201033380 . 六、發明說明： 【發明所屬之技術領域】 本發明，係關於提供一種燒結含油轴承等粉末户金用 原料粉所使用的青銅系燒結粉，特別是關於一種適於小型 化之燒結含油軸承之製造之微細粒子尺寸的青銅合金粉。 【先前技術】 燒結含油軸承，係藉由以粉末冶金法來進行 用燒結體中之原料粉末粒子間的間隙（空孔）， 於此空孔，而可在不供油下來使用。 適於燒結含油轴承之材質，常使用銅中含H)%左右之 錫的合金（青銅合金）。而青銅系燒結含油轴承之原料粉末， 則是使用鋼粉與錫粉之混合粉末或青銅合金粉末。 使用混合粉末的情形，由於錫粉會在燒結過程溶解， 於銅粉中擴散、合金化，故在燒結體會出現錫粉炼解所產 生之大的空孔（流出孔）。此流出孔雖然可有效地保持潤滑 油，但是隨著轴承的小型化，並不適合存在大的空孔，故 使用不會發生流出孔之青鋼合金粉的方法逐漸被採用。 青鋼合金粉之製造方法，具有霧化法，但由於粒 近球形，故燒結前之生壓胚的強度低，於製造步驟 不規則：破裂：：片等不良情形。因Λ ’亦常使用藉由以 〆狀來提南生壓胚強度之電解銅粉與錫粉混合後加 以燒㈣行合金化再加以粉碎的燒結部分合金粉。 另方面，為了因應隨著電動機小型化之軸承的小 化與軸接觸之軸承内周面的空孔，係被要求更微細且均 201033380 勻的分布。因此， ’所使用之原料粉末亦有必要使用較以往201033380. [Technical Field] The present invention relates to a bronze-based sintered powder for use in sintering raw materials such as oil-impregnated bearings and the like, and more particularly to a sintered oil-containing material suitable for miniaturization. Bronze alloy powder of fine particle size manufactured by bearings. [Prior Art] The sintered oil-impregnated bearing can be used without oil supply by performing a gap (pores) between the raw material powder particles in the sintered body by powder metallurgy. Suitable for sintering oil-impregnated bearings, alloys (bronze alloys) containing about 2% of tin in copper are often used. The raw material powder of the bronze-based sintered oil-impregnated bearing is a mixed powder of steel powder and tin powder or a bronze alloy powder. In the case of using a mixed powder, since the tin powder is dissolved in the sintering process and diffused and alloyed in the copper powder, large pores (outflow holes) generated by the tin powder refining occur in the sintered body. Although the outflow hole can effectively hold the lubricating oil, it is not suitable for the presence of large pores as the bearing is miniaturized, so that a method of using the green steel alloy powder which does not flow out of the hole is gradually employed. The method for producing the green steel alloy powder has an atomization method, but since the particles are nearly spherical, the strength of the green compact before sintering is low, and the manufacturing steps are irregular: rupture:: sheet and the like. Since Λ' is also often used, a sintered partial alloy powder which is obtained by mixing the electrolytic copper powder of the strength of the green embossing with the tin powder and then alloying it and then pulverizing it. On the other hand, in order to reduce the size of the bearing which is miniaturized with the motor and the hole in the inner peripheral surface of the bearing which is in contact with the shaft, it is required to be finer and evenly distributed in 201033380. Therefore, it is necessary to use the raw material powder used.
微細’則粉末的流動性就越加惡化。The fineness of the powder is deteriorated.
微細且均—之空孔的燒結含油軸承， 雖然可以得到分布有 ，但是粉末的流動性 差會有於加壓機之成形時原料粉無法充分填充於金屬模 具'且無法加快成形速度等使生產性下降的問題。 本發明人，先前曾提出一種使用尺寸不同之2種的電 解銅粉來製造燒結用青銅粉的方法（參照專利文獻i卜此方 法，流動性獲得提升，成形性亦獲得提高，顯示出作為青 銅之燒結體的良好特性。然而，此燒結用青銅粉，由於是 要得到大致上為完全的青銅粉，因此會有製造成本高、未 必可滿足要求的問題。 而為了對其加以改良，係進行了提高粉末之壓粉密度、 磨耗值（rattler value)等之成形性，並提升徑向壓碎強度 (radial crushing strength)等之燒結特性，進而可使成本降低 化之用以製造銅一錫糸粉的發明（參照專利文獻2)。此可有 效作為解決上述問題的方法。 本發明，係在此等製造青銅合金粉之一連串技術的過 程中，進一步提供一種用以得到適合製造小型化之燒結含 油轴承之微細粒子尺寸之青銅合金粉的技術。 專利文獻1 :日本特開昭62- 67102號公報 專利文獻2 : W02006/ 126353公報 201033380 【發明内容】 作為it相關機器等之各種電動機之軸承使用的燒結含 油抽承’隨著電動機的小型化，軸承本身的大小亦隨之小 型化，本發明之課題，係在於提供一種適合製造此小型化 之燒結含油轴承之微細粒子尺寸的青銅合金粉。且同時課 題在於得到一種即使是微細的原料粉末亦不會降低生產性 之具有流動性的青銅合金粉。 本發明人等得到下述見解：藉由使用以一 2〇〇Mesh之電 ® 解鋼粉作為原料的燒結青銅合金粉，並改進燒結條件，可 解決上述問題。 本發明根據此見解，提供： 1)一種燒結青銅合金粉之製造方法，其特徵在於，於還 原環境氣氛中以300°c〜600°c對以錫粉之配合比率8〜 llwt·%混合一 200Mesh之電解銅粉與_35〇Mesh之錫粉而 成的銅一錫混合粉加以燒結然後加以粉碎的預燒結步驟、 與再次於還原環境氣氛中以5〇〇。〇〜7〇〇。(：對經預燒結之粉 末加以燒結的正燒結步驟之後，對此燒結粉末進行粉碎、 篩選。 又，本發明提供一種燒結青銅合金粉之製造方法，其 特徵在於，係由下述步驟所構成： 對- 200Mesh之電解銅粉進行鐘錫而得到踢成為2〜 l〇wt%之複合粉末的步驟； 對該經鍍錫之銅所構成之複合粉末配合一 35〇Mesh之 錫氣將錫的比率調整成8〜】lwt%以得到混合粉的步驟； 於還原環境氣氛巾以則。c〜儀。c將此混合粉加以燒 201033380 結後再加以粉碎的預燒結步驟； 再次於還原環境氣氛中以50(rc〜700t將經預燒結之 粉末加以燒結的正燒結步驟； 進一步對此燒結粉末進行粉碎、篩選的步驟。 本發明之燒結青銅合金粉之製造方法，具有下述優異 之效果：可提供適合製造小型化之燒結含油軸承之微細粒 子尺寸的青銅合金粉，並且可得到即使為微細之原料粉， 亦不會使生產性下降之具有流動性的青鋼合金粉。 【實施方式】 本發明之粉末冶金用原料粉所使用的電解銅粉，雖然 一般係藉由電解法之步驟來製造，但是可使用以此方式所 製造之通常的電解銅粉（資料「新版粉末冶金」，渡邊尚著， 技術書院發行，昭和62年10月15日第5冊發行，參照第 15〜17頁）。 本發明’係使用以此方式所製造之電解銅粉的〜 200Mesh(小於200Mesh)之電解銅粉。此—2〇〇Mesh相當於 75// m(小於75# m)。超過此尺寸之電解銅粉，難以製造 微細的燒結青銅合金粉。 作為混合之錫粉，可使用通常之霧化錫粉。此錫粉， 係使用—350Mesh(小於350Mesh)之錫粉。此相當於一45“ m(小於45 // m)。此時’超過此尺寸之錫粉，由於無法充分 混合，故亦難以製造微細的燒結青銅合金粉。 然後’以錫粉之配合比率8〜1 lwt.%加以混合，得到 銅一錫混合粉。此混合比例雖為任意，但作為一般的燒結 201033380 含油軸承合金，係使其合於9wt.%錫或10wt %錫之銅〜錫 混合粉之故。 接著，於還原環境氣氛中以300。(：〜600°C對銅一錫混 合粉進行預燒結。若未達30(TC，則錫粉將不會發生變化， 與僅是混合之狀態並無不同，因此使其在3〇(rc以上。又， 若於超過600<>C之溫度，燒結塊會變得過硬，若將其加以粉 碎，則粉末形狀會呈圓形，使成型性變差，因此必須使其 在600°C以下。 八The sintered oil-impregnated bearing of the fine and uniform pores can be distributed, but the fluidity of the powder is poor, and the raw material powder cannot be sufficiently filled in the metal mold during the molding of the press machine, and the molding speed cannot be accelerated, so that productivity is obtained. The problem of falling. The present inventors have previously proposed a method of producing bronze powder for sintering using two kinds of electrolytic copper powders having different sizes (refer to the patent document i, the liquidity is improved, the formability is also improved, and it is shown as bronze. The good characteristics of the sintered body. However, since the bronze powder for sintering has a substantially complete bronze powder, there is a problem that the manufacturing cost is high and the requirements are not necessarily satisfactory. The moldability of powder compaction density, rattler value, etc. is increased, and the sintering characteristics such as radial crushing strength are improved, and the cost can be reduced to produce copper-tin-bismuth. The invention of powder (refer to Patent Document 2). This can be effectively used as a method for solving the above problems. The present invention further provides a sintering process suitable for manufacturing miniaturization in the process of manufacturing a series of bronze alloy powders. A technique of a bronze alloy powder having a fine particle size of an oil-impregnated bearing. Patent Document 1: Japanese Patent Laid-Open No. 62-67102 Document 2: W02006/ 126353 publication 201033380 [Summary of the invention] The sintered oil-impregnated suction used for the bearings of various motors such as the IT-related machine is reduced in size as the size of the motor is reduced, and the size of the bearing itself is also reduced. A bronze alloy powder having a fine particle size suitable for the production of the miniaturized sintered oil-impregnated bearing is provided, and at the same time, a bronze alloy powder having fluidity which does not reduce productivity even with a fine raw material powder is obtained. The present inventors have found that the above problem can be solved by using a sintered bronze alloy powder using a 2 Å Mesh electric steel solution as a raw material, and improving the sintering conditions. The present invention provides: 1) A method for producing a sintered bronze alloy powder, characterized in that a 200 Mesh electrolytic copper powder and _35 are mixed at a mixing ratio of 8 to llwt·% of tin powder in a reducing atmosphere at a mixing ratio of 300 ° C to 600 ° C. a pre-sintering step of sintering a copper-tin mixed powder of 锡Mesh tin powder and then pulverizing it, and again in a reducing atmosphere 5〇〇. 〇~7〇〇. (: After the positive sintering step of sintering the pre-sintered powder, the sintered powder is pulverized and screened. Further, the present invention provides a method for producing a sintered bronze alloy powder, which is characterized by the following steps : The step of - 200Mesh electrolyzed copper powder is carried out by adding a tin to a composite powder of 2 to l〇wt%; the composite powder composed of the tinned copper is combined with a 35 〇 Mesh tin gas to be tin The ratio is adjusted to 8~] lwt% to obtain the mixed powder; the reducing atmosphere is used to reduce the ambient temperature. c~ instrument. c the mixed powder is burned 201033380 and then pulverized by the pre-sintering step; A positive sintering step of sintering the pre-sintered powder by 50 (rc to 700 t; further pulverizing and screening the sintered powder. The method for producing the sintered bronze alloy powder of the present invention has the following excellent effects: It is possible to provide a bronze alloy powder suitable for producing a fine particle size of a sintered oil-impregnated bearing, and it is possible to obtain a fine raw material powder without causing productivity. The electrolytic copper powder used for the raw material powder for powder metallurgy of the present invention is generally produced by the steps of an electrolytic method, but can be produced in this manner. Ordinary electrolytic copper powder (data "new version of powder metallurgy", Watanabe is still available, published by the Technical College, issued on the 15th of October 15, 62, see pages 15 to 17). The present invention is used in this way. Manufactured electrolytic copper powder ~ 200Mesh (less than 200Mesh) electrolytic copper powder. This - 2 〇〇 Mesh is equivalent to 75 / / m (less than 75 # m). Exceeding this size of electrolytic copper powder, it is difficult to manufacture fine sintered bronze Alloy powder. As a mixed tin powder, the usual atomized tin powder can be used. This tin powder is a tin powder of -350 Mesh (less than 350 Mesh). This is equivalent to a 45" m (less than 45 // m). When the tin powder exceeding this size is not sufficiently mixed, it is difficult to produce fine sintered bronze alloy powder. Then, 'the mixture ratio of the tin powder is 8 to 1 lwt.% to obtain a copper-tin mixed powder. Although the mixing ratio is arbitrary, For general sintering 201033380 oil bearing alloy, it is made of 9wt.% tin or 10wt% tin copper to tin mixed powder. Next, in the reducing environment atmosphere to 300. (: ~ 600 ° C for copper one The tin mixed powder is pre-sintered. If it is less than 30 (TC, the tin powder will not change, and it is not different from the state of only mixing, so it is 3 〇 or more. If it exceeds 600 <>C, the agglomerate will become too hard, and if it is pulverized, the shape of the powder will be round, and the moldability will be deteriorated, so it is necessary to make it at 600 ° C or lower.
一接著將此預燒結粉加以粉碎後，再次於還原環境氣 氛中以50(TC〜70(TC進行正燒結。此時，若未達5〇(rc，則 燒結將不會進行，而無法改善流動性，因此係在5〇〇。〇以上 來進行燒結。又，若以超過7〇(rc之溫度，則燒結塊會變得 過硬粉碎後之粉末形狀會呈圓形，使成型性變差，因此 必須使其在700。。以下。將此燒結粉末加以粉碎，視需要進 行篩選，以去除粗粉，得到燒結青銅合金粉。 ,、述方式所製得之燒結青鋼合金粉，能輕易粉碎， 可得到l〇〇Mesh之燒結青銅合金微粉。 在以此方式進行預燒結與正燒結之2階段的燒結，於預 鲈 可某程度使錫擴散，部分地使其合金化，而於正燒 、一係為了進—步使錫擴散於鋼。藉此，相較於以往之！ 段的燒結，除·Γ I，仓 粉的缺點，亦即：ΓΓΓ 同時亦可改善使用微 青銅人^ 性下降的問題。以此方式所得之燒結 維持：分：流=為微粉’流動度係在術⑽以下，可 於上述中 雖顯示將錫粉配合於電解銅粉加以混合， 201033380 但是亦可預先對電解銅粉施以鍍錫。此情形，銅與錫之混 合狀態將會變得更加良好，當燒結結束時，具有可更加促 進鋼與錫之合金化的效果。 此情形，係首先對一200Mesh之電解銅粉進行鍍錫使成 為2〜l〇wt%錫，得到複合粉末。然後，於此鍍錫之銅所構 成之複合粉末配合一3 50Mesh之錫粉，得到將錫的比率調整 成8〜1 lwt%的混合粉。 以下，經過與前述同樣的步驟。亦即’於還原環境氣 氣中以300 C〜600 C將此混合粉加以燒結，進行預燒結， 將其加以粉碎之後，再次於還原環境氣氛中以5〇〇<t〜7〇〇〇c 進行正燒結。進一步將此燒結粉末加以粉碎 '篩選，來製 造燒結青銅合金粉。 藉此’相較於以往之1段的燒結，除了可進一步進行 合金化外，且同時亦可進一步改善使用微粉的缺點，亦即 流動性下降的問題。以此方式所得之燒結青銅合金粉，流 動度係在40s/ 50g以下’可維持充分之流動性。 實施例 接著’說明本發明之實施例。另，本實施例僅為一例 示，並非受到此例示之限制。亦即，於本發明之技術思想 的範圍内’亦包含實施例以外之全部態樣或變形。 (實施例1) 於還原環境氣氛中以50〇t對混合一200Mesh( — 75 /z 之電解銅粉91wt·%與一35〇Mesh(—45/zm)之錫粉9wt·% 所得之Cu — 9% Sn混合粉進行預燒結30分鐘。 此預燒結後’稍微加以粉碎，以1 〇〇Mesh( 1 50 /z m)之筛 201033380 將粗粉加以去除。進一步於還原環境氣氛中以65〇艺對此粉 末進行正燒結30分鐘。然後，將其加以粉碎，以i〇〇Mesh(i5〇 # m)之篩將粗粉加以去除，得到燒結青銅合金粉。 上述實施例1所使用之—2〇〇Mesh(—乃以⑷之電解銅 粉的粉末特性（視密度、流動度、粒度分布）示於表丨。此粉 末本身的流動度差，並不會流動。此電解銅粉之顯微鏡照 片示於圖1。視密度為2_10g/ cm3。另，電解銅粉，於以下 之實施例及比較例中亦有使用。 於實施例1所得之燒結青銅合金粉的粉末特性（視密 度、流動度、粒度分布）示於表2。如此表2所示，視密度 為2.24g/cm3，流動度為24.6(s/50g)，可得到能夠使用的 流動性。於實施例1所製得之燒結青銅合金粉的顯微鏡照 片示於圖2。 又’此燒結青鋼合金粉之生壓胚強度（磨耗值）示於表 3。此係生壓胚密度為6.0g/ cm3的磨耗值。於實施例1中， 得到1.3%之磨耗值。係得到適當之生壓胚強度（磨耗值）。 特性項目 原料銅粉 視密度（g/cm3) 2.10 流動度（s/50g) (不會流動） 粒度分布（％) + 150^m 0.0 +106//m 0.0 +75^m 1 0.1 + 63 /zm 5.2 + 45//m 12.1 —45^m 82.6 201033380 [表2】 特性項目 實施例1 實施例2 實施例3 實施例4 實施例5 視密度(g/cm3) 2.24 2.34 1.95 2.01 2.44 流動度（s/50g) 24.6 21.4 33.6 30.3 20.5 粒度分布（％) +150/zm 0.0 0.1 0.1 0.0 0.1 +106/zm 9.2 10.5 11.3 3.4 12.6 + 75"m 13.3 13.4 15.1 7.0 16.2 + 63 μ m 15.1 11.4 12.3 10.3 18.2 + 45 βπι 27.6 18.5 25.2 22.5 27.6 —45 /zm 34.8 46.1 36.1 56.8 25.3 特性項目 實施例6 比較例1 比較例2 比較例3 比較例4 視密度（g/cm3) 2.55 2.87 1.87 2.66 1.90 流動度（s/50g) 19.1 21.3 不會流動 22.4 不會流動 粒度分布（％) + 150^m 0.2 0.2 0.1 0.2 0.1 + 106//m 15.1 34.2 5.5 26.4 10.2 + 75 jum 18.6 26.3 6.3 30.8 16.7 + 63 18.0 11.1 10.5 13.3 13.4 + 45/zm 28.7 12.6 23.5 13.8 26.5 —45 19.4 15.6 54.1 15.5 33.1 [表3] 特性項目 實施例1 實施例2 實施例3 實施例4 實施例5 磨耗值（％) 1.3 2.3 0.8 0.7 3.7 特性項目 實施例6 比較例1 比較例2 比較例3 比較例4 磨耗值（％) 5.8 15.2 1.1 13.1 3.8 註）生壓胚密度：6.0g/cm3之磨耗值之比較。 201033380 (實施例2) 於還原環境氣氛中以30(TC對混合一200Mesh( — 75 " m)之電解銅粉91wt.%與- 350Mesh(—45"m)之錫粉9以 %所得之Cu—9% Sn混合粉進行預燒結3〇分鐘。接著，對 其以100Mesh(l 50 // m)之篩將粗粉加以去除。於還原環境氣 氛中以700°C對此粉末進行正燒結3〇分鐘。並且，將其加 以粉碎，然後以100MeSh(150#m)之篩將粗粉加以去除，得 到燒結青銅合金粉。 此結果不於表1、表2、表3。原料銅粉，係使用與實 施例1同樣的銅粉。如表2所示，視密度為2 34g/cm3， 流動度〜為21.4(s/50g)，可得到能夠使用的流動性。 又’此燒結青銅合金粉之生壓胚強度（磨耗值）如表3所 示，得到2 · 3 %的磨耗值。係得到適當之生壓胚強度（磨耗 值）。另，與實施例1同樣地，生壓胚密度為6 〇g/cm3之 磨耗值。 (實施例3) 於對一 200Mesh(—75# m)之電解銅粉鍍錫而成之〜含 有量為5.5%的鍍錫之銅粉，加入_35〇1^811(_45仁111)的錫 粉，得到銅與錫之比率調整成91wt % : 9wt%之混合粉， 於還原環境氣氛中以50CTC對此混合粉進行預燒結3〇分 鐘。接著，稍微將其加以粉碎，以1〇〇Mesh(15〇私m)之篩將 粗粉加以去除後，於還原環境氣氛中以6 5 〇 t對此粉末進行 正燒結30分鐘。並且，將其加以粉碎，以1〇〇Mesh(i5〇“ m)之篩將粗粉加以去除，製得燒結青銅合金粉。 此、、’α果示於表1、表2、表3。原料銅粉，係使用與實 11 201033380 施例1同樣的銅粉。如表2所示，視密度為19化/咖3， 流動度為33.6(s/ 50g)，雖較實施例i、2差，但可得到能 夠使用的流動性。 又，此燒結青銅合金粉之生壓胚強度（磨耗值）如表3所 示，得到0.8%的磨耗值。係得到適當之生壓胚強度（磨耗 值）。另，與實施例1同樣地，生壓胚密度為6 〇g/ cm3之 磨耗值。 (實施例4) 於還原環境氣氛中以300。(：對混合一200Mesh(— 75" ❹ m)之電解銅粉91wt.%與- 350MeSh(-45//m)之錫粉9wt %所得之Cu—9% Sn混合粉進行預燒結3〇分鐘。接著，對 其以100Mesh(l 50 // m)之篩將粗粉加以去除。於還原環境氣 氛中以500°C對此粉末進行正燒結30分鐘。並且，將其加 以粉碎，然後以100Mesh(150 v m)之篩將粗粉加以去除，得 到燒結青銅合金粉。 此結果示於表1、表2、表3。原料銅粉，係使用與實 施例1同樣的銅粉。如表2所示，視密度為2.01g/cm3， 〇 流動度為30.3(s/5 0g)，可得到能夠使用的流動性。 又’此燒結青銅合金粉之生壓胚強度（磨耗值）如表3所 示’得到0.7%的磨耗值。係得到適當之生壓胚強度（磨耗 值）。另’與實施例1同樣地，生壓胚密度為6.0g/ cm3之 磨耗值。 (實施例5) 於還原環境氣氛中以600°C對混合一 200Mesh( — 75 # m)之電解銅粉91wt.%與一350Mesh(—45em)之錫粉9wt. 12 201033380 %所得之Cu—9% Sn混合粉進行預燒結3〇分鐘。接著，對 其以100Mesh(150em)之篩將粗粉加以去除。於還原環境氣 氛中以500°C對此粉末進行正燒結3〇分鐘。並且，將其加 以粉碎，然後以i 0〇MeSh(150 " m)之篩將粗粉加以去除，、得 到燒結青銅合金粉。 此結果示於表1、表2、表3 ^原料銅粉，係使用與實 施例1同樣的銅粉。如表2所示，視密度為2.44g/ cm3， 流動度為20.5(s/ 50g)，可得到能夠使用的流動性。 又，此燒結青銅合金粉之生壓胚強度（磨耗值）如表3所 示，得到3.7%的磨耗值。係得到適當之生壓胚強度（磨耗 值）。另’與實施例1同樣地，生壓胚密度為6 〇g/cm3之 磨耗值：。 (實施例6) 於還原環境氣氛中以600。(：對混合一 2〇〇MesM _ 75 y m)之電解銅粉91wt.%與—35〇Mesh(_45ym)之錫粉9wt. %所得之Cu— 9% Sn混合粉進行預燒結3〇分鐘。接著，對 ^ 其以l〇〇Mesh(15〇vm)之篩將粗粉加以去除。於還原環境氣 氛中以700°C對此粉末進行正燒結3〇分鐘。並且，將其加 以粉碎，然後以100Mesh(l50/Zm)之筛將粗粉加以去除，得 到燒結青銅合金粉。 此結果示於表1、表2、表3。原料銅粉，係使用與實 施例1同樣的銅粉。如表2所示，視密度為2>55g/em3， 流動度為19.1(s/50g)，可得到能夠使用的流動性。 又，此燒結青銅合金粉之生壓胚強度（磨耗值）如表3所 示，得到5.8%的磨耗值。係得到適當之生壓胚強度（磨耗 13 201033380 值）。另，與實施例i同樣地，生壓胚密度為6〇g/cm3之 磨耗值。 (比較例1) 於還原環境氣氛中以500°C對混合—2〇〇Mesh( _ 75 v m)之電解銅粉91就％與一35〇Mesh(—45#m)之錫粉 %所得之Cu-9% Sn混合粉進行預燒結3〇分鐘後，稍微加 以粉碎，以100Mesh(150# m)之篩將粗粉加以去除。接著， 於還原環境氣氛中以75(TC對此粉末進行燒結3〇分鐘。並 且，將其加以粉碎，然後以100Mesh(15〇 # m)之篩將粗粉加 q 以去除’製得燒結青銅合金粉。 此結果示於表1、表2、表3。原料銅粉，係使用與實 施例1同樣的銅粉。於此比較例i中，正燒結之溫度為75〇 C，係以咼於本發明之條件的溫度進行燒結的結果。 視密度為2.87g/cm3,流動度係21.3(s/5〇g)之能夠使 用的流動性，但燒結塊變硬，故難以粉碎，粉碎粉之形狀 呈圓形。此燒結青銅合金粉之顯微鏡照片示於圖3。此結 果’為生壓胚強度之指標的磨耗值惡化至。又，粉 ❹ 碎後之篩選中，粗粉（+ 100Mesh)在3〇%以上，生產性變差。 (比較例2) 於還原環境氣氛中以65(TC對混合一200Mesh( — 75 v 111)之電解銅粉91;^%與一35〇厘以}1(_45“〇1)之錫粉9〜 %所得之Cu〜9%Sn混合粉進行燒結30分鐘後，加以粉 碎，以l〇〇MeSh(l50#m)之篩將粗粉加以去除，製得燒結青 銅合金粉。 此、纟。果示於表1、表2、表3。原料鋼粉，係使用與實 14 201033380 施例1同樣的銅粉。於此比較例2中，不進行預燒結，係 以一次燒結來製造燒結青銅合金粉的情形。視密度為1 87g / cm3。另一方面，粉末之流動度差，測量流動度時因無法 從漏斗連續地流下而停止，故無法測量流動度。為生壓胚 強度之指標的磨耗值為1.丨％。 (比較例3) 於還原環境氣氛中以250°C對混合一200Mesh(—75从 m)之電解銅粉91败％與—35〇Μ_(—45em)之錫粉9wt _ %所得之9% Sn混合粉進行預燒結3〇分鐘後，稍微加 以粉碎，以lOOMesh(15〇/zm)之篩將粗粉加以去除。接著， 於還原環境氣氛中以75(rc對此粉末進行燒結3〇分鐘。並 且，將其加以粉碎，然後以l〇〇Mesh(150"m)之篩將粗粉加 以去除’製得燒結青銅合金粉。 此結果示於表1、表2、表3。原料銅粉，係使用與實施 例1同樣的鋼粉。於此比較例3中，預燒結溫度為25〇它， 糸乂低於本發明之條件的溫度來燒結，並且正燒結之溫度為 750 C，係以高於本發明之條件的溫度進行燒結的結果。 視密度為2.66g/cm3,流動度係22 4(s/5〇g)之能夠使 用的流動性，但燒結塊變硬，故難以粉碎，與比較例1同 樣地’粉碎粉之形狀呈圓形。 此結果，為生壓胚強度之指標的磨耗值惡化至131%。 (比較例4) 於還原環境氣氛中以65(rc對混合—2〇〇Mesh(一 75以 =)之電解鋼粉91wt.%與—3观esh(—45"m)之錫粉_ %所得之Cu — 9%Sn混合粉進行預燒結3〇分鐘後，稍微加 15 201033380 以粉碎，以100Mesh(150/z m)之篩將粗粉加以去除。接著， 於還原環境氣氛中以450t對此粉末進行燒結30分鐘。並 且，將其加以粉碎，然後以l〇OMesh(15〇/zm)之篩將粗粉加 以去除，製得燒結青銅合金粉。 此結果示於表1、表2、表3。原料銅粉，係使用與實 施例1同樣的銅粉。於此比較例4中，預燒結溫度為65〇 C，係以高於本發明之條件的溫度來燒結，並且正燒結之 溫度為45(TC，係以低於本發明之條件的溫度進行燒結的結 果。視密度A 1.90g/cm、另一方面，以此方式所得之粉 〇 末雖然並不是全部皆不會流動’但是無法從漏斗連續地流 下而會在中途間歇地流動’故無法加以測量，無法成為能 夠使用之流動性。 又，為生壓胚強度之指標的磨耗值為38%，雖為良好， 但由於流動性S，故不適合作為轴承用原料粉。 產業上之可利用性 、、士 ^上所不，藉由本發明之燒結青銅合金粉之製造方 法具有下述優異之效果··可提供—種微細粒子尺寸的I❹ 銅合金粉’並且可得到一種即使為微細之原料粉，亦不會 使生產性下降之具有流動性的青銅合金粉，因此，適用作 :燒3油軸承等粉末冶金用原料粉所使用的青銅系燒結 ;、寺別疋適於小型化之燒結含油軸承之製造之微細粒子 尺寸的青銅合金粉。 【圖式簡單說明】 係原料所使用之一 2〇〇Mesh銅粉的顯微鏡照片。 16 201033380 圖2，係實施例1所得之燒結青銅合金粉的顯微鏡照片。 圖3，係比較例1所得之燒結青銅合金粉的顯微鏡照片。 【主要元件符號說明】 無After the pulverized powder is pulverized, it is again sintered in a reducing atmosphere at 50 (TC to 70 (TC). At this time, if it is less than 5 〇 (rc, sintering will not proceed, and it cannot be improved). The fluidity is therefore sintered at a temperature of 5 〇〇 or more. If the temperature exceeds 7 〇 (the temperature of rc, the agglomerate will become too hard and the shape of the powder will be round, which will deteriorate the formability. Therefore, it is necessary to make it 700. Hereinafter, the sintered powder is pulverized, and if necessary, it is screened to remove the coarse powder to obtain a sintered bronze alloy powder, and the sintered green steel alloy powder obtained by the method can be easily used. After pulverization, a sintered bronze alloy fine powder of l〇〇Mesh can be obtained. In this way, the two-stage sintering of the pre-sintering and the positive sintering is performed, and the tin can be diffused to some extent in the pre-twisting, and partially alloyed, and Burning, the first step is to make the tin diffuse into the steel. In this way, compared with the previous! Sintering of the segment, except for the 缺点I, the shortcomings of the silo powder, namely: ΓΓΓ can also improve the use of micro bronze people ^ The problem of declining sex. The burning in this way Maintenance: minute: flow = micro-powder's fluidity is below (10), although it can be mixed with electrolytic copper powder in the above, 201033380, but tin plating can be applied to the electrolytic copper powder in advance. The mixed state of copper and tin will become better. When the sintering is finished, it has the effect of promoting the alloying of steel and tin. In this case, first, a 200Mesh electrolytic copper powder is tinned to become 2 〜l〇wt% tin, a composite powder is obtained. Then, the composite powder composed of the tin-plated copper is blended with a tin powder of 3 50 Mesh to obtain a mixed powder in which the ratio of tin is adjusted to 8 to 1 lwt%. The same procedure as described above is carried out, that is, the mixed powder is sintered at 300 C to 600 C in a reducing atmosphere, pre-sintered, pulverized, and then again in a reducing atmosphere at 5 〇〇 <;t~7〇〇〇c is subjected to positive sintering. Further, the sintered powder is pulverized and screened to produce a sintered bronze alloy powder. Thus, in comparison with the conventional one-stage sintering, in addition to further alloying, And Further, the disadvantage of using the fine powder, that is, the problem of lowering the fluidity, can be further improved. The sintered bronze alloy powder obtained in this manner has a fluidity of 40 s / 50 g or less 'to maintain sufficient fluidity. The present invention is not limited by the examples, and is intended to include all aspects or modifications other than the embodiments within the scope of the technical idea of the present invention. 1) Cu-9% mixed with a 200Mesh (-75/z electrolytic copper powder 91wt·% and a 35〇Mesh (-45/zm) tin powder 9wt·% in a reducing atmosphere at 50〇t The Sn mixed powder was pre-sintered for 30 minutes. After this pre-sintering, it was slightly pulverized, and the coarse powder was removed by a sieve of 1 〇〇Mesh (1 50 /z m) 201033380. The powder was further sintered for 30 minutes at 65 liters in a reducing atmosphere. Then, it was pulverized, and the coarse powder was removed by a sieve of i〇〇Mesh (i5〇 #m) to obtain a sintered bronze alloy powder. The powder characteristics (visual density, fluidity, particle size distribution) of the electrolytic copper powder used in the above-mentioned Example 1 are shown in Table 1. The powder itself has poor fluidity and does not The microscopic photograph of the electrolytic copper powder is shown in Fig. 1. The apparent density is 2_10 g/cm3. In addition, the electrolytic copper powder is also used in the following examples and comparative examples. The sintered bronze alloy powder obtained in Example 1 The powder characteristics (visual density, fluidity, and particle size distribution) are shown in Table 2. As shown in Table 2, the apparent density was 2.24 g/cm3 and the fluidity was 24.6 (s/50 g), and fluidity which can be used was obtained. A micrograph of the sintered bronze alloy powder prepared in Example 1 is shown in Fig. 2. Further, the green compaction strength (abrasion value) of the sintered green steel alloy powder is shown in Table 3. The density of the green compact is 6.0. The wear value of g/cm3. In Example 1, a wear value of 1.3% was obtained, and the appropriate raw briquette strength (wear value) was obtained. Characteristic item raw material copper powder apparent density (g/cm3) 2.10 fluidity (s /50g) (no flow) Particle size distribution (%) + 150^m 0.0 +106//m 0.0 +75^m 1 0.1 + 63 /zm 5.2 + 45//m 12.1 - 45^m 82.6 201033380 [Table 2] Characteristic item Example 1 Example 2 Example 3 Example 4 Example 5 Apparent density (g/cm3) 2.24 2.34 1.95 2.01 2.44 Fluidity (s/50g) 24.6 21.4 33.6 30.3 20.5 Particle size distribution (%) +150/zm 0.0 0.1 0.1 0.0 0.1 +106/zm 9.2 10.5 11.3 3.4 12.6 + 75"m 13.3 13.4 15.1 7.0 16.2 + 63 μ m 15.1 11.4 12.3 10.3 18.2 + 45 βπι 27.6 18.5 25.2 22.5 27.6 —45 /zm 34.8 46.1 36.1 56.8 25.3 Characteristic item Example 6 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Apparent density (g/cm3) 2.55 2.87 1.87 2.66 1.90 Fluidity (s/50g) 19.1 21.3 No flow 22.4 No flow particle size distribution (%) + 150^m 0.2 0.2 0.1 0.2 0.1 + 106//m 15.1 34.2 5.5 26.4 10.2 + 75 jum 18.6 26.3 6.3 30.8 16.7 + 63 18.0 11.1 10.5 13.3 13.4 + 45/zm 28.7 12.6 23.5 13.8 26.5 - 45 19.4 15.6 54.1 15.5 33.1 [Table 3] Characteristic item Example 1 Example 2 Example 3 Example 4 Example 5 Abrasion value ( %) 1.3 2.3 0.8 0.7 3.7 Characteristic project example 6 ratio Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Abrasion Value (%) 5.8 15.2 1.1 13.1 3.8 Note) Comparison of the wear density of the green compact: 6.0 g/cm3. 201033380 (Example 2) In a reducing atmosphere, 30% of TC is mixed with a 200Mesh (-75 " m) electrolytic copper powder 91wt.% and -350Mesh (-45"m) tin powder 9% The Cu-9% Sn mixed powder was pre-sintered for 3 minutes. Then, the coarse powder was removed by a sieve of 100 Mesh (l 50 // m). The powder was sintered at 700 ° C in a reducing atmosphere. 3 minutes. Further, it was pulverized, and then the coarse powder was removed by a 100 MeSh (150 #m) sieve to obtain a sintered bronze alloy powder. The results are not shown in Table 1, Table 2, and Table 3. Raw material copper powder, The same copper powder as in Example 1 was used. As shown in Table 2, the apparent density was 2 34 g/cm 3 and the fluidity was 21.4 (s/50 g), and fluidity which can be used was obtained. As shown in Table 3, the briquetting strength (abrasion value) of the powder obtained an abrasion value of 2·3%, and the appropriate raw briquette strength (abrasion value) was obtained. In the same manner as in Example 1, the green compact was produced. The wear value of the density is 6 〇g/cm3. (Example 3) The plating of the electrolytic copper powder of a 200 Mesh (-75# m) is made to a plating amount of 5.5%. The copper powder is added with _35〇1^811 (_45仁111) tin powder, and the ratio of copper to tin is adjusted to 91wt%: 9wt% mixed powder, and the mixed powder is pre-treated at 50CTC in a reducing atmosphere. Sintering for 3 minutes. Then, it was pulverized slightly, and the coarse powder was removed by a sieve of 1 〇〇Mesh (15 〇m), and then the powder was sintered at 65 〇t in a reducing atmosphere. In the minute, and pulverizing it, the coarse powder was removed by a sieve of 1 〇〇Mesh (i5〇"m) to obtain a sintered bronze alloy powder. This, 'α fruit is shown in Table 1, Table 2, Table 3. The raw material copper powder is the same copper powder as that of the example 11 201033380. As shown in Table 2, the apparent density is 19%/coffee 3, and the fluidity is 33.6 (s/50g), although compared with the example i The difference is 2, but the fluidity that can be used can be obtained. Further, the green compaction strength (abrasion value) of the sintered bronze alloy powder is as shown in Table 3, and an abrasion value of 0.8% is obtained. (Abrasion value). Similarly, in the same manner as in Example 1, the green density of the green compact was 6 〇g/cm3 (Example 4) in a reducing atmosphere. Pre-sintering of Cu-9% Sn mixed powder obtained by mixing 91 wt.% of electrolytic copper powder of 91 Mesh (-75" ❹ m) with 9 wt% of tin powder of -350 MeSh (-45//m) 3 minutes. Then, the coarse powder was removed by a sieve of 100 Mesh (l 50 // m). The powder was positively sintered at 500 ° C for 30 minutes in a reducing atmosphere. Further, it was pulverized, and then the coarse powder was removed by a 100 Mesh (150 v m) sieve to obtain a sintered bronze alloy powder. The results are shown in Table 1, Table 2, and Table 3. As the raw material copper powder, the same copper powder as in Example 1 was used. As shown in Table 2, the apparent density was 2.01 g/cm3, and the 流动 fluidity was 30.3 (s/5 0 g), and fluidity which can be used was obtained. Further, the green compaction strength (abrasion value) of this sintered bronze alloy powder was as shown in Table 3, and an abrasion value of 0.7% was obtained. The appropriate raw briquette strength (wear value) is obtained. Further, in the same manner as in Example 1, the green density of the green compact was 6.0 g/cm3. (Example 5) In a reducing atmosphere, a mixture of 200 Mesh (-75 #m) of electrolytic copper powder 91 wt.% and a 350 Mesh (-45 em) of tin powder 9 wt. 12 201033380 % Cu was mixed at 600 ° C in a reducing atmosphere. The 9% Sn mixed powder was pre-sintered for 3 minutes. Next, the coarse powder was removed by a sieve of 100 Mesh (150 cm). The powder was sintered at 500 ° C for 3 minutes in a reducing atmosphere. Further, it was pulverized, and then the coarse powder was removed by a sieve of i 0 〇 MeSh (150 " m) to obtain a sintered bronze alloy powder. The results are shown in Table 1, Table 2, and Table 3^ Raw material copper powder, and the same copper powder as in Example 1 was used. As shown in Table 2, the apparent density was 2.44 g/cm3, and the fluidity was 20.5 (s/50 g), and fluidity which can be used was obtained. Further, the green compaction strength (abrasion value) of the sintered bronze alloy powder was as shown in Table 3, and an abrasion value of 3.7% was obtained. The appropriate raw briquette strength (wear value) is obtained. Further, in the same manner as in the first embodiment, the wear density of the green compact was 6 〇g/cm3. (Example 6) At 600 in a reducing atmosphere. (: For the mixing of 2 〇〇 MesM _ 75 y m), the electrolytic copper powder 91 wt.% and the -35 〇 Mesh (_45 ym) tin powder 9 wt. % of the obtained Cu-9% Sn mixed powder were pre-sintered for 3 minutes. Next, the coarse powder was removed by a sieve of l〇〇Mesh (15〇vm). The powder was sintered at 700 ° C for 3 minutes in a reducing atmosphere. Further, it was pulverized, and then the coarse powder was removed by a 100 Mesh (l50/Zm) sieve to obtain a sintered bronze alloy powder. The results are shown in Table 1, Table 2, and Table 3. As the raw material copper powder, the same copper powder as in Example 1 was used. As shown in Table 2, the apparent density was 2 > 55 g/cm3, and the fluidity was 19.1 (s/50 g), and fluidity which can be used was obtained. Further, the green compaction strength (abrasion value) of the sintered bronze alloy powder was as shown in Table 3, and an abrasion value of 5.8% was obtained. The appropriate raw briquette strength (wearing 13 201033380 value) is obtained. Further, in the same manner as in Example i, the green density of the green compact was 6 〇 g/cm 3 . (Comparative Example 1) A mixture of -2 〇〇 Mesh ( _ 75 vm) electrolytic copper powder 91 % and a 35 〇 Mesh (-45 #m) tin powder in a reducing atmosphere at 500 ° C The Cu-9% Sn mixed powder was pre-sintered for 3 minutes, then slightly pulverized, and the coarse powder was removed by a 100 Mesh (150 #m) sieve. Next, the powder was sintered at 75 (TC) for 3 minutes in a reducing atmosphere. Further, it was pulverized, and then the coarse powder was added with a sieve of 100 Mesh (15 Å #m) to remove 'sintered bronze. The results are shown in Table 1, Table 2, and Table 3. The raw material copper powder was the same copper powder as in Example 1. In Comparative Example i, the temperature of the positive sintering was 75 〇C, which was 咼The result of sintering at the temperature of the conditions of the present invention. The apparent density is 2.87 g/cm3, and the fluidity is 21.3 (s/5 〇g). The flowability can be used, but the agglomerates become hard, so it is difficult to pulverize, and the pulverized powder The shape is circular. The micrograph of the sintered bronze alloy powder is shown in Fig. 3. The result is that the wear value of the index of the strength of the raw blast is deteriorated. Also, in the screening after the mash, the coarse powder (+ 100 Mesh ) 3% or more, the productivity is deteriorated. (Comparative Example 2) In a reducing atmosphere, 65 (TC vs. a 200 Mesh (-75 v 111) electrolytic copper powder 91; ^% and a 35 〇 }1 (_45 "〇1) tin powder 9~% of the obtained Cu~9%Sn mixed powder is sintered for 30 minutes, and then pulverized to l〇〇MeSh(l50# The coarse powder is removed by the sieve of m) to obtain a sintered bronze alloy powder. This and 纟 are shown in Table 1, Table 2, and Table 3. The raw material steel powder is the same copper powder as that of the actual example 14 201033380. In Comparative Example 2, the case where the sintered bronze alloy powder was produced by primary sintering without performing pre-sintering was observed, and the apparent density was 1 87 g / cm 3 . On the other hand, the fluidity of the powder was poor, and the fluidity was not measured. The fluidity was not continuously measured from the funnel, and the fluidity could not be measured. The wear value of the index of the strength of the green compact was 1. 丨%. (Comparative Example 3) A 200 Mesh was mixed at 250 ° C in a reducing atmosphere (( 75 from the m) electrolytic copper powder 91% of the loss and -35 〇Μ _ (-45em) tin powder 9wt _% of the obtained 9% Sn mixed powder pre-sintered for 3 〇 minutes, slightly smashed to lOOMesh (15 〇 The coarse powder is removed by a sieve of /zm). Then, the powder is sintered at 75 (rc for 3 minutes in a reducing atmosphere), and it is pulverized, and then l〇〇Mesh (150 "m) Sintered bronze powder was prepared by removing the coarse powder from the sieve. The results are shown in Table 1, Table 2, and Table 3. For the copper powder, the same steel powder as in Example 1 was used. In Comparative Example 3, the pre-sintering temperature was 25 Å, and 糸乂 was sintered at a temperature lower than the conditions of the present invention, and the sintering temperature was 750 C. The result of sintering at a temperature higher than the conditions of the present invention. The apparent density is 2.66 g/cm 3 , and the fluidity is 22 4 (s/5 〇 g), but the sintered block becomes hard, so It was difficult to pulverize, and the shape of the pulverized powder was circular as in Comparative Example 1. As a result, the wear value of the index of the strength of the green compact was deteriorated to 131%. (Comparative Example 4) In the reducing atmosphere, 65 wt.% of the electrolytic steel powder of the mixture of -2 〇〇 Mesh (a 75 ==) and the tin powder of -3 esh (-45 " m) _ % The obtained Cu-9%Sn mixed powder was pre-sintered for 3 minutes, then slightly added to 15 201033380 to be pulverized, and the coarse powder was removed by a 100 Mesh (150/zm) sieve. Then, in a reducing atmosphere, 450t was used. The powder was sintered for 30 minutes, and it was pulverized, and then the coarse powder was removed by a sieve of l〇OMesh (15 〇/zm) to obtain a sintered bronze alloy powder. The results are shown in Table 1, Table 2, and Table. 3. The raw material copper powder was the same copper powder as in Example 1. In Comparative Example 4, the pre-sintering temperature was 65 〇C, which was sintered at a temperature higher than the conditions of the present invention, and the temperature of the sintering was performed. 45 (TC, the result of sintering at a temperature lower than the conditions of the present invention. The apparent density A is 1.90 g/cm, and on the other hand, although not all of the powder obtained in this manner does not flow 'but It is impossible to continuously flow down from the funnel and will flow intermittently in the middle. Therefore, it cannot be measured, and it cannot be made In addition, the wear value of the index of the strength of the green compact is 38%, although it is good, but it is not suitable as a raw material powder for bearings because of the fluidity S. Industrial availability, By the method for producing a sintered bronze alloy powder of the present invention, the following excellent effects are provided: · A fine copper particle size I ❹ copper alloy powder can be provided and a fine raw material powder can be obtained without producing Bronze alloy powder with fluidity which is degraded, so it is suitable for use as a bronze-based sintering for powder metallurgy raw material powders such as fired 3 oil bearings; and fine particles for the manufacture of sintered oil-impregnated bearings suitable for miniaturization The size of the bronze alloy powder. [Simple description of the drawing] A micrograph of a 2 〇〇 Mesh copper powder used as a raw material. 16 201033380 Fig. 2 is a micrograph of the sintered bronze alloy powder obtained in Example 1. A micrograph of the sintered bronze alloy powder obtained in Comparative Example 1. [Explanation of main component symbols]
1717