JP2017172043A - Ag-Cu ALLOY POWDER AND MANUFACTURING METHOD THEREFOR - Google Patents
Ag-Cu ALLOY POWDER AND MANUFACTURING METHOD THEREFOR Download PDFInfo
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Abstract
Description
本発明は、Ａｇ−Ｃｕ合金粉末およびその製造方法に関し、特に、ろう材や導電性ペーストなどに使用するのに適したＡｇ−Ｃｕ合金粉末およびその製造方法に関する。 The present invention relates to an Ag—Cu alloy powder and a method for producing the same, and more particularly to an Ag—Cu alloy powder suitable for use in a brazing material, a conductive paste, and the like, and a method for producing the same.
Ａｇ−Ｃｕ合金粉末は、ろう材や導電性ペーストなどに使用されており、Ａｇ−Ｃｕろう材を使用して金属導体層とセラミックの絶縁基板を接合する方法が知られている（例えば、特許文献１参照）。このようなＡｇ−Ｃｕろう材を使用して金属導体層とセラミック基板を接合すると、金属導体層上に搭載された半導体チップの動作による大電流と熱を金属導体層とＡｇ−Ｃｕろう材を介してセラミック基板に逃がすことができる。 Ag-Cu alloy powder is used for brazing material, conductive paste, and the like, and a method of joining a metal conductor layer and a ceramic insulating substrate using Ag-Cu brazing material is known (for example, patents). Reference 1). When such a Ag—Cu brazing material is used to join the metal conductor layer and the ceramic substrate, the large current and heat generated by the operation of the semiconductor chip mounted on the metal conductor layer can be applied to the metal conductor layer and the Ag—Cu brazing material. Through the ceramic substrate.
ろう材や導電性ペーストに使用するＡｇ−Ｃｕ合金粉末の粒子径を小さくすると、粒子間の接触点の増加による導電性の向上を図ることができるため、粒子径の小さいＡｇ−Ｃｕ合金粉末が望まれている。このような粒子径の小さいＡｇ−Ｃｕ合金粉末を製造する方法として、高圧水アトマイズ法によって平均粒径１〜１５μｍの球状の銀銅合金粉を製造する方法が提案されている（例えば、特許文献２参照）。 When the particle diameter of the Ag-Cu alloy powder used for the brazing material and the conductive paste is reduced, the conductivity can be improved by increasing the contact points between the particles. Therefore, the Ag-Cu alloy powder having a small particle diameter can be obtained. It is desired. As a method for producing such an Ag—Cu alloy powder having a small particle size, a method for producing a spherical silver-copper alloy powder having an average particle size of 1 to 15 μm by a high-pressure water atomization method has been proposed (for example, Patent Documents). 2).
しかし、Ａｇ−Ｃｕ合金粉末の粒子径を小さくすると、酸素含有量が高くなり易く、導電性が低下し易いという問題がある。特許文献２の方法で製造した銀銅合金粉の酸素含有量も０．２質量％程度と高く、酸素含有量をさらに低下させることが望まれている。また、特許文献１に記載されているように、Ａｇ−Ｃｕろう材を使用して金属導体層とセラミック基板を接合する場合には、７００℃以上の高温で加熱して接合する必要があり、この加熱の際にＡｇ−Ｃｕろう材が大きく収縮すると、金属導体層とセラミック基板との熱による収縮の差が大きくなって、セラミック基板に応力がかかり、セラミック基板の割れやクラックの発生の原因になる。
However, when the particle diameter of the Ag—Cu alloy powder is reduced, there is a problem that the oxygen content tends to increase and the conductivity tends to decrease. The oxygen content of the silver-copper alloy powder produced by the method of
したがって、本発明は、このような従来の問題点に鑑み、粒子径が小さく、酸素含有量が低く且つ熱による収縮率が低いＡｇ−Ｃｕ合金粉末およびその製造方法を提供することを目的とする。 Therefore, in view of such conventional problems, an object of the present invention is to provide an Ag—Cu alloy powder having a small particle diameter, a low oxygen content, and a low shrinkage rate due to heat, and a method for producing the same. .
本発明者らは、上記課題を解決するために鋭意研究した結果、銀と銅を溶解した溶湯を落下させながら、非酸化性雰囲気中において高圧水を吹き付けて急冷凝固させることによって得られた粉末を、還元処理することにより、粒子径が小さく、酸素含有量が低く且つ熱による収縮率が低いＡｇ−Ｃｕ合金粉末を製造することができることを見出し、本発明を完成するに至った。 As a result of diligent research to solve the above problems, the inventors of the present invention have obtained powder obtained by spraying high-pressure water in a non-oxidizing atmosphere and rapidly solidifying it while dropping a molten metal in which silver and copper are dissolved. As a result of the reduction treatment, it was found that an Ag—Cu alloy powder having a small particle diameter, a low oxygen content, and a low shrinkage rate due to heat can be produced, and the present invention has been completed.
すなわち、本発明によるＡｇ−Ｃｕ合金粉末の製造方法は、銀と銅を溶解した溶湯を落下させながら、非酸化性雰囲気中において高圧水を吹き付けて急冷凝固させることによって得られた粉末を、還元処理することを特徴とする。このＡｇ−Ｃｕ合金粉末の製造方法において、非酸化性雰囲気が窒素雰囲気であるのが好ましく、還元処理が水素雰囲気中において熱処理することによって行われるのが好ましい。また、高圧水が水圧２０〜１６０ＭＰａで吹き付けられるのが好ましい。 That is, the method for producing an Ag—Cu alloy powder according to the present invention reduces the powder obtained by rapidly solidifying by blowing high-pressure water in a non-oxidizing atmosphere while dropping a molten metal in which silver and copper are dissolved. It is characterized by processing. In this method for producing an Ag—Cu alloy powder, the non-oxidizing atmosphere is preferably a nitrogen atmosphere, and the reduction treatment is preferably performed by heat treatment in a hydrogen atmosphere. Moreover, it is preferable that high-pressure water is sprayed at a water pressure of 20 to 160 MPa.
また、本発明によるＡｇ−Ｃｕ合金粉末は、平均粒径が１〜２０μｍ、酸素含有量が０．１質量％以下であり、且つ４００℃における収縮率が６％以下であることを特徴とする。このＡｇ−Ｃｕ合金粉末は、ＢＥＴ比表面積が０．０１〜１ｍ２／ｇであるのが好ましく、タップ密度が３ｇ／ｃｍ３以上であるのが好ましく、炭素含有量が０．１質量％以下であるのが好ましい。 In addition, the Ag—Cu alloy powder according to the present invention has an average particle diameter of 1 to 20 μm, an oxygen content of 0.1% by mass or less, and a shrinkage rate at 400 ° C. of 6% or less. . The Ag—Cu alloy powder preferably has a BET specific surface area of 0.01 to 1 m 2 / g, preferably has a tap density of 3 g / cm 3 or more, and has a carbon content of 0.1% by mass or less. Is preferred.
また、本発明による導電性ペーストまたはろう材ペーストは、上記のＡｇ−Ｃｕ合金粉末と溶剤からなることを特徴とする。また、本発明による粉末ろう材は、Ａｇ−Ｃｕ合金粉末からなることを特徴とする。さらに、本発明による接合方法は、上記のろう材ペーストまたは粉末ろう材を被接合物間に介在させて加熱することにより、被接合物同士を接合することを特徴とする。この接合方法において、被接合物の一方がセラミック基板であるとともに他方が金属部材であるのが好ましく、加熱が７００〜１２００℃で行われるのが好ましい。 Moreover, the conductive paste or brazing paste according to the present invention is characterized by comprising the above Ag-Cu alloy powder and a solvent. Moreover, the powder brazing material according to the present invention is characterized by comprising an Ag-Cu alloy powder. Furthermore, the bonding method according to the present invention is characterized in that the objects to be bonded are bonded to each other by heating the brazing material paste or the powder brazing material interposed between the objects to be bonded. In this bonding method, it is preferable that one of the objects to be bonded is a ceramic substrate and the other is a metal member, and heating is preferably performed at 700 to 1200 ° C.
なお、本明細書中において、「平均粒径」とは、（ヘロス法によって）レーザー回折式粒度分布測定装置により測定した体積基準の累積５０％粒子径（Ｄ５０径）をいう。 In the present specification, the “average particle diameter” refers to a volume-based cumulative 50% particle diameter (D 50 diameter) measured by a laser diffraction particle size distribution measuring apparatus (by the Helos method).
本発明によれば、粒子径が小さく、酸素含有量が低く且つ熱による収縮率が低いＡｇ−Ｃｕ合金粉末を製造することができる。 According to the present invention, an Ag—Cu alloy powder having a small particle size, a low oxygen content, and a low shrinkage rate due to heat can be produced.
本発明によるＡｇ−Ｃｕ合金粉末の製造方法の実施の形態では、銀と銅を溶解した溶湯を落下させながら、非酸化性雰囲気中において（好ましくは水圧２０〜１６０ＭＰａ、さらに好ましくは水圧２０〜１５０ＭＰａで）高圧水を吹き付けて急冷凝固させることによって得られた（スラリーを固液分離して得られた固形物を乾燥して得られた）粉末を、還元処理して、Ａｇ−Ｃｕ合金粉末を得る。なお、必要に応じて、固形物を乾燥する前に水洗してもよく、乾燥した後に解砕したり、分級して、粒度を調整してもよい。 In the embodiment of the method for producing an Ag—Cu alloy powder according to the present invention, a molten metal in which silver and copper are dissolved is dropped in a non-oxidizing atmosphere (preferably a water pressure of 20 to 160 MPa, more preferably a water pressure of 20 to 150 MPa. The powder obtained by spraying high-pressure water and rapidly solidifying by solidification (obtained by drying the solid obtained by solid-liquid separation of the slurry) is subjected to a reduction treatment to obtain an Ag-Cu alloy powder. obtain. If necessary, the solid matter may be washed with water before drying, or may be crushed or classified after drying to adjust the particle size.
高圧水を吹き付ける、所謂水アトマイズ法によりＡｇ−Ｃｕ合金粉末を製造すると、粒子径が小さいＡｇ−Ｃｕ合金粉末を得ることができる。粒子径が小さいＡｇ−Ｃｕ合金粉末をろう材や導電性ペーストに使用すると、導電性を向上させることができる。一方、Ａｇ−Ｃｕ合金粉末の粒子径が小さくなると、酸素含有量が高くなり易く、酸素含有量が高くなると、導電性が低下し易くなるという問題がある。また、Ａｇ−Ｃｕ合金粉末の粒子径が同程度であれば、酸素含有量が高くなると、加熱による収縮率も大きくなる。本発明によるＡｇ−Ｃｕ合金粉末の製造方法の実施の形態では、非酸化性雰囲気中において水アトマイズ法により製造したＡｇ−Ｃｕ合金粉末を還元処理することにより、Ａｇ−Ｃｕ合金粉末の粒子の表面の酸素だけでなく、粒子の内部の酸素の量も低下させることができ、粒子全体の酸素含有量を低下させることができる。特に、水アトマイズ法により製造したＡｇ−Ｃｕ合金粉末を還元処理することにより、Ａｇ−Ｃｕ合金粉末の粒子の表面の酸素を除去するだけでは、粒子全体の酸素含有量を十分に低下させることができないが、非酸化性雰囲気中において水アトマイズ法によりＡｇ−Ｃｕ合金粉末を製造すれば、粒子の内部の酸素の量を低下させることができ、Ａｇ−Ｃｕ合金粉末の粒子径が同程度であれば、加熱による収縮率を低下させることもできる。なお、高圧水を吹き付けることにより、銀と銅を溶解した溶湯を急冷凝固させて得られたＡｇ−Ｃｕ合金粉末は、非共晶合金粉末になる。 When an Ag—Cu alloy powder is produced by a so-called water atomization method in which high-pressure water is sprayed, an Ag—Cu alloy powder having a small particle diameter can be obtained. When Ag-Cu alloy powder having a small particle diameter is used for brazing material or conductive paste, the conductivity can be improved. On the other hand, when the particle diameter of the Ag—Cu alloy powder is small, there is a problem that the oxygen content tends to be high, and when the oxygen content is high, the conductivity tends to be low. Moreover, if the particle diameter of the Ag—Cu alloy powder is approximately the same, the shrinkage rate due to heating increases as the oxygen content increases. In the embodiment of the method for producing an Ag—Cu alloy powder according to the present invention, the surface of the particles of the Ag—Cu alloy powder is reduced by reducing the Ag—Cu alloy powder produced by the water atomization method in a non-oxidizing atmosphere. In addition to the oxygen, the amount of oxygen inside the particles can be reduced, and the oxygen content of the entire particles can be reduced. In particular, by reducing the Ag—Cu alloy powder produced by the water atomization method, it is possible to sufficiently reduce the oxygen content of the entire particle simply by removing the oxygen on the surface of the particle of the Ag—Cu alloy powder. However, if the Ag—Cu alloy powder is produced by the water atomization method in a non-oxidizing atmosphere, the amount of oxygen inside the particles can be reduced, and the particle diameter of the Ag—Cu alloy powder should be approximately the same. For example, the shrinkage rate due to heating can be reduced. Note that the Ag—Cu alloy powder obtained by rapidly solidifying a molten metal in which silver and copper are dissolved by spraying high-pressure water becomes a non-eutectic alloy powder.
なお、非酸化性雰囲気として、窒素、アルゴン、ヘリウムなどの不活性雰囲気や、水素、一酸化炭素などの還元性雰囲気が挙げられるが、コストや安全性の観点から、窒素雰囲気であるのが好ましい。また、還元処理の方法として、水素雰囲気や一酸化炭素雰囲気中において熱処理する、気相還元法が挙げられるが、コストや安全性の観点から、水素雰囲気中における熱処理（水素還元処理）であるのが好ましい。この熱処理における加熱温度は１２０〜３２０℃であるのが好ましく、熱処理後の粉末の凝集を防止するために、１２０〜２６０℃であるのがさらに好ましい。また、熱処理時間は５〜２０時間であるのが好ましい。 In addition, examples of the non-oxidizing atmosphere include an inert atmosphere such as nitrogen, argon, and helium, and a reducing atmosphere such as hydrogen and carbon monoxide. From the viewpoint of cost and safety, a nitrogen atmosphere is preferable. . Further, as a reduction treatment method, there is a gas phase reduction method in which heat treatment is performed in a hydrogen atmosphere or a carbon monoxide atmosphere. However, from the viewpoint of cost and safety, the heat treatment (hydrogen reduction treatment) is performed in a hydrogen atmosphere. Is preferred. The heating temperature in this heat treatment is preferably 120 to 320 ° C, and more preferably 120 to 260 ° C in order to prevent aggregation of the powder after the heat treatment. The heat treatment time is preferably 5 to 20 hours.
上述したＡｇ−Ｃｕ合金粉末の製造方法の実施の形態により、本発明によるＡｇ−Ｃｕ合金粉末の実施の形態を製造することができる。 According to the embodiment of the method for producing the Ag—Cu alloy powder described above, the embodiment of the Ag—Cu alloy powder according to the present invention can be produced.
また、本発明によるＡｇ−Ｃｕ合金粉末の実施の形態は、平均粒径が１〜２０μｍ（加熱による収縮率を小さくするためには、好ましくは３〜１８μｍ、さらに好ましくは５〜１６μｍ）であり、酸素含有量が０．１質量％以下（好ましくは０．０８質量％以下、さらに好ましくは０．０５質量％以下）であり、４００℃における収縮率が６％以下（好ましくは５％以下、さらに好ましくは３％以下、最も好ましくは１．５％以下）である。このＡｇ−Ｃｕ合金粉末の形状は、好ましくは粒状または（略）球状である。Ａｇ−Ｃｕ合金粉末のＡｇとＣｕの質量割合（Ａｇ：Ｃｕ）は、好ましくは３０：７０〜８０：２０であり、さらに好ましくは４０：６０〜７５：２５である。Ａｇ−Ｃｕ合金粉末のＢＥＴ比表面積は、０．０１〜１ｍ２／ｇであるのが好ましく、０．０３〜０．６ｍ２／ｇであるのがさらに好ましく、０．０５〜０．２ｍ２／ｇであるのが最も好ましい。Ａｇ−Ｃｕ合金粉末のタップ密度は、Ａｇ−Ｃｕ合金粉末をろう材ペーストや導電性ペーストに使用する場合に粉末の充填性を高めるために、３ｇ／ｃｍ３以上であるのが好ましく、５ｇ／ｃｍ３以上であるのがさらに好ましく、５〜６ｇ／ｃｍ３であるのが最も好ましい。Ａｇ−Ｃｕ合金粉末の炭素含有量は、Ａｇ−Ｃｕ合金粉末をろう材や導電性ペーストに使用する場合に加熱により発生するガスにより被接合物との密着性が低下するのを防止するために、０．１質量％以下であるのが好ましく、０．０５質量％以下であるのがさらに好ましく、０．０２質量％以下であるのが最も好ましい。 In the embodiment of the Ag—Cu alloy powder according to the present invention, the average particle size is 1 to 20 μm (preferably 3 to 18 μm, more preferably 5 to 16 μm for reducing the shrinkage ratio by heating). The oxygen content is 0.1% by mass or less (preferably 0.08% by mass or less, more preferably 0.05% by mass or less), and the shrinkage at 400 ° C. is 6% or less (preferably 5% or less, More preferably, it is 3% or less, and most preferably 1.5% or less. The shape of the Ag—Cu alloy powder is preferably granular or (substantially) spherical. The mass ratio (Ag: Cu) of Ag and Cu in the Ag—Cu alloy powder is preferably 30:70 to 80:20, and more preferably 40:60 to 75:25. BET specific surface area of the Ag-Cu alloy powder is preferably from 0.01~1m 2 / g, more preferably from 0.03~0.6m 2 / g, 0.05~0.2m 2 Most preferred is / g. The tap density of the Ag—Cu alloy powder is preferably 3 g / cm 3 or more in order to increase the powder filling property when the Ag—Cu alloy powder is used for brazing filler metal paste or conductive paste. More preferably, it is cm 3 or more, and most preferably 5 to 6 g / cm 3 . The carbon content of the Ag-Cu alloy powder is to prevent the adhesion with the workpiece to be lowered by the gas generated by heating when the Ag-Cu alloy powder is used for brazing material or conductive paste. The content is preferably 0.1% by mass or less, more preferably 0.05% by mass or less, and most preferably 0.02% by mass or less.
本発明によるＡｇ−Ｃｕ合金粉末の実施の形態は、導電性に優れるとともに、加熱による収縮率が低いため、ろう材に使用するのに適している。Ａｇ−Ｃｕ合金粉末をそのまま粉末ろう材として使用してもよいし、溶剤と混合してろう材ペーストとして使用してもよい。ろう材ペーストは、必要に応じてバインダ樹脂を含んでもよい。ろう材ペーストに混合する溶剤として、メチルセルソルブ、エチルセルソルブ、イソホロン、トルエン、酢酸エチル、テレピネオール、ジエチレングリコール、モノブチルエーテル、テキサノールなどの有機溶剤を使用することができ、バインダ樹脂として、セルロース系樹脂や、（メタ）アクリル樹脂などを使用することができる。 The embodiment of the Ag—Cu alloy powder according to the present invention is suitable for use in a brazing material because it is excellent in conductivity and has a low shrinkage ratio due to heating. Ag-Cu alloy powder may be used as a powder brazing material as it is, or may be mixed with a solvent and used as a brazing material paste. The brazing material paste may contain a binder resin as necessary. Organic solvents such as methyl cellosolve, ethyl cellosolve, isophorone, toluene, ethyl acetate, terpineol, diethylene glycol, monobutyl ether, and texanol can be used as the solvent to be mixed with the brazing paste, and the cellulose resin as the binder resin Alternatively, (meth) acrylic resin or the like can be used.
本発明によるＡｇ−Ｃｕ合金粉末の実施の形態をろう材ペーストまたは粉末ろう材に使用し、このろう材ペーストまたは粉末ろう材を（好ましくは被接合物の少なくとも一方に印刷などにより塗布することにより）被接合物間に介在させて（好ましくは７００〜１２００℃の温度で）加熱してろう材ペーストまたは粉末ろう材中のＡｇ−Ｃｕ合金粉末を焼結させることにより、被接合物同士（好ましくはセラミック基板と金属部材）を接合することができる。セラミック基板として、アルミナ、ジルコニア、窒化アルミニウム、窒化ケイ素などからなる絶縁基板を使用することができる。金属部材として、アルミニウムや銅などの金属板や金属導体層などを使用することができる。 The embodiment of the Ag-Cu alloy powder according to the present invention is used for brazing paste or powder brazing material, and this brazing paste or powder brazing material is applied (preferably by printing or the like on at least one of the objects to be joined). ) Sintering the Ag—Cu alloy powder in the brazing filler metal paste or the powder brazing material by heating (preferably at a temperature of 700 to 1200 ° C.) between the objects to be joined together (preferably Can join a ceramic substrate and a metal member). As the ceramic substrate, an insulating substrate made of alumina, zirconia, aluminum nitride, silicon nitride, or the like can be used. As the metal member, a metal plate such as aluminum or copper, a metal conductor layer, or the like can be used.
本発明によるＡｇ−Ｃｕ合金粉末の実施の形態は、導電性に優れるとともに、加熱による収縮率が低いため、ろう材ペーストまたは粉末ろう材に使用してセラミック基板と金属部材を接合する際に加熱しても、セラミック基板にかかる応力を小さくし、セラミック基板の割れやクラックの発生を防止することができる。本発明によるＡｇ−Ｃｕ合金粉末の実施の形態をろう材ペーストまたは粉末ろう材に使用してセラミック基板と金属部材を接合して得られた積層体は、パワーモジュール用の放熱板として使用することができる。 The embodiment of the Ag-Cu alloy powder according to the present invention is excellent in electrical conductivity and has a low shrinkage ratio due to heating. Therefore, when the ceramic substrate and the metal member are joined to each other using the brazing paste or powder brazing material, heating is performed. Even so, it is possible to reduce the stress applied to the ceramic substrate and prevent the ceramic substrate from being cracked or cracked. The laminate obtained by joining the ceramic substrate and the metal member using the embodiment of the Ag-Cu alloy powder according to the present invention for the brazing paste or powder brazing material is used as a heat radiating plate for a power module. Can do.
本発明によるＡｇ−Ｃｕ合金粉末の実施の形態は、導電性に優れるとともに、加熱による収縮率が低いため、溶剤と混合して（好ましくは６００〜１０００℃程度の高温で焼成する）焼成温度が高い焼結型導電性ペーストに使用することができる。導電性ペーストに混合する溶剤として、飽和脂肪族炭化水素類、不飽和脂肪族炭化水素類、ケトン類、芳香族炭化水素類、グリコールエーテル類、エステル類、アルコール類などの有機溶剤を使用することができる。また、必要に応じて、エチルセルロースや（メタ）アクリル樹脂などのバインダ樹脂を有機溶剤に溶解したビヒクル、ガラスフリット、無機酸化物、分散剤などを導電性ペーストに添加してもよい。 The embodiment of the Ag-Cu alloy powder according to the present invention is excellent in conductivity and has a low shrinkage ratio due to heating, so that it is mixed with a solvent (preferably fired at a high temperature of about 600 to 1000 ° C.). It can be used for high sintered conductive paste. Use organic solvents such as saturated aliphatic hydrocarbons, unsaturated aliphatic hydrocarbons, ketones, aromatic hydrocarbons, glycol ethers, esters, and alcohols as solvents to be mixed with the conductive paste. Can do. If necessary, a vehicle, glass frit, inorganic oxide, dispersant, or the like in which a binder resin such as ethyl cellulose or (meth) acrylic resin is dissolved in an organic solvent may be added to the conductive paste.
以下、本発明によるＡｇ−Ｃｕ合金粉末およびその製造方法の実施例について詳細に説明する。 Hereinafter, examples of the Ag-Cu alloy powder and the method for producing the same according to the present invention will be described in detail.
［実施例１］
（純度９９．９９質量％の）ショット銀７．２ｋｇと（純度９９．９９質量％の）銅ボール２．８ｋｇを１２００℃に加熱して溶解した溶湯をタンディッシュ下部から落下させながら、水アトマイズ装置により窒素雰囲気中において水圧７０ＭＰａ、水量１６０Ｌ／分で２０℃の高圧水を吹き付けて急冷凝固させ、得られたスラリーを固液分離し、固形分を水洗し、乾燥し、解砕して得られた粉末を、水素雰囲気中において２００℃で１０時間加熱して熱処理（水素還元処理）した後、解砕し、篩分して、球状のＡｇ−Ｃｕ合金粉末を得た。
[Example 1]
While atomizing 7.2 kg of shot silver (purity 99.99 mass%) and 2.8 kg of copper balls (purity 99.99 mass%) by heating to 1200 ° C., dropping the molten metal from the bottom of the tundish, It is obtained by rapid solidification by spraying high-pressure water of 20 ° C. at a water pressure of 70 MPa and a water volume of 160 L / min in a nitrogen atmosphere, and solid-liquid separation of the resulting slurry, washing the solid with water, drying and crushing. The obtained powder was heated at 200 ° C. for 10 hours in a hydrogen atmosphere and heat treated (hydrogen reduction treatment), and then crushed and sieved to obtain a spherical Ag—Cu alloy powder.
このようにして得られたＡｇ−Ｃｕ合金粉末について、ＢＥＴ比表面積、タップ密度、酸素含有量、炭素含有量および粒度分布を求めるとともに、粉末Ｘ線回折法（ＸＲＤ）による測定を行った。 About the obtained Ag-Cu alloy powder, the BET specific surface area, the tap density, the oxygen content, the carbon content and the particle size distribution were determined and measured by a powder X-ray diffraction method (XRD).
ＢＥＴ比表面積は、ＢＥＴ比表面積測定器（ユアサアイオニクス株式会社製の４ソーブＵＳ）を使用し、測定器内に１０５℃で２０分間窒素ガスを流して脱気した後、３０体積％の窒素と７０体積％のヘリウムの混合ガスを流しながら、ＢＥＴ１点法により測定した。その結果、ＢＥＴ比表面積は０．１６ｍ２／ｇであった。 The BET specific surface area was measured by using a BET specific surface area measuring device (4 Sorb US made by Yuasa Ionics Co., Ltd.), degassing by flowing nitrogen gas at 105 ° C. for 20 minutes, and then adding 30% by volume of nitrogen. And BET one-point method while flowing a mixed gas of 70 volume% helium. As a result, the BET specific surface area was 0.16 m 2 / g.
タップ密度（ＴＡＰ）は、特開２００７−２６３８６０号公報に記載された方法と同様に、Ａｇ−Ｃｕ合金粉末を内径６ｍｍの有底円筒形のダイに充填して合金粉末層を形成し、この合金粉末層の上面に０．１６０Ｎ／ｍ２の圧力を均一に加えた後、合金粉末層の高さを測定し、この合金粉末層の高さの測定値と、充填された合金粉末の重量とから、合金粉末の密度を求めて、Ａｇ−Ｃｕ合金粉末のタップ密度とした。その結果、タップ密度は５．１６ｇ／ｃｍ３であった。 The tap density (TAP) is formed by filling Ag—Cu alloy powder into a bottomed cylindrical die having an inner diameter of 6 mm to form an alloy powder layer, as in the method described in Japanese Patent Application Laid-Open No. 2007-263860. After uniformly applying a pressure of 0.160 N / m 2 on the upper surface of the alloy powder layer, the height of the alloy powder layer is measured, and the measured value of the height of the alloy powder layer and the weight of the filled alloy powder are measured. From the above, the density of the alloy powder was determined and used as the tap density of the Ag-Cu alloy powder. As a result, the tap density was 5.16 g / cm 3 .
酸素含有量は、酸素・窒素・水素分析装置（株式会社堀場製作所製のＥＭＧＡ−９２０）により測定した。その結果、酸素含有量は０．０３質量％であった。 The oxygen content was measured with an oxygen / nitrogen / hydrogen analyzer (EMGA-920 manufactured by Horiba, Ltd.). As a result, the oxygen content was 0.03% by mass.
炭素含有量は、炭素・硫黄分析装置（堀場製作所製のＥＭＩＡ−２２０Ｖ）により測定した。その結果、炭素含有量は０．０１０質量％であった。 The carbon content was measured by a carbon / sulfur analyzer (EMIA-220V manufactured by Horiba, Ltd.). As a result, the carbon content was 0.010% by mass.
粒度分布は、レーザー回折式粒度分布測定装置（ＳＹＭＰＡＴＥＣ社製のへロス粒度分布測定装置（ＨＥＬＯＳ＆ＲＯＤＯＳ（気流式の乾燥モジュール）））を使用して、分散圧５ｂａｒで測定した。その結果、累積１０％粒子径（Ｄ１０）は２．４μｍ、累積２５％粒子径（Ｄ２５）は３．８μｍ、累積５０％粒子径（Ｄ５０）は５．９μｍ、累積７５％粒子径（Ｄ７５）は９．２μｍ、累積９０％粒子径（Ｄ９０）は１４．４μｍ、累積９９％粒子径（Ｄ９９）は２２．５μｍであった。 The particle size distribution was measured at a dispersion pressure of 5 bar using a laser diffraction particle size distribution measuring device (Heros particle size distribution measuring device (HELOS & RODOS (airflow drying module) manufactured by SYMPATEC)). As a result, the cumulative 10% particle size (D 10 ) was 2.4 μm, the cumulative 25% particle size (D 25 ) was 3.8 μm, the cumulative 50% particle size (D 50 ) was 5.9 μm, and the cumulative 75% particle size. (D 75 ) was 9.2 μm, cumulative 90% particle size (D 90 ) was 14.4 μm, and cumulative 99% particle size (D 99 ) was 22.5 μm.
また、得られたＡｇ−Ｃｕ合金粉末について、Ｘ線回折装置（株式会社リガク製のＲＩＮＴ Ｕｌｔｉｍａ ＩＩＩ）を使用して、Ｃｏ管球により、電圧４０ｋＶ、電流３０ｍＡ、スキャン速度２°／分、測定間隔０．０１°の条件で、１０〜９０°／２θの範囲を測定して、Ｘ線回折（ＸＲＤ）による結晶構造の評価を行った。この測定結果を図１に示す。図１に示すように、ＡｇとＣｕの単相は確認されず、非共晶合金粉末であることがわかった。 Moreover, about the obtained Ag-Cu alloy powder, using an X-ray diffraction apparatus (RINT Ultimate III manufactured by Rigaku Co., Ltd.), a voltage of 40 kV, a current of 30 mA, a scanning speed of 2 ° / min, measurement was performed using a Co tube. The range of 10 to 90 ° / 2θ was measured under the condition of an interval of 0.01 °, and the crystal structure was evaluated by X-ray diffraction (XRD). The measurement results are shown in FIG. As shown in FIG. 1, a single phase of Ag and Cu was not confirmed, and it was found to be a non-eutectic alloy powder.
［実施例２］
水アトマイズにおける水圧を３０ＭＰａとした以外は、実施例１と同様の方法により、球状のＡｇ−Ｃｕ合金粉末を得た。このＡｇ−Ｃｕ合金粉末について、実施例１と同様の方法により、ＢＥＴ比表面積、タップ密度、酸素含有量、炭素含有量および粒度分布を求めた。
[Example 2]
A spherical Ag—Cu alloy powder was obtained in the same manner as in Example 1 except that the water pressure in water atomization was changed to 30 MPa. About this Ag-Cu alloy powder, the BET specific surface area, tap density, oxygen content, carbon content and particle size distribution were determined by the same method as in Example 1.
その結果、Ａｇ−Ｃｕ合金粉末のＢＥＴ比表面積は０．０６ｍ２／ｇ、タップ密度は５．５４ｇ／ｃｍ３、酸素含有量は０．０３質量％、炭素含有量は０．００５質量％であり、累積１０％粒子径（Ｄ１０）は６．５μｍ、累積２５％粒子径（Ｄ２５）は９．４μｍ、累積５０％粒子径（Ｄ５０）は１５．０μｍ、累積７５％粒子径（Ｄ７５）は２６．０μｍ、累積９０％粒子径（Ｄ９０）は４０．３μｍ、累積９９％粒子径（Ｄ９９）は６８．３μｍであった。 As a result, the BET specific surface area of the Ag—Cu alloy powder was 0.06 m 2 / g, the tap density was 5.54 g / cm 3 , the oxygen content was 0.03 mass%, and the carbon content was 0.005 mass%. Yes, the cumulative 10% particle diameter (D 10 ) is 6.5 μm, the cumulative 25% particle diameter (D 25 ) is 9.4 μm, the cumulative 50% particle diameter (D 50 ) is 15.0 μm, and the cumulative 75% particle diameter ( D 75 ) was 26.0 μm, the cumulative 90% particle size (D 90 ) was 40.3 μm, and the cumulative 99% particle size (D 99 ) was 68.3 μm.
［実施例３］
水アトマイズにおける水圧を１５０ＭＰａとした以外は、実施例１と同様の方法により、球状のＡｇ−Ｃｕ合金粉末を得た。このＡｇ−Ｃｕ合金粉末について、実施例１と同様の方法により、ＢＥＴ比表面積、タップ密度、酸素含有量、炭素含有量および粒度分布を求めた。
[Example 3]
A spherical Ag—Cu alloy powder was obtained in the same manner as in Example 1 except that the water pressure in water atomization was set to 150 MPa. About this Ag-Cu alloy powder, the BET specific surface area, tap density, oxygen content, carbon content and particle size distribution were determined by the same method as in Example 1.
その結果、Ａｇ−Ｃｕ合金粉末のＢＥＴ比表面積は０．５８ｍ２／ｇ、タップ密度は４．４５ｇ／ｃｍ３、酸素含有量は０．０８質量％、炭素含有量は０．０１３質量％であり、累積１０％粒子径（Ｄ１０）は１．１μｍ、累積２５％粒子径（Ｄ２５）は１．７μｍ、累積５０％粒子径（Ｄ５０）は２．６μｍ、累積７５％粒子径（Ｄ７５）は３．７μｍ、累積９０％粒子径（Ｄ９０）は５．０μｍ、累積９９％粒子径（Ｄ９９）は８．２μｍであった。 As a result, the BET specific surface area of the Ag—Cu alloy powder was 0.58 m 2 / g, the tap density was 4.45 g / cm 3 , the oxygen content was 0.08 mass%, and the carbon content was 0.013 mass%. Yes, cumulative 10% particle size (D 10 ) is 1.1 μm, cumulative 25% particle size (D 25 ) is 1.7 μm, cumulative 50% particle size (D 50 ) is 2.6 μm, cumulative 75% particle size ( D 75 ) was 3.7 μm, the cumulative 90% particle diameter (D 90 ) was 5.0 μm, and the cumulative 99% particle diameter (D 99 ) was 8.2 μm.
［比較例１］
（純度９９．９９質量％の）ショット銀５．０ｋｇと（純度９９．９９質量％の）銅ボール５．０ｋｇを１２００℃に加熱して溶解した溶湯をタンディッシュ下部から落下させながら、実施例１と同様の水アトマイズ装置により大気中において水圧１５０ＭＰａ、水量１６０Ｌ／分で２０℃の高圧水を吹き付けて急冷凝固させ、得られたスラリーを固液分離し、固形分を水洗し、乾燥し、解砕して得られた粉末を、水素雰囲気中において１４０℃で１０時間加熱して熱処理（水素還元処理）した後、解砕し、篩分して、球状のＡｇ−Ｃｕ合金粉末を得た。
[Comparative Example 1]
While dropping 5.0 kg of shot silver (with a purity of 99.99% by mass) and 5.0 kg of copper ball (with a purity of 99.99% by mass) at 1200 ° C., the molten metal was dropped from the bottom of the tundish while being dropped. 1 is sprayed with high pressure water of 20 ° C. at a water pressure of 150 MPa and an amount of water of 160 L / min in the atmosphere to rapidly cool and solidify, and the resulting slurry is separated into solid and liquid, and the solid content is washed with water and dried. The powder obtained by pulverization was heated in a hydrogen atmosphere at 140 ° C. for 10 hours for heat treatment (hydrogen reduction treatment), then crushed and sieved to obtain spherical Ag—Cu alloy powder. .
このようにして得られたＡｇ−Ｃｕ合金粉末について、実施例１と同様の方法により、ＢＥＴ比表面積、タップ密度、酸素含有量、炭素含有量および粒度分布を求めた。 For the Ag—Cu alloy powder thus obtained, the BET specific surface area, tap density, oxygen content, carbon content and particle size distribution were determined by the same method as in Example 1.
その結果、Ａｇ−Ｃｕ合金粉末のＢＥＴ比表面積は０．９７ｍ２／ｇ、タップ密度は３．０９ｇ／ｃｍ３、酸素含有量は０．２７質量％、炭素含有量は０．０１４質量％であり、累積１０％粒子径（Ｄ１０）は１．０μｍ、累積２５％粒子径（Ｄ２５）は１．６μｍ、累積５０％粒子径（Ｄ５０）は２．３μｍ、累積７５％粒子径（Ｄ７５）は３．４μｍ、累積９０％粒子径（Ｄ９０）は４．９μｍ、累積９９％粒子径（Ｄ９９）は９．４μｍであった。 As a result, the BET specific surface area of the Ag—Cu alloy powder is 0.97 m 2 / g, the tap density is 3.09 g / cm 3 , the oxygen content is 0.27 mass%, and the carbon content is 0.014 mass%. Yes, the cumulative 10% particle size (D 10 ) is 1.0 μm, the cumulative 25% particle size (D 25 ) is 1.6 μm, the cumulative 50% particle size (D 50 ) is 2.3 μm, and the cumulative 75% particle size ( D 75 ) was 3.4 μm, the cumulative 90% particle size (D 90 ) was 4.9 μm, and the cumulative 99% particle size (D 99 ) was 9.4 μm.
［比較例２］
水アトマイズにおける雰囲気を大気とし、水素還元を行わなかった以外は、実施例１と同様の方法により、球状のＡｇ−Ｃｕ合金粉末を得た。このＡｇ−Ｃｕ合金粉末について、実施例１と同様の方法により、ＢＥＴ比表面積、タップ密度、酸素含有量、炭素含有量および粒度分布を求めた。
[Comparative Example 2]
A spherical Ag—Cu alloy powder was obtained by the same method as in Example 1 except that the atmosphere in water atomization was air and hydrogen reduction was not performed. About this Ag-Cu alloy powder, the BET specific surface area, tap density, oxygen content, carbon content and particle size distribution were determined by the same method as in Example 1.
その結果、Ａｇ−Ｃｕ合金粉末のＢＥＴ比表面積は０．２８ｍ２／ｇ、タップ密度は４．６４ｇ／ｃｍ３、酸素含有量は０．２１質量％、炭素含有量は０．００７質量％であり、累積１０％粒子径（Ｄ１０）は２．２μｍ、累積２５％粒子径（Ｄ２５）は３．４μｍ、累積５０％粒子径（Ｄ５０）は５．５μｍ、累積７５％粒子径（Ｄ７５）は８．６μｍ、累積９０％粒子径（Ｄ９０）は１２．５μｍ、累積９９％粒子径（Ｄ９９）は１９．０μｍであった。 As a result, the BET specific surface area of the Ag—Cu alloy powder was 0.28 m 2 / g, the tap density was 4.64 g / cm 3 , the oxygen content was 0.21 mass%, and the carbon content was 0.007 mass%. Yes, cumulative 10% particle size (D 10 ) is 2.2 μm, cumulative 25% particle size (D 25 ) is 3.4 μm, cumulative 50% particle size (D 50 ) is 5.5 μm, cumulative 75% particle size ( D 75 ) was 8.6 μm, the cumulative 90% particle diameter (D 90 ) was 12.5 μm, and the cumulative 99% particle diameter (D 99 ) was 19.0 μm.
［比較例３］
水アトマイズにおける雰囲気を大気とし、水素還元温度を１４０℃とした以外は、実施例１と同様の方法により、球状のＡｇ−Ｃｕ合金粉末を得た。このＡｇ−Ｃｕ合金粉末について、実施例１と同様の方法により、ＢＥＴ比表面積、タップ密度、酸素含有量、炭素含有量および粒度分布を求めた。
[Comparative Example 3]
A spherical Ag—Cu alloy powder was obtained in the same manner as in Example 1 except that the atmosphere in the water atomization was air and the hydrogen reduction temperature was 140 ° C. About this Ag-Cu alloy powder, the BET specific surface area, tap density, oxygen content, carbon content and particle size distribution were determined by the same method as in Example 1.
その結果、Ａｇ−Ｃｕ合金粉末のＢＥＴ比表面積は０．２５ｍ２／ｇ、タップ密度は４．６８ｇ／ｃｍ３、酸素含有量は０．１４質量％、炭素含有量は０．００９質量％であり、累積１０％粒子径（Ｄ１０）は２．３μｍ、累積２５％粒子径（Ｄ２５）は３．６μｍ、累積５０％粒子径（Ｄ５０）は５．８μｍ、累積７５％粒子径（Ｄ７５）は９．３μｍ、累積９０％粒子径（Ｄ９０）は１４．２μｍ、累積９９％粒子径（Ｄ９９）は２３．３μｍであった。 As a result, the BET specific surface area of the Ag—Cu alloy powder was 0.25 m 2 / g, the tap density was 4.68 g / cm 3 , the oxygen content was 0.14 mass%, and the carbon content was 0.009 mass%. Yes, the cumulative 10% particle size (D 10 ) is 2.3 μm, the cumulative 25% particle size (D 25 ) is 3.6 μm, the cumulative 50% particle size (D 50 ) is 5.8 μm, and the cumulative 75% particle size ( D 75 ) was 9.3 μm, the cumulative 90% particle size (D 90 ) was 14.2 μm, and the cumulative 99% particle size (D 99 ) was 23.3 μm.
［比較例４］
水アトマイズにおける雰囲気を大気とした以外は、実施例１と同様の方法により、球状のＡｇ−Ｃｕ合金粉末を得た。このＡｇ−Ｃｕ合金粉末について、実施例１と同様の方法により、ＢＥＴ比表面積、タップ密度、酸素含有量、炭素含有量および粒度分布を求めた。
[Comparative Example 4]
A spherical Ag—Cu alloy powder was obtained in the same manner as in Example 1 except that the atmosphere in water atomization was air. About this Ag-Cu alloy powder, the BET specific surface area, tap density, oxygen content, carbon content and particle size distribution were determined by the same method as in Example 1.
その結果、Ａｇ−Ｃｕ合金粉末のＢＥＴ比表面積は０．２４ｍ２／ｇ、タップ密度は４．７８ｇ／ｃｍ３、酸素含有量は０．１３質量％、炭素含有量は０．００８質量％であり、累積１０％粒子径（Ｄ１０）は２．４μｍ、累積２５％粒子径（Ｄ２５）は３．７μｍ、累積５０％粒子径（Ｄ５０）は５．９μｍ、累積７５％粒子径（Ｄ７５）は９．４μｍ、累積９０％粒子径（Ｄ９０）は１４．１μｍ、累積９９％粒子径（Ｄ９９）は２３．５μｍであった。 As a result, the BET specific surface area of the Ag—Cu alloy powder was 0.24 m 2 / g, the tap density was 4.78 g / cm 3 , the oxygen content was 0.13 mass%, and the carbon content was 0.008 mass%. Yes, the cumulative 10% particle size (D 10 ) is 2.4 μm, the cumulative 25% particle size (D 25 ) is 3.7 μm, the cumulative 50% particle size (D 50 ) is 5.9 μm, and the cumulative 75% particle size ( D 75 ) was 9.4 μm, the cumulative 90% particle diameter (D 90 ) was 14.1 μm, and the cumulative 99% particle diameter (D 99 ) was 23.5 μm.
［比較例５］
水アトマイズにおける雰囲気を大気とし、水素還元温度を３００℃とした以外は、実施例１と同様の方法により、球状のＡｇ−Ｃｕ合金粉末を得た。このＡｇ−Ｃｕ合金粉末について、実施例１と同様の方法により、ＢＥＴ比表面積、タップ密度、酸素含有量、炭素含有量および粒度分布を求めた。
[Comparative Example 5]
A spherical Ag—Cu alloy powder was obtained in the same manner as in Example 1 except that the atmosphere in water atomization was air and the hydrogen reduction temperature was 300 ° C. About this Ag-Cu alloy powder, the BET specific surface area, tap density, oxygen content, carbon content and particle size distribution were determined by the same method as in Example 1.
その結果、Ａｇ−Ｃｕ合金粉末のＢＥＴ比表面積は０．２０ｍ２／ｇ、タップ密度は３．７４ｇ／ｃｍ３、酸素含有量は０．１２質量％、炭素含有量は０．００７質量％であり、累積１０％粒子径（Ｄ１０）は３．７μｍ、累積２５％粒子径（Ｄ２５）は５．６μｍ、累積５０％粒子径（Ｄ５０）は８．２μｍ、累積７５％粒子径（Ｄ７５）は１１．７μｍ、累積９０％粒子径（Ｄ９０）は１６．４μｍ、累積９９％粒子径（Ｄ９９）は２３．７μｍであった。 As a result, the BET specific surface area of the Ag—Cu alloy powder is 0.20 m 2 / g, the tap density is 3.74 g / cm 3 , the oxygen content is 0.12% by mass, and the carbon content is 0.007% by mass. Yes, the cumulative 10% particle size (D 10 ) is 3.7 μm, the cumulative 25% particle size (D 25 ) is 5.6 μm, the cumulative 50% particle size (D 50 ) is 8.2 μm, and the cumulative 75% particle size ( D 75 ) was 11.7 μm, cumulative 90% particle diameter (D 90 ) was 16.4 μm, and cumulative 99% particle diameter (D 99 ) was 23.7 μm.
［比較例６］
水アトマイズにおける雰囲気を大気とした以外は、実施例３と同様の方法により、球状のＡｇ−Ｃｕ合金粉末を得た。このＡｇ−Ｃｕ合金粉末について、実施例１と同様の方法により、ＢＥＴ比表面積、タップ密度、酸素含有量、炭素含有量および粒度分布を求めた。
[Comparative Example 6]
A spherical Ag—Cu alloy powder was obtained in the same manner as in Example 3 except that the atmosphere in water atomization was air. About this Ag-Cu alloy powder, the BET specific surface area, tap density, oxygen content, carbon content and particle size distribution were determined by the same method as in Example 1.
その結果、Ａｇ−Ｃｕ合金粉末のＢＥＴ比表面積は０．６５ｍ２／ｇ、タップ密度は３．７９ｇ／ｃｍ３、酸素含有量は０．１４質量％、炭素含有量は０．０２８質量％であり、累積１０％粒子径（Ｄ１０）は０．９μｍ、累積２５％粒子径（Ｄ２５）は１．５μｍ、累積５０％粒子径（Ｄ５０）は２．３μｍ、累積７５％粒子径（Ｄ７５）は３．５μｍ、累積９０％粒子径（Ｄ９０）は５．５μｍ、累積９９％粒子径（Ｄ９９）は１１．２μｍであった。 As a result, the BET specific surface area of the Ag—Cu alloy powder was 0.65 m 2 / g, the tap density was 3.79 g / cm 3 , the oxygen content was 0.14 mass%, and the carbon content was 0.028 mass%. Yes, the cumulative 10% particle size (D 10 ) is 0.9 μm, the cumulative 25% particle size (D 25 ) is 1.5 μm, the cumulative 50% particle size (D 50 ) is 2.3 μm, and the cumulative 75% particle size ( D 75 ) was 3.5 μm, the cumulative 90% particle diameter (D 90 ) was 5.5 μm, and the cumulative 99% particle diameter (D 99 ) was 11.2 μm.
また、実施例１〜３と比較例２、４および６で得られたＡｇ−Ｃｕ合金粉末について、熱機械的分析（ＴＭＡ）を行って、Ａｇ−Ｃｕ合金粉末の収縮率を求めた。Ａｇ−Ｃｕ合金粉末の収縮率（％）は、Ａｇ−Ｃｕ合金粉末０．１ｇを円筒形の金型に入れ、９８０ｍＮの荷重をかけて成形した試料を、熱機械的分析装置（株式会社日立ハイテクサイエンス製のＴＭＡ／ＳＳ６２００）を用いて、窒素雰囲気中において室温から８００℃まで昇温速度１０℃／分で加熱した場合の試料の長さを測定して、｛（加熱前の試料の長さ）−（加熱後の試料の長さ）｝×１００／（加熱前の試料の長さ）から求めた。その結果、４００℃における収縮率は、実施例１では１．２％（膨張率−１．２％）、実施例２では０．４％（膨張率−０．４％）、実施例３では４．９％（膨張率−４．９％）、比較例２では１．７％（膨張率−１．７％）、比較例４では１．７％（膨張率−１．７％）、比較例６では１０．０％（膨張率−１０．０％）であった。 Moreover, about the Ag-Cu alloy powder obtained in Examples 1-3 and Comparative Examples 2, 4, and 6, the thermomechanical analysis (TMA) was performed and the shrinkage rate of Ag-Cu alloy powder was calculated | required. The shrinkage rate (%) of the Ag—Cu alloy powder was determined by placing a sample obtained by placing 0.1 g of the Ag—Cu alloy powder in a cylindrical mold and applying a load of 980 mN to a thermomechanical analyzer (Hitachi Co., Ltd.). Using a high-tech science TMA / SS6200), the length of the sample when heated from room temperature to 800 ° C. at a heating rate of 10 ° C./min in a nitrogen atmosphere was measured, and {(length of the sample before heating) )-(Length of sample after heating)} × 100 / (length of sample before heating). As a result, the shrinkage rate at 400 ° C. was 1.2% (expansion rate −1.2%) in Example 1, 0.4% (expansion rate −0.4%) in Example 2, and in Example 3. 4.9% (expansion coefficient -4.9%), Comparative Example 2 1.7% (expansion coefficient -1.7%), Comparative Example 4 1.7% (expansion coefficient -1.7%), In Comparative Example 6, it was 10.0% (expansion rate-10.0%).
これらの実施例および比較例のＡｇ−Ｃｕ合金粉末の製造条件および特性を表１および表２に示す。また、熱機械的分析の結果を図２〜図６に示す。 Tables 1 and 2 show the production conditions and characteristics of the Ag—Cu alloy powders of these examples and comparative examples. Moreover, the result of a thermomechanical analysis is shown in FIGS.
表１〜表２からわかるように、実施例１〜３では、粒子径が小さく、酸素含有量が（０．１質量％以下と）低く且つ加熱による収縮率が低いＡｇ−Ｃｕ合金粉末を得ることができる。 As can be seen from Tables 1 and 2, in Examples 1 to 3, Ag-Cu alloy powders having a small particle diameter, a low oxygen content (less than 0.1% by mass), and a low shrinkage rate due to heating are obtained. be able to.
また、図３に示すように、窒素雰囲気中で水アトマイズを行って得られた実施例１〜３のＡｇ−Ｃｕ合金粉末では、４００℃における収縮率が、それぞれ１．２％、０．４％、４．９％と低く、粒径が大きいほど加熱による収縮率が小さくなることがわかる。また、図４に示すように、大気雰囲気中で水アトマイズを行って得られた比較例４および６のＡｇ−Ｃｕ合金粉末でも、粒径が大きいほど加熱による収縮率が小さくなることがわかる。さらに、図５および図６に示すように、窒素雰囲気中で水アトマイズを行って得られた実施例１および３のＡｇ−Ｃｕ合金粉末では、大気雰囲気中で水アトマイズを行って得られた比較例４および６のＡｇ−Ｃｕ合金粉末と比べて、加熱による収縮率が小さくなることがわかる。
Moreover, as shown in FIG. 3, in the Ag-Cu alloy powders of Examples 1 to 3 obtained by performing water atomization in a nitrogen atmosphere, the shrinkage rates at 400 ° C. are 1.2% and 0.4%, respectively. %, 4.9%, and it can be seen that the larger the particle size, the smaller the shrinkage due to heating. Moreover, as shown in FIG. 4, it can be seen that, even in the Ag—Cu alloy powders of Comparative Examples 4 and 6 obtained by performing water atomization in an air atmosphere, the shrinkage rate due to heating decreases as the particle size increases. Further, as shown in FIG. 5 and FIG. 6, the Ag—Cu alloy powders of Examples 1 and 3 obtained by performing water atomization in a nitrogen atmosphere were compared with those obtained by performing water atomization in the air atmosphere. Compared to the Ag—Cu alloy powders of Examples 4 and 6, it can be seen that the shrinkage rate due to heating is small.
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