200427533 (1) 玖、發明說明 【發明所屬之技術領域】 本發明一般係關於選擇性雷射燒結，特別（但未排除 )係關於用於選擇性雷射燒結之金屬粉末組成物，其中， 藉照光於金屬粉末層上而形成燒結層及藉由層合這樣的燒 結層，製得具所欲形狀的三維標物件。本發明亦係關於製 造金屬粉末組成物之方法及使用此金屬粉末組成物製得的 三維物件。 【先前技術】 已經知道利用選擇性雷射燒結製造三維物件之方法， 其中，光束（具方向性的能量束’如：雷射）先照射於金 屬粉末組成物層的預定部分以形成燒結層。藉此得到的燒 結層之後以新的金屬粉末組成物層覆蓋，光束照射於新層 的預定部分以形成新的燒結層，其與位於下方的層結合。 重覆實施這些方法，以形成燒結物件或三維物件，其中， 多個燒結層完全層合於另一者上。藉由控制光束的能量密 度，此方法得以得到不同狀態（包括有許多空間（孔）位 於成形物件內部的狀態和金屬粉末組成物實質上完全熔解 之後固化的狀態（即，密度（燒結密度）約100%的狀態 )的成形物件。因此，此方法可用以形成被要求具平滑表 面的模具。此外，此方法使得成形物件表面區域具高密度 ，內部區域具低密度，其間的區域具中密度。成形物件具 不同密度時，不會損及平滑表面的成形速率。 -5- (2) (2)200427533 但是，製造此具不同表面和內部密度的成形物件時， 所用金屬粉末組成物的特性必須不同於一般粉末燒結所用 金屬粉末組成物。 例如，金屬粉末組成物的粒徑必須小於各粉末層厚度 。較小粒徑提高粉末組成物的塡充密度及成形期間的光束 吸收性，並因此不僅能夠提高成形密度，同時也能降低表 面糙度。但粒徑過小有時會造成粉末組成物黏結，使粉末 組成物的塡充密度降低及使其無法均勻地形成粉末薄層。 此外，爲使成形物件具有所須強度，經光束照射的部 分和位於下方的燒結層之結合面積較大且黏合強度高。此 外，經光束照射部分必須不能於其上表面上有大幅升高或 突起。如果這樣的升高高於欲形成於其上的粉末層厚度， 有時會難以形成粉末層。 此外，因爲不必要的金屬粉末黏合於成形物件表面上 ，須加工移除不必要的金屬粉末以露出高密度表面區域， 故要求成形物件須具有良好工作性質。 成形物件表面不能有大裂紋存在，顧及流體介質（如 :冷卻水）會穿透（如：注射模塑模具），希望其內部結 構沒有細微裂紋。 經光束照射的金屬粉末組成物部分或完全熔解，之後 藉後續快速冷卻固化而轉變成燒結材料。熔解期間內的高 潤濕度提高熔融材料和鄰近燒結材料之間之結合面積，流 動性高則減少上升或突起。因此，高潤濕度和高流動性爲 所欲者。 -6- (3) (3)200427533 就前述者，此申請案的發明者提出一種金屬粉末組成 物，述於日本公開專利說明書第200 1 - 1 5 2204號。此金屬 粉末組成物含有鉻鉬鋼粉末、磷銅或錳銅粉末和鎳粉。鉻 鉬鋼因其強度或韌度而被採用，磷銅或錳銅因其潤濕性或 流動性而被採用，而鎳則因其工作性質而被採用。 前述金屬粉末組成物於得到表面區域和內部區域之間 密度不同的成形物件及改善潤濕性、流動性和工作性質（ 機械性質）方面提供良好結果。 如附圖1 1所示者，其爲自慣用金屬粉末組成物得到 的成形物件截面的2 5倍放大照片，高密度燒結部分有微 小裂紋形成於其中’此在成形物件作爲成形模具時，特別 會損及成形物件。 【發明內容】 本發明意欲克服前述缺點。 據此，本發明的一個目的是要提出一種可用於選擇性 雷射燒結的金屬粉末組成物，以於燒結時得到無微細裂紋 且成形性質優良的成形物件。 本發明的另一目的是提出一種簡便製造前述金屬粉末 組成物之方法。 本發明的另一目的是提出一種成形物件，其可作爲注 射模塑模具。 欲達到前述和其他目的，根據本發朋之金屬粉末組成 物包括以鐵爲基礎的粉末材料、鎳和/或鎳合金粉末材料 (4) (4)200427533 、銅和/或銅合金粉末材料和石墨粉末材料。此石墨粉末 材料用以改善熔解期間的潤濕性或減少固化期間的細微裂 紋。 較佳情況中，石墨粉末材料比例由0.2重量％至1.〇 重量％。如果石墨粉末材料低於0.2重量。/。或超過1.〇重量 % ’減少細微裂紋的效果降低。 更佳情況中，石墨粉末材料比例由0.2重量％至1.〇 重量％時，就減少細微裂紋或改善成形性質觀點，以鐵爲 基礎的粉末材料比例由6 0重量％至9 0重量％，鎳和/或 鎮合金粉末材料比例由5重量％至3 5重量％，銅和/或銅 合金粉末材料比例由5重量％至1 5重量％。 更特定言之’如果鎳和/或鎳合金粉末材料比例低於 5重量％ ’成形物件常有裂紋。另一方面，如果鎳和/或 鎳合金粉末材料比例超過3 5重量％，成形物件迅速冷卻 時的熱縮率大且易與成形板（如：鐵製）分離。如果銅和 /或銅合金粉末材料比例低於5重量％，熔解期間的潤濕 性或流動性（選擇性雷射燒結用材料需要者）會減損。另 一方面，如果銅和/或銅合金粉末材料比例高於1 5重量 % ’成形物件（含更多銅的鐵合金）與成形板之間的黏合 力減低，會使得成形物件與成形板分離。 以鐵爲基礎的粉末材料包括鉻鉬鋼粉末材料之時，或 者，銅合金粉末材料包括銅錳合金材料之時，添加石墨粉 末材料可進一步改善成形物件性質。 特別佳的情況中，鉻鉬鋼粉末材料比例由6 0重量％ -8 - (5)200427533 至80重: 銅f孟合金 末材料比 雖然 料及銅和 微米爲佳 徑小於鎳 料之平均 於鎳和/ 平均粒徑 如果 料或銅和 成粉末組 其難以形 粉末層厚 形。 爲使 球形且顆 石墨粉末 非球形顆 合金粉末 爲基礎的 於25微 物”，其: 量％，鎳粉末材料比例由1 5重量％至25重量％， 粉末材料比例由5重量％至〗5重量％，而石墨粉 例由0 · 2重量％至0.7 5重量。/〇。 、鐵爲基礎的粉末材料、鎳和/或鎳合金粉末材 /或銅合金粉末材料的平均粒徑以5微米至5 〇 更izt丨、胃況中’以鐵爲基礎的粉末材料的平均粒 和/或鎳合金粉末材料和銅和/或銅合金粉末材 粒徑。所用以鐵爲基礎的粉末材料的平均粒徑低 或鎳合金粉末材料及銅和/或銅合金粉末材料之 的3/4特別佳。 以鐵爲基礎的粉末材料、鎳和/或鎳合金粉末材 /或銅合金粉末材料的平均粒徑低於5微米，造 成物的黏合性，粉末組成物的流動性會降低並使 成高密度粉末層。如果平均粒徑超過5〇微米， 度無法低於5 0微米，此使其難以達到高精確成 金屬粉末組成物以高密度均勻層合，粉末顆粒以 粒尺寸分佈相當窄爲佳。但當金屬粉末組成物與 材料一起添加時，以鐵爲基礎的粉末材料主要由 粒構成且鎳和/或鎳合金粉末材料及銅和/或銅 材料主要由球形顆粒構成更佳。特別地，當以鐵 粉末材料是鉻鉬鋼粉末材料時，其平均粒徑以低 米爲佳。此金屬粉末組成物可爲“粒化的粉末組成 通常是藉由將極細粉末顆粒以黏合劑加以固化而 -9- (6) 200427533 得的球形顆粒。 製造根據本發明之金屬粉末組成物之方法的 ••將石墨薄片混入以鐵爲基礎的粉末材料、鎳和 金粉末材料及銅和/或銅合金粉末材料中，並粉 合物。此方法有利於容易操作和石墨均勻分佈。 因爲燒結前述金屬粉末組成物而得的三維物 無裂紋且內部結構中幾乎沒有細微裂紋，所以此 的表面區域和內部區域可以有密度差且可作爲注 具0 【實施方式】 此申請案係基於分別於2003年2月25日禾 7月28日於日本提出申請的第2003-48263 281 520號，茲將其中所述者全數列入參考。 附圖1說明用於選擇性雷射燒結的設備。所 括用以形成粉末層10之粉末層形成單元2、用 結層11的燒結層形成單元3及用以移除低密度 層移除單元4。粉末層形成單元形成預定厚度At 層1 〇，其方式是：先將選擇性雷射燒結施用於 動桌20 (其藉圓筒垂直移動於有限空間中）， 均化刮板21使粉末組成物均化。燒結層形成單 燒結層11，其方式是：來自雷射光產生器30的 掃描光學系統（包括反射器3 1之類）照射在粉> 。以使用雷射振盪器1〇作爲雷射光產生器30爲 特徵在於 /或鎳合 碎所得混 件表面上 三維物件 射模塑模 I 2003 年 和 2003- 示設備包 以形成燒 表層的表 1的粉末 可垂直移 之後使用 ΐ； 3形成 雷射經由 〔層1 0上 佳，以使 -10- (7) (7)200427533 用白鐵鏡作爲反射器3 1爲佳。表層移除單元4包括XY 驅動單元4 0位於粉末層形成單元2底部上及修整機4 1位 於ΧΥ驅動單元40上。以使用切割機（如：終硏磨機、 鑽孔機之類）作爲修整機械4 1爲佳。 附圖2說明如何使用前述設備製造三維物件。如此處 所示者，先將金屬粉末組成物施用於位於可垂直移動桌 2〇上方的底質22，其可作爲間距調整器以調整燒結層形 成單元3和燒結層之間的間距。施用於底質22上的粉末 組成物之後以均化刮板2 1均化以形成第一個粉末層1 0， 光束（雷射光束）L照射在第一個粉末層1 0的所欲部分 以燒結，藉此形成與底質22結合的燒結層1 1。 之後，可垂直移動桌20降低預定長度，再度施用金 屬粉末組成物並使用均化刮板2 1使其均化而形成第二個 粉末層1 〇。光束L再度照射於第二個粉末層1 0的所欲部 分以使其燒結，藉此形成另一燒結層1 1與位於下方的燒 結層1 1結合。 重覆實施在可垂直移動桌20降低之後形成新粉末層 10的程序以及光束L照射在新粉末層10所欲部分以形成 新燒結層1 1的程序’藉此製得三維標的物件。以使用 C〇2雷射作爲光束爲佳。說明書中，三維物件是成形模具 ，各粉末層的較佳厚度約〇.〇5毫米。 雷射照射路徑數據顯示器和切割路徑數據顯示器製自 事先指出所欲形狀設計的三維CAD數據。決定雷射照射 路徑時，由各部件的輪廓數據（以等距（△ Η是〇·〇5毫 -11 · (8) (8)200427533 米時，此爲〇·〇5毫米）切割得自三維CAD模型的STL數 據而得）定義目標形狀。較佳情況中，光束照射使得三維 物件的至少一個表面區域被燒結而具有高密度（如，孔隙 度低於5 % )，而三維物件內部被燒結而具低密度。換言 之，模型數據被分成用於表面區域和用於內部區域者，光 束照射條件，使得內部區域多孔而表面區域具高密度（因 大部分粉末組成物熔解於其中），使其能夠以高速得到具 緻密表面的成形物件。 形成多個燒結層11的期間內，其總厚度達由工具長 度（如：硏磨前端41)決定的特定値，表層移除單元4 經活化以切割之前已成形的三維物件表面。例如，直徑1 毫米之硏磨前端4 1的工具（球終端硏磨機）和長3毫米 的有效刮板可達3毫米切割深度。據此，如果粉末層1 〇 厚度Atl是0.05毫米，形成六十個燒結層時，表層移除 單元4被活化。 表層移除單元4可移除粉末黏合於成形物件表面而形 成的低密度表層，並可同時切除一部分高密度區域，藉此 使高密度區域外露於成形物件全表面。此處，使得燒結層 1 1形狀尺寸略大於所欲形狀。 如前述者，由三維CAD數據得到切割路徑和雷射照 射路徑。雖然由所謂的輪廓線處理決定切割路徑，切割路 徑的垂直距離不一定要與燒結期間的層合間距相同。如果 標的物件的斜面和緩，減低垂直距離可得平滑表面。 雖然在說明用的實施例中，設備包括表層移除單元4 -12- 200427533 Ο) 以進行成形期間內的切割工作，本發明亦可用於在成形期 間內未使用表層移除單元且未施以切割操作的一般選擇性 雷射燒結。 附圖3所示者是摻有石墨粉末的成形物件截面’圖中 特別可看出成形物件中的石墨點。 石墨粉末相對於金屬粉末組成物之比例以低於約1重 量％爲佳。特別地，以鐵爲基礎的粉末比例是60-90重量 %，鎳粉和/或鎳合金粉末是5 - 3 5重量％，銅粉和/或銅 合金粉末是5-15重量％時，石墨粉末比例以在0.2-1 ·〇重 量％範圍內爲佳。如果石墨粉末比例超過1重量％ ’減少 細微裂紋的效果顯著降低，使得細微產生程度類似於未添 加石墨粉末之時。 以分別使用鉻鉬鋼粉末和銅錳合金粉末作爲以鐵爲基 礎的粉末和銅合金粉末爲佳。滿足此二條件中之至少一者 時，可改善摻有石墨粉末的成形物件特性。 鉻鉬鋼粉末比例是60-80重量％時，鎳粉末是15-25 重量％，銅錳合金粉末是 5-15重量％，石墨粉末是0.2-0.7 5重量％，高密度部分沒有細微裂紋，高密度部分和低 密度部分皆可得到所欲成形性質。 較佳情況中，所有以鐵爲基礎的粉末、鎳粉和/或鎳 合金粉末和銅粉和/或銅合金粉末的平均粒徑是5-50微 米。如果顆粒直徑過小，粉末組成物會凝聚。據此，粉末 層10的厚度Atl是〇.〇5毫米時，平均粒徑設定於約30 微米。 -13- (10) (10)200427533 因爲金屬粉末組成物通常以高密度均勻層合，所以粉 末顆粒以球形且顆粒尺寸分佈較窄爲佳。但添加石墨粉末 時，較佳情況中，以鐵爲基礎的粉末材料主要由非球形顆 粒構成且鎳和/或鎳合金粉末材料及銅和/或銅合金粉末 材料主要由球形顆粒構成更佳。特別地，當以鐵爲基礎的 粉末材料是主要由非球形顆粒構成的鉻鉬鋼粉末材料時， 其平均粒徑以低於2 5微米並亦低於鎳和/或鎳合金粉末 材料或銅和/或銅合金粉末材料之平均粒徑的3/4爲佳， 此可得到良好結果。 _ 實例 使用 SCM440 (絡鉬鋼）粉末（其主要由非球形顆粒 構成，平均粒徑2 0微米，請參考附圖4 ) 、Ni (鎳）粉 末（主要由球形顆粒構成，平均粒徑3 0微米，請參考附 圖5 )和CuMnNi (銅錳合金，製自，如，Cu-1 0重量％ Mn-3重量％Ni )粉末（主要由球形顆粒構成，平均粒徑 3 〇微米，請參考附圖6 )製得六種類型的金屬粉末組成物 。此六種類型的金屬粉末組成物與下列不同比例的c (石 墨）添加。 Ο 7 0 重量 ％SCM440 - 21 重量 9 重量 0/〇 CuMnNi b) 70 重量 ％SCM440~ 21 重量％化 - 9 重量 ％ CuMnNi200427533 (1) 发明. Description of the invention [Technical field to which the invention belongs] The present invention generally relates to selective laser sintering, and in particular (but not excluded) relates to a metal powder composition for selective laser sintering, wherein The sintered layer is formed by irradiating the metal powder layer with light, and the sintered layer is laminated to obtain a three-dimensional target object having a desired shape. The present invention also relates to a method for manufacturing a metal powder composition and a three-dimensional object made using the metal powder composition. [Prior art] A method for manufacturing a three-dimensional object by selective laser sintering has been known, in which a light beam (a directional energy beam 'such as a laser) is first irradiated to a predetermined portion of a metal powder composition layer to form a sintered layer. The sintered layer thus obtained is then covered with a new metal powder composition layer, and a predetermined portion of the new layer is irradiated with a light beam to form a new sintered layer, which is combined with the layer located below. These methods are repeatedly performed to form a sintered object or a three-dimensional object, in which a plurality of sintered layers are completely laminated on the other. By controlling the energy density of the light beam, this method can obtain different states (including a state where many spaces (holes) are located inside the shaped object and a state where the metal powder composition is substantially completely melted and solidified (that is, the density (sintered density) is about 100% state). Therefore, this method can be used to form a mold that is required to have a smooth surface. In addition, this method allows the surface area of the molded object to have a high density, the inner area to have a low density, and the area in between to have a medium density. When the shaped objects have different densities, the forming rate of the smooth surface will not be impaired. -5- (2) (2) 200427533 However, when manufacturing this shaped object with different surface and internal densities, the characteristics of the metal powder composition used must be It is different from the metal powder composition used in general powder sintering. For example, the particle size of the metal powder composition must be smaller than the thickness of each powder layer. A smaller particle size improves the filling density of the powder composition and the light absorption during molding, and therefore not only It can increase the forming density and reduce the surface roughness. However, if the particle size is too small, it may cause powder The final composition is bonded, which reduces the filling density of the powder composition and prevents it from forming a thin powder layer uniformly. In addition, in order to have the required strength of the formed object, the combined area of the part irradiated with the light beam and the sintered layer located below Larger and higher adhesive strength. In addition, the part irradiated by the beam must not have a large rise or protrusion on its upper surface. If such an increase is higher than the thickness of the powder layer to be formed on it, it may sometimes be difficult to form a powder In addition, because unnecessary metal powder is adhered to the surface of the formed article, the unnecessary metal powder must be processed to remove the high-density surface area, so the formed article must have good working properties. The surface of the formed article must not have large cracks. Existing, taking into account that fluid media (such as cooling water) will penetrate (such as: injection molding molds), it is hoped that its internal structure does not have micro cracks. The metal powder composition irradiated by the beam is partially or completely melted, and then solidified by subsequent rapid cooling And converted to sintered material. High wetting during melting improves the molten material and adjacent sintered material The bonding area between them will reduce the rise or protrusion if the fluidity is high. Therefore, high wettability and fluidity are desirable. -6- (3) (3) 200427533 As for the foregoing, the inventor of this application A metal powder composition is proposed and described in Japanese Laid-Open Patent Specification No. 200 1-1 5 2204. This metal powder composition contains chromium molybdenum steel powder, phosphor copper or manganese copper powder, and nickel powder. Because of its strength or Toughness is used, phosphorous copper or manganese copper is used because of its wettability or fluidity, and nickel is used because of its working properties. The foregoing metal powder composition has different density between the obtained surface area and the internal area. It provides good results in terms of improved wettability, flowability, and working properties (mechanical properties). As shown in FIG. 11, it is a 25-fold magnification of the cross-section of the molded article obtained from the conventional metal powder composition. In the photo, micro-cracks are formed in the high-density sintered part. 'This is especially the case when the molded article is used as a molding die. SUMMARY OF THE INVENTION The present invention is intended to overcome the aforementioned disadvantages. Accordingly, it is an object of the present invention to provide a metal powder composition which can be used for selective laser sintering, so as to obtain a molded article having no micro cracks and excellent forming properties during sintering. Another object of the present invention is to propose a method for easily producing the aforementioned metal powder composition. Another object of the present invention is to provide a shaped article which can be used as an injection molding mold. To achieve the foregoing and other objectives, the metal powder composition according to the present invention includes iron-based powder materials, nickel and / or nickel alloy powder materials (4) (4) 200427533, copper and / or copper alloy powder materials, and graphite Powder material. This graphite powder material is used to improve wettability during melting or to reduce fine cracks during curing. In a preferred case, the proportion of the graphite powder material is from 0.2% by weight to 1.0% by weight. If the graphite powder material is less than 0.2 weight. /. Or if it exceeds 1.0 wt%, the effect of reducing fine cracks is reduced. More preferably, when the proportion of graphite powder material is from 0.2% to 1.0% by weight, from the viewpoint of reducing fine cracks or improving forming properties, the proportion of iron-based powder material is from 60% to 90% by weight. The proportion of nickel and / or town alloy powder material is from 5% to 35% by weight, and the proportion of copper and / or copper alloy powder material is from 5% to 15% by weight. More specifically, 'if the proportion of the nickel and / or nickel alloy powder material is less than 5% by weight', the formed article often has cracks. On the other hand, if the proportion of the nickel and / or nickel alloy powder material exceeds 35% by weight, the thermal shrinkage of the formed article when it is rapidly cooled is large and it is easy to separate from the formed plate (for example, made of iron). If the proportion of the copper and / or copper alloy powder material is less than 5% by weight, the wettability or fluidity (when required for a selective laser sintering material) during melting will be impaired. On the other hand, if the proportion of copper and / or copper alloy powder material is higher than 15% by weight, the reduced adhesion between the formed article (an iron alloy containing more copper) and the formed plate will cause the formed article to separate from the formed plate. When iron-based powder materials include chrome-molybdenum steel powder materials, or when copper alloy powder materials include copper-manganese alloy materials, the addition of graphite powder materials can further improve the properties of formed objects. In a particularly good case, the proportion of chrome-molybdenum steel powder material is from 60% by weight -8-(5) 200427533 to 80%: Copper f Meng alloy powder material ratio although the material and copper and micron are better than the average diameter of nickel material is smaller than nickel And / average particle size If the material or copper and powder into a powder group it is difficult to shape the powder layer thick. In order to make spherical and graphite powder non-spherical alloy powder based on 25 ", its: the amount%, the proportion of nickel powder material from 15% to 25% by weight, the proportion of powder material from 5% to 5% The average particle size of graphite powder is from 0.2 to 0.75% by weight. The average particle size of iron-based powder material, nickel and / or nickel alloy powder material, or copper alloy powder material is 5 microns. To 50%, the average particle size of the iron-based powder material and / or the nickel alloy powder material and the copper and / or copper alloy powder material in the stomach condition. The average particle size of the iron-based powder material used. Low diameter or 3/4 of nickel alloy powder materials and copper and / or copper alloy powder materials are particularly preferred. Average particle size of iron-based powder materials, nickel and / or nickel alloy powder materials, or copper alloy powder materials Below 5 microns, it will cause the adhesion of the material, and the fluidity of the powder composition will be reduced to form a high-density powder layer. If the average particle size exceeds 50 microns, the degree cannot be less than 50 microns, which makes it difficult to achieve high Precision metal powder composition with high density Evenly laminated, it is better that the powder particles have a relatively narrow particle size distribution. However, when the metal powder composition is added with the material, the iron-based powder material is mainly composed of particles and the nickel and / or nickel alloy powder material and copper and It is more preferable that the copper material is mainly composed of spherical particles. In particular, when the iron powder material is a chromium molybdenum steel powder material, its average particle size is preferably low rice. This metal powder composition may be a "granulated powder" The composition is usually spherical particles obtained by -9- (6) 200427533 by solidifying extremely fine powder particles with a binder. Method of manufacturing metal powder composition according to the present invention: • Graphite flakes are mixed into iron-based powder materials, nickel and gold powder materials and copper and / or copper alloy powder materials, and powdered. This method facilitates easy handling and uniform graphite distribution. Because the three-dimensional object obtained by sintering the aforementioned metal powder composition has no cracks and almost no micro cracks in the internal structure, the surface area and the internal area can have a density difference and can be used as injection molds. [Embodiment] This application is based on No. 2003-48263 281 520, filed in Japan on February 25, 2003 and July 28, 2003, all of which are hereby incorporated by reference. Figure 1 illustrates an apparatus for selective laser sintering. It includes a powder layer forming unit 2 for forming a powder layer 10, a sintered layer forming unit 3 using a junction layer 11, and a low density layer removing unit 4. The powder layer forming unit forms the At layer 10 with a predetermined thickness by first applying selective laser sintering to the movable table 20 (which is moved vertically in a limited space by a cylinder), and the homogenizing blade 21 makes the powder composition average. The sintered layer forms a single sintered layer 11 by irradiating a scanning optical system (including a reflector 31 and the like) from the laser light generator 30 on the powder >. The use of the laser oscillator 10 as the laser light generator 30 is characterized in that the three-dimensional object injection molding mold I on the surface of the mixed part obtained by nickel smashing is shown in Tables 1 and 2003 of the equipment package to form a burned surface. After the powder can be moved vertically, ΐ is used; 3 forms a laser via [layer 10 is better, so that -10- (7) (7) 200427533 is better to use a iron mirror as a reflector 31. The surface layer removing unit 4 includes an XY driving unit 40 on the bottom of the powder layer forming unit 2 and a dresser 41 on the XY driving unit 40. It is better to use a cutting machine (such as a final honing machine, a drilling machine, etc.) as the finishing machine 41. Figure 2 illustrates how the three-dimensional object can be manufactured using the aforementioned equipment. As shown here, the metal powder composition is first applied to the substrate 22 located above the vertically movable table 20, which can be used as a pitch adjuster to adjust the gap between the sintered layer forming unit 3 and the sintered layer. After applying the powder composition on the substrate 22, it is homogenized with a homogenizing blade 21 to form a first powder layer 10, and a light beam (laser beam) L is irradiated on a desired portion of the first powder layer 10 By sintering, a sintered layer 11 is bonded to the substrate 22. Thereafter, the table 20 may be moved vertically to lower the predetermined length, and the metal powder composition may be applied again and homogenized using a homogenizing blade 21 to form a second powder layer 10. The light beam L is again irradiated to a desired portion of the second powder layer 10 to sinter it, thereby forming another sintered layer 11 and combining it with the sintered layer 11 located below. The process of forming a new powder layer 10 after the vertical movable table 20 is lowered and the process of irradiating a desired portion of the new powder layer 10 with the light beam L to form a new sintered layer 11 are repeated to thereby obtain a three-dimensional target object. It is better to use a C02 laser as the light beam. In the description, the three-dimensional object is a forming mold, and the preferred thickness of each powder layer is about 0.05 mm. The laser irradiation path data display and the cutting path data display are made from three-dimensional CAD data indicating a desired shape design in advance. When determining the laser irradiation path, the contour data of each part (at equal distance (△ Η is 0.05 mm-11 (8) (8) 200427533 meters, which is 0.05 mm) were cut from From the STL data of a 3D CAD model) to define the target shape. Preferably, at least one surface area of the three-dimensional object is sintered to have a high density (for example, the porosity is less than 5%), while the inside of the three-dimensional object is sintered to have a low density. In other words, the model data is divided into those for the surface area and those for the inner area. The beam irradiation conditions make the inner area porous and the surface area has a high density (because most of the powder composition melts therein), making it possible to obtain the tool at high speed. Shaped objects on dense surfaces. During the formation of the plurality of sintered layers 11, the total thickness thereof reaches a specific thickness determined by the length of the tool (such as the honing front end 41), and the surface layer removing unit 4 is activated to cut the surface of the three-dimensional object that has been formed before. For example, a tool (ball-end honing machine) with a diameter of 1 mm and a honing front end of 41 and an effective scraper length of 3 mm can reach a cutting depth of 3 mm. Accordingly, if the thickness of the powder layer 10 is 0.05 mm and the sixty sintered layers are formed, the surface layer removing unit 4 is activated. The surface layer removing unit 4 can remove the low-density surface layer formed by the powder adhering to the surface of the formed object, and can simultaneously cut off a part of the high-density area, thereby exposing the high-density area to the entire surface of the formed object. Here, the shape size of the sintered layer 11 is made slightly larger than the desired shape. As described above, the cutting path and the laser irradiation path are obtained from the three-dimensional CAD data. Although the cutting path is determined by the so-called contour line processing, the vertical distance of the cutting path does not have to be the same as the lamination pitch during sintering. If the slope of the target object is gentle, reduce the vertical distance to obtain a smooth surface. Although in the illustrative embodiment, the apparatus includes a surface layer removal unit 4 -12- 200427533 〇) to perform cutting work during the forming period, the present invention can also be used without a surface layer removal unit and not applied during the forming period General selective laser sintering for cutting operations. Figure 3 shows a section of a shaped article doped with graphite powder. In particular, the graphite dots in the shaped article can be seen. The ratio of the graphite powder to the metal powder composition is preferably less than about 1% by weight. In particular, when the proportion of iron-based powder is 60-90% by weight, nickel powder and / or nickel alloy powder is 5-35% by weight, and copper powder and / or copper alloy powder is 5-15% by weight, graphite The powder ratio is preferably in the range of 0.2 to 1.0% by weight. If the proportion of graphite powder exceeds 1% by weight, the effect of reducing fine cracks is significantly reduced, so that the degree of fine generation is similar to that when graphite powder is not added. It is preferable to use chromium-molybdenum steel powder and copper-manganese alloy powder as iron-based powder and copper alloy powder, respectively. When at least one of these two conditions is satisfied, the properties of a shaped article doped with graphite powder can be improved. When the proportion of chrome molybdenum steel powder is 60-80% by weight, nickel powder is 15-25% by weight, copper-manganese alloy powder is 5-15% by weight, graphite powder is 0.2-0.7 5% by weight, and there are no micro cracks in high density parts. Both the high-density portion and the low-density portion can obtain desired forming properties. Preferably, all iron-based powders, nickel powders and / or nickel alloy powders and copper powders and / or copper alloy powders have an average particle size of 5-50 microns. If the particle diameter is too small, the powder composition will agglomerate. Accordingly, when the thickness At1 of the powder layer 10 is 0.05 mm, the average particle diameter is set to about 30 m. -13- (10) (10) 200427533 Since the metal powder composition is usually laminated uniformly at a high density, it is preferable that the powder particles are spherical and have a narrow particle size distribution. However, when graphite powder is added, it is more preferable that the iron-based powder material is mainly composed of non-spherical particles and the nickel and / or nickel alloy powder material and copper and / or copper alloy powder material are mainly composed of spherical particles. In particular, when the iron-based powder material is a chromium-molybdenum steel powder material mainly composed of non-spherical particles, its average particle size is less than 25 microns and also lower than nickel and / or nickel alloy powder materials or copper And / or the average particle diameter of the copper alloy powder material is preferably 3/4, and good results are obtained. _ Examples use SCM440 (molybdenum steel) powder (which is mainly composed of non-spherical particles, with an average particle size of 20 microns, please refer to Figure 4), Ni (nickel) powder (which is mainly composed of spherical particles, with an average particle size of 30) Micron, please refer to Figure 5) and CuMnNi (copper-manganese alloy, made of, for example, Cu-1 0% by weight Mn-3% by weight Ni) powder (mainly composed of spherical particles, the average particle size is 30 microns, please refer to Fig. 6) Six types of metal powder compositions are prepared. These six types of metal powder compositions are added with c (graphite) in the following different ratios. 〇 7 0% by weight SCM440-21% by weight 9% 0 / 〇 CuMnNi b) 70% by weight SCM440 ~ 21% by weight-9% by weight CuMnNi
+ 0.2重量％ C+ 0.2% by weight C
c) 70重量％50河440 - 21 重量％>^ - 9 重量 ％ CuMnNi + 0.4重量％ C -14- (11) (11)200427533c) 70% by weight 50% 440-21% by weight > ^-9% by weight CuMnNi + 0.4% by weight C -14- (11) (11) 200427533
d) 70 重重 ％SCM440 - 21 重量％!^ - 9 重量 ％ CuMnNi + 0.5重量％ Cd) 70% by weight SCM440-21% by weight! ^-9% by weight CuMnNi + 0.5% by weight C
e) 70 重量 °/〇SCM440 - 21 重量％^ - 9 重量。/〇 CuMnNi + 0.7 5 重量 ％ C f ) 7 0 重重 ％SCM440 - 21 重量 ％ N i - 9 重量 ％ C u Μ η N i + K 0重量％ c 於下列條件下使用六種類型金屬粉末組成物（a )( Ο進行此選擇性雷射燒結。 粉末層厚度：〇·〇5毫米 所用雷射：200瓦特C02雷射（輸出：90%) 掃描速率：75毫米/秒 掃描間距：〇 . 2 5毫米 使用不含石墨的金屬粉末組成物（a)者有大量細微 裂紋，使用添加〇 · 5重量％石墨的金屬粉末組成物（d )則 無細微裂紋（請參考附圖3 )。使用添加0.4重量％石墨 的金屬粉末組成物（c )僅有些微細微裂紋（請參考附圖 3 )。使用添加〇·2重量％石墨的金屬粉末組成物（b )和 使用添加〇·75重量％石墨的金屬粉末組成物（e )相較於 使用未添加石墨的金屬粉末組成物（a)之時，前者的細 微裂紋減少。使用添加1 .〇重量°/。石墨的金屬粉末組成物 (f )觀察到的細微裂紋數目比使用金屬粉末組成物（a ) 時略少或相同。 於下列條件下製得密度不同的三維物件。 i )高密度部分 -15· (12) (12)200427533 掃描速率：7 5毫米/秒 掃描間距：0.2 5毫米 i i )中密度部分 掃描速率：1 5 0毫米/秒 掃描間距：0.5毫米 Π i )低密度部分 掃描速率：200毫米/秒 掃描間距：0.3毫米 製造三維物件時，高密度部分和中密度部分各層被施 以雷射照射，低密度部分則是每兩層施以雷射照射。 使用摻有石墨粉末的金屬粉末組成物’獲致良好流動 性（可流動性）。 含有鉻鉬鋼粉末（主要由球形顆粒構成，平均粒徑 30微米，與其他非鐵金屬粉末的平均粒徑相同）的另一 金屬粉末組成物製成與金屬粉末組成物（d )組成相同者 。此金屬粉末組成物於下列條件下燒結。 粉末層厚度：0.05毫米 所用雷射：200瓦特C02雷射（輸出：90% ) 掃描速率：75毫米/秒 掃描間距：0.25毫米 相較於使用金屬粉末組成物（d )，使用此金屬粉末 組成物，雖然觀察到一些細微裂紋且因孔洞存在而使密度 下降至某程度，但可得到實質上良好的成形物件。 使用CuP (銅_磷）合金粉末代替金屬粉末組成物（ -16- (13) (13)200427533 d )中的銅-錳合金粉末，製得另一金屬粉末組成物並於 相同條件燒結。此C.uP合金粉末主要由球形顆粒構成且 平均粒徑是3 0微米。使用此金屬粉末組成物，觀察到裂 紋存在且燒結層上表面不均勻，此會阻礙下一粉末層之形 成。此外，燒結層的轉橫向強度不足。 使用C ιιΡ (銅-磷）合金粉末代替金屬粉末組成物（ d )中的銅-錳合金粉末，製得另一金屬粉末組成物並於 相同條件燒結。此處，此銅_磷合金粉末主要由球形顆粒 構成且平均粒徑是3 0微米，而鉻鉬鋼粉末主要由球形顆 粒構成且平均粒徑是3 0微米，此與其他非鐵金屬粉末的 平均粒徑相同。相較於使用銅-磷合金粉末（主要由球形 顆粒構成且平均粒徑是30微米）和鉻鉬鋼粉末（主要由 非球形顆粒構成且平均粒徑是20微米）者，雖然可得到 較佳結果，但有細微裂紋存在。 摻有銅-磷合金粉末的金屬粉末及摻有銅-鎂合金粉 末的金屬粉末差別在於細微裂紋。認爲後者的細微裂紋因 雷射燒結期間內的熔解欠佳引起，使用平均粒徑低於其他 非鐵金屬粉末的鉻鉬鋼粉末則促進熔解並因此減少細微裂 紋數目。 相較於使用主要由球形顆粒構成之鉻鉬鋼粉末，使用 主要由非球形顆粒構成之鉻鉬鋼粉末時’石墨粉末有效散 佈於鉻鉬鋼粉末各顆粒表面。添加石墨粉末對於前者的助 益更甚於後者。 石墨粉末與含有以鐵爲基礎的粉末、鎳粉和/或鎳合 -17- (14) (14)200427533 金粉末及銅粉和/或銅合金粉末混合時’附圖7所示的石 墨薄片先加至金屬粉末組成物中’之後於硏缽中粉碎或硏 磨。附圖8所示者是無石墨粉末的所得混合物。其原因在 於石墨有效散佈於金屬粉末組成物表面’在鉻鉬鋼粉末主 要由非球形顆粒構成時更是如此。相較於只有石墨粉末與 金屬粉末組成物混合的情況，此時可得到良好成形性質且 細微裂紋數目較少。 此外，製得另一金屬粉末組成物並燒結，其顆粒最大 長度低於以鐵爲基礎的粉末之平均顆粒直徑，特別是低於 1 〇微米。此燒結層具有滲碳效果，藉由雷射照射，碳進 入鐵以降低熔解期間內的熔點。因爲熔解期間內的流動性 質獲改善，燒結層的表面不均勻度降低。 此外，由最大長度爲1至數微米的超細顆粒組成的石 墨粉末可以作爲碳黑，即，細碳粉末，其可藉由天然氣或 液態烴的不完全燃燒或熱分解反應而製得。這樣的石墨粉 末亦可藉噴射硏磨得到。 雖然附圖3中的黑點代表石墨澱積，較佳情況中，用 以製造碳化物的一或多種元素先與鐵混合。如果一或多種 元素（如：Cr (鉻）、Mo (鉬）、W (鎢）、V (釩）之 類）與鐵混合，於固化時自熔融相澱積的碳會與這樣的元 素結合而轉變成碳化物，便能防止碳澱積。 附圖9是SEM照片，其中W (鎢）粉末加至前述金 屬粉末組成物（d)中（70重量％ SCM440- 21重量％ Ni - 9重量％(：11河11>^ + 0.5重量％匸+ 0.5重量％\\〇 ，而 -18- (15) (15)200427533 附圖10是SEM照片’其中SC M44〇以含有許多製造碳化 物之元素的SKH鋼粉代替，（70重量％ SKH - 21重量。/。 Ni - 9重量％ CuMnNi + 0.5重量。/〇C )。這些照片顯示， 相較於附圖3所示之得自金屬粉末組成物（d )的成形物 件，此成形物件的碳澱積數減少。碳澱積數目減少有助於 高密度、高強度和高硬度成型，澱積的碳存在增進機械加 工之後的表面糙度。 藉選擇性雷射燒結前文所討論的金屬粉末組成物而得 到的三維物件具有足敷用於注射模塑模具的性質。 雖然已藉實例並參考附圖地完全描述本發明，嫻於此 技術者仍知道各種變化和修飾。因此，除非這樣的變化和 修飾背離本發明之精神和範圍，否則它們亦含括於本發明 之中。 【圖式簡單說明】 由較佳實施例之描述並參考附圖，會更明瞭本發明的 前述和其他目的，附圖中，類似組件使用類似參考代號， 其中： 附圖1是使用根據本發明之金屬粉末組成物製造三維 物件的設備透視圖； 附圖2是製得的三維物件的放大圖； 附圖3是自摻有石墨粉末的金屬粉末得到之成形物件 截面的25倍放大照片； 网寸匱1 4是主要由非球形顆粒構成的鉻鉬鋼粉末的 -19- (16) (16)200427533 SEM照片； 附圖5是主要由球形顆粒構成的鎳粉末的s E M照片 附圖6是主要由球形顆粒構成的銅錳合金粉末的 SEM照片； 附圖7是石墨薄片的SEM照片； 附圖8是數種粉末之混合物的SEM照片； 附圖9是摻有製造碳化物之元素的金屬粉末得到的成 形物件截面之25倍放大照片； 附圖10是由含有製造碳化物的元素之以鐵爲基礎的 粉末與金屬粉末得到的成形物件截面之25倍放大照片； 附·圖11是自慣用金屬粉末得到的成形物件截面之25 倍放大照片。 主要元件對照表 2 粉 末 層 形 成 單 元 3 燒 結 層 形 成 單 元 4 表 層 移 除 單 元 10 粉 末 層 11 燒 結 層 20 可 垂 直 移 動 桌 21 均 化 刮 板 30 雷 射 光 產 生 器 3 1 反 射 器 -20- 200427533 (17) 40 ΧΥ驅動單元 4 1 修整機械 22 底質 L 光束 Δ 11 厚度 »21e) 70 weight ° / 〇SCM440-21 weight% ^-9 weight. / 〇CuMnNi + 0.7 5 wt% C f) 7 0 wt% SCM440-21 wt% Ni-9 wt% C u M η N i + K 0 wt% c Use of six types of metal powder composition under the following conditions (A) (0) This selective laser sintering is performed. Powder layer thickness: 0.05 mm Laser used: 200 Watt C02 laser (output: 90%) Scanning rate: 75 mm / s Scanning pitch: 0.2 5 mm using graphite-free metal powder composition (a) has a lot of fine cracks, using 0.5% by weight of graphite-added metal powder composition (d) has no fine cracks (please refer to Figure 3). The metal powder composition (c) of 0.4% by weight graphite has only some slight cracks (please refer to FIG. 3). The metal powder composition (b) with addition of 0.2% by weight graphite and the use of 0.75% by weight graphite The metal powder composition (e) has a finer crack than the metal powder composition (a) to which graphite is not added. The use of the metal powder composition (f) to which graphite is added by 1.0 wt. Observed number of fine cracks than with gold The powder composition (a) is slightly less or the same. Three-dimensional objects with different densities are produced under the following conditions. I) High-density part-15 · (12) (12) 200427533 Scanning rate: 75 mm / s Scanning pitch: 0.2 5 mm ii) Scan rate of medium density part: 150 mm / s Scan pitch: 0.5 mm Π i) Scan rate of low density part: 200 mm / s Scan pitch: 0.3 mm When manufacturing three-dimensional objects, high density parts and medium Each layer of the density part is irradiated with laser light, while the low density part is irradiated with laser light every two layers. A graphite powder-doped metal powder composition is used to obtain good flowability (flowability). Another metal powder composition containing chromium-molybdenum steel powder (mainly composed of spherical particles, with an average particle diameter of 30 microns, the same as the average particle diameter of other non-ferrous metal powders) is made the same as the metal powder composition (d) . This metal powder composition was sintered under the following conditions. Powder layer thickness: 0.05 mm Laser used: 200 Watt C02 laser (output: 90%) Scanning rate: 75 mm / s Scanning pitch: 0.25 mm Compared to using a metal powder composition (d), this metal powder composition Although some fine cracks were observed and the density was reduced to a certain degree due to the existence of holes, substantially good shaped articles were obtained. CuP (copper_phosphorus) alloy powder was used in place of the copper-manganese alloy powder in the metal powder composition (-16- (13) (13) 200427533 d) to prepare another metal powder composition and sintered under the same conditions. This C.uP alloy powder is mainly composed of spherical particles and the average particle diameter is 30 micrometers. With this metal powder composition, cracks were observed and the upper surface of the sintered layer was uneven, which hindered the formation of the next powder layer. In addition, the sintered layer has insufficient lateral strength. The Cu-P (copper-phosphorus) alloy powder was used instead of the copper-manganese alloy powder in the metal powder composition (d), another metal powder composition was prepared and sintered under the same conditions. Here, the copper-phosphorus alloy powder is mainly composed of spherical particles and the average particle diameter is 30 micrometers, while the chromium-molybdenum steel powder is mainly composed of spherical particles and the average particle diameter is 30 micrometers. The average particle size is the same. Compared with the use of copper-phosphorus alloy powder (mainly composed of spherical particles and average particle diameter of 30 microns) and chromium-molybdenum steel powder (mainly composed of non-spherical particles and average particle diameter of 20 microns), although better As a result, fine cracks existed. The difference between a metal powder doped with a copper-phosphorus alloy powder and a metal powder doped with a copper-magnesium alloy powder lies in fine cracks. It is believed that the latter's fine cracks are caused by poor melting during the laser sintering period, and the use of chromium-molybdenum steel powder with an average particle size lower than that of other non-ferrous metal powders promotes melting and thus reduces the number of fine cracks. Compared to using chromium-molybdenum steel powder mainly composed of spherical particles, when using chromium-molybdenum steel powder mainly composed of non-spherical particles, the graphite powder is effectively dispersed on the surface of each particle of the chromium-molybdenum steel powder. Adding graphite powder is more beneficial to the former than to the latter. When graphite powder is mixed with iron-based powder, nickel powder and / or nickel alloy-17- (14) (14) 200427533 gold powder and copper powder and / or copper alloy powder, the graphite flakes shown in FIG. 7 It is added to the metal powder composition first, and then pulverized or honed in a mortar. Figure 8 shows the resulting mixture of graphite-free powder. The reason for this is that graphite is effectively dispersed on the surface of the metal powder composition ', especially when the chromium-molybdenum steel powder is mainly composed of non-spherical particles. Compared with the case where only the graphite powder and the metal powder composition are mixed, good forming properties can be obtained at this time and the number of fine cracks is small. In addition, another metal powder composition was prepared and sintered, and the maximum particle length thereof was lower than the average particle diameter of the iron-based powder, and particularly lower than 10 m. This sintered layer has a carburizing effect. By laser irradiation, carbon enters iron to reduce the melting point during melting. Because the fluidity during the melting period is improved, the surface unevenness of the sintered layer is reduced. In addition, graphite powder composed of ultrafine particles having a maximum length of 1 to several micrometers can be used as carbon black, that is, fine carbon powder, which can be produced by incomplete combustion or thermal decomposition reaction of natural gas or liquid hydrocarbon. Such graphite powder can also be obtained by jet honing. Although the black dots in Figure 3 represent graphite deposition, preferably, one or more elements used to make carbides are first mixed with iron. If one or more elements (such as Cr (Chromium), Mo (Molybdenum), W (Tungsten), V (Vanadium), etc.) are mixed with iron, the carbon deposited from the molten phase during solidification will combine with such elements Conversion to carbides prevents carbon deposition. Figure 9 is a SEM photograph in which W (tungsten) powder is added to the aforementioned metal powder composition (d) (70% by weight SCM440-21% by weight Ni-9% by weight (: 11 River 11 > ^ + 0.5% by weight) + 0.5% by weight \\ 〇, and -18- (15) (15) 200427533 Figure 10 is a SEM photograph 'where SC M44〇 is replaced by SKH steel powder containing many carbide-making elements, (70% by weight SKH- 21% by weight Ni-9% by weight CuMnNi + 0.5% by weight. These photos show that compared to the shaped article obtained from the metal powder composition (d) shown in FIG. The number of carbon deposits is reduced. The reduced number of carbon deposits contributes to high density, high strength and high hardness molding, and the presence of deposited carbon improves the surface roughness after machining. Metal powders discussed earlier by selective laser sintering The three-dimensional object obtained from the composition has the property of being sufficiently applied to an injection molding mold. Although the present invention has been fully described by way of examples and with reference to the accompanying drawings, those skilled in the art still know various changes and modifications. Therefore, unless such Changes and modifications depart from the spirit and scope of the present invention Otherwise, they are also included in the present invention. [Brief description of the drawings] The foregoing and other objects of the present invention will be made clearer by describing the preferred embodiments with reference to the accompanying drawings. In the drawings, similar components use similar reference numerals. In which: Figure 1 is a perspective view of a device for manufacturing a three-dimensional object using the metal powder composition according to the present invention; Figure 2 is an enlarged view of the manufactured three-dimensional object; Figure 3 is obtained from a metal powder doped with graphite powder A 25-times enlarged photograph of the section of the formed object; the mesh size 14 is a -19- (16) (16) 200427533 SEM photograph of a chromium-molybdenum steel powder mainly composed of non-spherical particles; Figure 5 is composed mainly of spherical particles S EM photograph of nickel powder Figure 6 is a SEM photograph of a copper-manganese alloy powder mainly composed of spherical particles; Figure 7 is a SEM photograph of graphite flakes; Figure 8 is a SEM photograph of a mixture of several powders; 9 is a 25-times enlarged photograph of a cross-section of a shaped object obtained by mixing metal powder with a metal-making element; FIG. 10 is obtained from iron-based powder and metal powder containing a metal-making element 25 times magnified photo of the cross section of the shaped object; Attached Figure 11 is a 25 times magnified photo of the cross section of the shaped object obtained from the conventional metal powder. Main component comparison table 2 Powder layer forming unit 3 Sintered layer forming unit 4 Surface layer removing unit 10 Powder Layer 11 Sintered layer 20 Vertically movable table 21 Homogenizing scraper 30 Laser light generator 3 1 Reflector-20- 200427533 (17) 40 XY drive unit 4 1 Trimming machine 22 Substrate L beam Δ 11 Thickness »21