluated. The evaluation results are as described in the column of “brazing material color tone” in Table 2.
From this evaluation, it was confirmed that Examples 1 to 22 that were not discolored by the pickling treatment had platinum quality (harmonicity from a color viewpoint) equivalent to that of platinum or platinum alloy as the base metal. On the other hand, since the conventional examples 23 and 24 discolored by the pickling treatment were silver and gold, respectively, it became clear that they were different in color from the base metals platinum and platinum alloys. In addition, the conventional example 25, which has been discolored by the pickling treatment, is less glossy and cloudy than the examples 1-22, and thus clearly differs in color tone from platinum and platinum alloys that are base metals. became.
[0028]
【The invention's effect】
As described above, according to the invention of this application, the brazing material is basically a brazing material composed of the remaining platinum and impurities in an antimony ratio of 4% to less than 18.5% in terms of the weight blending ratio. In addition, it has good wettability with the base material platinum and platinum alloy, and has excellent bondability. Therefore, it has sufficient mechanical strength, and the surface roughness of the brazed part is small. In addition, after brazing The required pickling treatment does not change the color, and further, the platinum is the same as the base material of platinum and the platinum alloy, and the weight blending ratio is 0% of that of the above alloy based alloy. By adding at least one of 0.05-5.0%, tin 0.05-5.0%, gallium 0.05-5.0%, germanium 0.05-5.0%, Reduction, improvement of brazing workability, wetting with platinum or platinum alloy of base material It improved joint strength improvement, the function of the surface roughness reduction, etc., an excellent effect of being able to promote improved effects are achieved.
Claims (2)
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JP18509594A JP3687996B2 (en) | 1994-07-15 | 1994-07-15 | Brazing material for platinum and platinum alloys |
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JP18509594A JP3687996B2 (en) | 1994-07-15 | 1994-07-15 | Brazing material for platinum and platinum alloys |
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JP3687996B2 true JP3687996B2 (en) | 2005-08-24 |
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CN112861076B (en) * | 2021-01-05 | 2023-12-26 | 广东省科学院资源综合利用研究所 | Platinum-palladium grade prediction method based on linear regression model |
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