TW201829799A - Hard alloy suitable for additive manufacture - Google Patents
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本發明係關於合金材料之相關技術領域,尤指一種適於積層製程的硬質合金。The present invention relates to the technical field of alloy materials, and more particularly to a cemented carbide suitable for a lamination process.
2009年,美國材料試驗協會(American Society for Testing and Materials, ASTM)將快速原型(Rapid Prototyping, RP)、快速製造(Rapid Manufacturing, RM)、3D列印(3D printing, 3DP)等先進技術統一正名為積層製造(Additive Manufacturing, AM)。積層製造的主要生產流程包括:步驟(1):透過電腦軟體設計出一具特定外觀的立體圖;以及步驟(2):根據該具特定外觀的立體圖,使用特定的成型設備(俗稱:3D印表機)以液化或粉末化的固體材料逐層地列印出一立體產品。In 2009, the American Society for Testing and Materials (ASTM) unified advanced technologies such as Rapid Prototyping (RP), Rapid Manufacturing (RM), and 3D printing (3DP). It is called Additive Manufacturing (AM). The main production process of laminated manufacturing includes: step (1): designing a stereoscopic view with a specific appearance through computer software; and step (2): using a specific molding device according to the stereoscopic view with a specific appearance (commonly known as: 3D printing table) Machine) A solid product is liquefied or powdered to print a three-dimensional product layer by layer.
台灣專利號:TWI532852係揭示一種可應用於雷射積層製程的合金粉體,其中,該合金粉體係於元素組成(elemental compositions)上包括:重量百分比介於52-60 wt%之間的鎳元素與鐵元素、重量百分比介於16-22 wt%之間的鈷或錳、其餘部分則添加鉻元素或鋁元素予以補足。該合金粉體之多個樣品的成分組成係示於下表(1)之中。 表(1)
由表(1),吾人可以得知雖然台灣專利號:TWI532852所揭示的合金粉體可利用雷射積層製程而被加工成硬度介於HV265至HV550之間的半成品,但是因為該半成品的硬度不夠高,是以無法進一步地被加工成為須具備超高硬度與耐磨耗性質的高速銑加工設備(High speed machining, HSM)之切削刀具。From Table (1), we can know that although the alloy powder disclosed in Taiwan Patent No.: TWI532852 can be processed into a semi-finished product with a hardness between HV265 and HV550 by a laser lamination process, the hardness of the semi-finished product is insufficient. High is a cutting tool that cannot be further processed into a high speed machining (HSM) that requires ultra-high hardness and wear resistance.
如熟悉合金製造的工程技術人員所熟知的,硬質合金(hard alloy)目前已被廣泛應用於高速銑加工設備之切削刀具的生產製造,其組成上係主要包括:質硬的碳化物與質軟的黏結相金屬(binding phase metal);其中,所述質硬的碳化物通常為碳化鎢(WC),且所述質軟的黏結相金屬通常為鈷(Co)。雖然鈷作為黏結相金屬係提升結合基體對於碳化鎢顆粒的支撐,但是卻也降低了純碳化鎢的高硬度、高耐磨性等特殊性質;此外,鈷也包括價格高昂、取得不易以及具生物毒性等缺點。基於這樣的理由,熟悉硬質合金製造的工程技術人員於是逐漸地以鐵(Fe)或鎳(Ni)取代鈷作為硬質合金之中的黏結相金屬;例如,碳化鈦-鎳(TiC-Ni)便為另一種硬質合金。As is well known to those skilled in the art of alloy manufacturing, hard alloys have been widely used in the manufacture of cutting tools for high-speed milling equipment, and their composition mainly includes: hard carbides and soft materials. A binding phase metal; wherein the hard carbide is typically tungsten carbide (WC), and the soft phase of the binder phase is typically cobalt (Co). Although cobalt as a binder phase metal enhances the support of the bonded matrix for tungsten carbide particles, it also reduces the special properties of pure tungsten carbide with high hardness and high wear resistance; in addition, cobalt also includes high price, difficulty in obtaining, and biological Disadvantages such as toxicity. For this reason, engineers familiar with the manufacture of cemented carbides have gradually replaced cobalt with iron (Fe) or nickel (Ni) as a binder phase metal in cemented carbides; for example, titanium carbide-nickel (TiC-Ni) For another hard alloy.
基於硬質合金材料具有高硬度的機械性質,一些研究人員曾經嘗試著利用積層製程將傳統的硬質合金粉末加工成為一個硬質合金成品。結果顯示,利用積層製程所製造出的硬質合金會具有裂痕(crack)或孔洞(voids, pores)等缺陷。本案發明人經分析後發現,基於傳統硬質合金材料係由高熔點的碳化鎢與低熔點的鈷所組成,因此在進行例如雷射燒結(laser sintering)之積層製程的過程中,硬質合金材料會於多次的快速熔融與快速冷卻凝固的轉換過程中,因為兩種主要成分的熔點差過大而衍生出許多問題,例如:熱脹冷縮、內應力集中、(晶格)高度方向性等。Based on the mechanical properties of cemented carbide materials with high hardness, some researchers have tried to process traditional cemented carbide powder into a finished carbide product using a lamination process. The results show that the cemented carbide produced by the lamination process has defects such as cracks or voids, pores. The inventors of the present invention have found that the conventional cemented carbide material is composed of high melting point tungsten carbide and low melting point cobalt, so in the process of performing a layering process such as laser sintering, the cemented carbide material will During the conversion process of multiple rapid melting and rapid cooling solidification, many problems arise due to the excessive melting point difference between the two main components, such as thermal expansion and contraction, internal stress concentration, and (lattice) high directivity.
因此,有鑑於傳統硬質合金材料無法直接地適用於積層製程,本案之發明人於是嘗試著設計出可以作為硬質合金之黏結相金屬的一種新式高熵合金,並接續地研發完成本發明之一種適於積層製程的硬質合金。Therefore, in view of the fact that traditional cemented carbide materials cannot be directly applied to the lamination process, the inventors of the present invention have attempted to design a new high-entropy alloy which can be used as a cemented phase metal of cemented carbide, and successively developed a suitable one for the present invention. Cemented carbide for the lamination process.
本發明之主要目的在於提供一種適於積層製程的硬質合金。習知的硬質合金通常包含質硬的碳化物與質軟的黏結相金屬(binding phase metal)等黏結相金屬,其中,鈷為常用的黏結相金屬,但降低了純碳化鎢的硬度與耐磨性。不同於習知的硬質合金的組成,本發明特別以至少四種金屬元素組成一合金材料,並以至少一種碳化物及該合金材料構成一種適於積層製程的硬質合金。並且,實驗資料係證實,本發明之硬質合金係能夠利用例如雷射燒結之積層製程或者傳統真空燒結製程對於上述碳化物粉末與合金材料粉末進行加工之後而製得。同時,所製得的硬質合金係具有至少HV1100以上的維氏硬度值。The main object of the present invention is to provide a cemented carbide suitable for a lamination process. Conventional cemented carbides usually contain a hard phase carbide and a soft phase phase metal such as a binding phase metal. Among them, cobalt is a commonly used binder phase metal, but reduces the hardness and wear resistance of pure tungsten carbide. Sex. Unlike the conventional composition of cemented carbide, the present invention particularly comprises an alloy material of at least four metal elements, and at least one carbide and the alloy material constitute a cemented carbide suitable for a lamination process. Further, the experimental data confirmed that the cemented carbide of the present invention can be obtained by processing the above-described carbide powder and alloy material powder by, for example, a laminate process of laser sintering or a conventional vacuum sintering process. At the same time, the obtained cemented carbide has a Vickers hardness value of at least HV1100 or more.
為了達成上述本發明之主要目的,本案之發明人係提供一種適於積層製程的硬質合金之一實施例,其組成上係包括: 至少一種碳化物,係可為下列任一者:碳化鎢、碳化矽、碳化硼、碳 化鈦、碳化鉭、碳化鈮、碳化鉬、碳化鋯、碳化鉻、碳化釩、上述 任兩者之組合、或上述任兩者以上之組合; 至少四種黏結相金屬元素,係選自於下列群組之中:鋁(Al)、鈷 (Co)、鉻(Cr)、銅(Cu)、鐵(Fe)、鎳(Ni)、錳(Mn)、鈦(Ti)、釩 (V)、矽(Si)、鋅(Zn)、與錫(Sn); 其中,所述碳化物係具有範圍介於50 wt%至95 wt%之間的一碳化物 重量百分比; 其中,所述至少四種黏結相金屬元素係具有範圍介於5 wt%至50 wt%之間的一黏結相金屬重量百分比;並且,每一種黏結相金屬元 素係具有一金屬元素莫耳數,且該金屬元素莫耳數係大於所有黏結 相金屬元素之一總金屬元素莫耳數的5%。In order to achieve the above-mentioned primary object of the present invention, the inventors of the present invention provide an embodiment of a cemented carbide suitable for a lamination process, the composition comprising: at least one carbide, which may be any of the following: tungsten carbide, Tantalum carbide, boron carbide, titanium carbide, tantalum carbide, tantalum carbide, molybdenum carbide, zirconium carbide, chromium carbide, vanadium carbide, a combination of any two of the above, or a combination of any two or more thereof; at least four bonding phase metal elements , selected from the group consisting of aluminum (Al), cobalt (Co), chromium (Cr), copper (Cu), iron (Fe), nickel (Ni), manganese (Mn), titanium (Ti) And vanadium (V), bismuth (Si), zinc (Zn), and tin (Sn); wherein the carbide system has a weight percentage of a single carbide ranging from 50 wt% to 95 wt%; The at least four binder phase metal elements have a binder phase metal weight percentage ranging from 5 wt% to 50 wt%; and each binder phase metal element has a metal element mole number, and The metal element molar number is greater than one of all the bonding phase metal elements 5% of the number of metal elements mole.
於上述本發明之適於積層製程的硬質合金之實施例中,係可進一步地調整所述硬質合金之碳元素含量,用以防止缺碳相或石墨相出現於該硬質合金之基體結構中。In the above embodiment of the cemented carbide suitable for the lamination process of the present invention, the carbon content of the cemented carbide may be further adjusted to prevent the carbon-deficient phase or the graphite phase from appearing in the matrix structure of the cemented carbide.
於上述本發明之適於積層製程的硬質合金之實施例中,其中,該至少一種碳化物應用於所述硬質合金之一製程原料可為一碳化物粉末;並且,該至少四種黏結相金屬元素應用於所述硬質合金之一製程原料可為一高熵合金粉末或一多元合金粉末。In an embodiment of the above-described cemented carbide suitable for the lamination process of the present invention, wherein the at least one carbide is applied to one of the cemented carbides, the raw material of the process may be a carbide powder; and the at least four bonded phase metals The element may be applied to one of the cemented carbides as a high-entropy alloy powder or a multi-alloy powder.
為了能夠更清楚地描述本發明所提出之一種適於積層製程的硬質合金,以下將配合圖式,詳盡說明本發明之較佳實施例。In order to more clearly describe a cemented carbide suitable for the lamination process proposed by the present invention, a preferred embodiment of the present invention will be described in detail below with reference to the drawings.
本發明係為一種適於積層製程的硬質合金,其組成上係包括:至少一種碳化物與至少四種黏結相金屬元素;其中,所述碳化物可為下列任一者:碳化鎢、碳化矽、碳化硼、碳化鈦、碳化鉭、碳化鈮、碳化鉬、碳化鋯、碳化鉻、碳化釩、上述任兩者之組合、或上述任兩者以上之組合。另一方面,所述至少四種黏結相金屬元素係選自於下列群組之中:鋁(Al)、鈷(Co)、鉻(Cr)、銅(Cu)、鐵(Fe)、鎳(Ni)、錳(Mn)、鈦(Ti)、釩(V)、矽(Si)、鋅(Zn)、與錫(Sn)。The present invention is a cemented carbide suitable for a lamination process, the composition comprising: at least one carbide and at least four binder phase metal elements; wherein the carbide may be any of the following: tungsten carbide, tantalum carbide Boron carbide, titanium carbide, tantalum carbide, tantalum carbide, molybdenum carbide, zirconium carbide, chromium carbide, vanadium carbide, a combination of any two of the above, or a combination of any two or more of the foregoing. In another aspect, the at least four binder phase metal elements are selected from the group consisting of aluminum (Al), cobalt (Co), chromium (Cr), copper (Cu), iron (Fe), nickel ( Ni), manganese (Mn), titanium (Ti), vanadium (V), bismuth (Si), zinc (Zn), and tin (Sn).
於本發明中,該碳化物係具有範圍介於50wt%至95wt%之間的一碳化物重量百分比,且該至少四種黏結相金屬元素係具有範圍介於5wt%至50wt%之間的一黏結相金屬重量百分比。值得進一步說明的是,每一種黏結相金屬元素係必須具有一金屬元素莫耳數,且該金屬元素莫耳數大於所有黏結相金屬元素之一總金屬元素莫耳數的5%。In the present invention, the carbide has a weight percentage of one carbide ranging from 50 wt% to 95 wt%, and the at least four binder phase metal elements have a range ranging from 5 wt% to 50 wt%. Bonding phase metal weight percentage. It is worth furthering that each of the binder phase metal elements must have a metal element mole number, and the metal element mole number is greater than 5% of the total metal element mole number of one of the all phase phase metal elements.
第First 11 實施例:Example:
本發明之技術重點在於:以高熵合金取代應用於習知硬質合金之中的黏結相金屬,例如:鈷(Co)、鐵(Fe)、或鎳(Ni),藉以開發出適於積層製程之一種新穎的硬質合金。於第1實施例中,係以六方晶格結構(Hexagonal crystal structure)之碳化鎢(WC)粉末作為本發明之硬質合金的碳化物,並以莫耳組成上包含Al0.5
CoCrCuFeNi之高熵合金(High Entropy Alloy, HEA)粉末作為黏結相金屬之製程原料;其中,鋁(Al)、鈷(Co)、鉻(Cr)、銅(Cu)、鐵(Fe)、與鎳(Ni)之間的莫耳比為0.5:1:1:1:1:1。此外,又添加了微量的碳元素以防止缺碳相之出現。該碳化鎢、該高熵合金與該碳元素的配方係整理於下表(2)之中。 表(2)
請參閱圖1所顯示的碳化鎢、高熵合金與碳元素之混粉的背向散射電子顯微影像圖。吾人可以發現到,利用機械合金製法(例如:行星式球磨法、震動式球磨法、或攪拌式球磨法)所製得之碳化鎢、高熵合金與碳元素之混粉,其背向散射電子顯微影像係顯示出不規則的形狀。進一步地,本案發明人將碳化鎢、高熵合金與碳元素之混粉分別執行一真空燒結製程與一雷射燒結製程,進以獲得本發明之硬質合金的多個樣品。Please refer to the backscattered electron micrograph of tungsten carbide, high-entropy alloy and carbon mixed powder shown in Figure 1. We can find the backscattered electrons of tungsten carbide, high-entropy alloy and carbon mixed powder prepared by mechanical alloying method (for example, planetary ball milling, vibrating ball milling, or agitating ball milling). The microscopic image shows an irregular shape. Further, the inventor of the present invention separately performs a vacuum sintering process and a laser sintering process on the mixed powder of tungsten carbide, high-entropy alloy and carbon element to obtain a plurality of samples of the cemented carbide of the present invention.
接著,請參閱圖2所顯示本發明之一種適於積層製造的硬質合金之第1樣品與第2樣品電子顯微影像圖。其中,圖2之中的影像(a)係顯示利用真空燒結製程所製得之第1樣品係主要包括硬質合金結構11(亦即,WC結構),並且可於硬質合金結構11的表面上觀察到黏結金屬相12以及第1種缺碳相13。經分析後可確定該第1種缺碳相13為M2 C結構的富鉻相(Cr-rich phase)。另一方面,圖2之中的影像(b)係顯示利用真空燒結製程所製得之第2樣品係主要包括硬質合金結構11,並且可於硬質合金結構11的表面上觀察到第2種缺碳相13’,經分析後可確定該第2種缺碳相13’為M6 C結構的η相。Next, please refer to the electron micrograph of the first sample and the second sample of a cemented carbide suitable for lamination production of the present invention shown in FIG. The image (a) in FIG. 2 shows that the first sample obtained by the vacuum sintering process mainly includes the cemented carbide structure 11 (that is, the WC structure), and can be observed on the surface of the cemented carbide structure 11. To the bonded metal phase 12 and the first carbon-deficient phase 13. After analysis, it can be confirmed that the first carbon-deficient phase 13 is a Cr-rich phase of an M 2 C structure. On the other hand, the image (b) in Fig. 2 shows that the second sample system obtained by the vacuum sintering process mainly includes the cemented carbide structure 11, and the second type of defect can be observed on the surface of the cemented carbide structure 11. The carbon phase 13' can be determined to determine that the second carbon-deficient phase 13' is the η phase of the M 6 C structure.
繼續地,請參閱圖3所顯示硬質合金之第3樣品的電子顯微影像圖。其中,圖3之中的影像(a)係顯示利用雷射燒結製程所製得之第3樣品係主要包括硬質合金結構11(亦即,WC結構),並且於該硬質合金結構11的表面的一特定區域上並無觀察到任何缺碳相之形成。另一方面,圖3之中的影像(b)係顯示第1種缺碳相13(即,M2 C結構)係出現在該第3樣品之硬質合金結構11的表面的其它特定區域之上。Continuing, please refer to the electron micrograph of the third sample of cemented carbide shown in FIG. The image (a) in FIG. 3 shows that the third sample system obtained by the laser sintering process mainly includes the cemented carbide structure 11 (that is, the WC structure), and is on the surface of the cemented carbide structure 11. No formation of any carbon-deficient phase was observed on a particular area. On the other hand, the image (b) in Fig. 3 shows that the first carbon-deficient phase 13 (i.e., M 2 C structure) appears on other specific regions of the surface of the cemented carbide structure 11 of the third sample. .
進一步地,請參閱圖4,係顯示該硬質合金之第3樣品的剖面電子顯微影像圖。觀察圖4之後,吾人可輕易地發現利用雷射燒結製程所製得之第3樣品並無具有明顯的裂痕(crack)或孔洞(voids, pores)等缺陷。除此之外,如下表(3)所記載的,本發明之硬質合金的第1樣品、第2樣品與第3樣品的維氏硬度分別為HV994、HV1452以及HV1167。因此,實驗結果係證實本發明之碳化鎢、高熵合金與碳元素之混粉的第1實施例,係的確能以例如雷射燒結之積層製程或者傳統真空燒結製程加工成所謂的硬質合金。 表(3)
第First 22 實施例:Example:
完成第1實施例的3個硬質合金的樣品之後,本案發明人係基於完成第1實施例的相關經驗,而進一步地設計並完成本發明之硬質合金的第2實施例。於第2實施例之中,本案發明人係以六方密集結構(Hexagonal close-packed structure)之碳化鎢(W2
C)粉末作為本發明之硬質合金的碳化物,並以莫耳組成上包含Al0.5
CoCrCuFeNi之高熵合金(High Entropy Alloy, HEA)粉末作為黏結相金屬之製程原料。該碳化鎢與該高熵合金的配方係整理於下表(4)之中。進一步地,本案發明人將碳化鎢與高熵合金之混粉執行雷射燒結製程,進以獲得本發明之硬質合金的第4樣品;並且,利用維氏硬度試驗機可以測得第4樣品(W2
C-HEA)的硬度為HV1782。 表(4)
第First 33 實施例:Example:
完成第1實施例的3個硬質合金的樣品之後,本案發明人係基於完成第1實施例的相關經驗,而進一步地設計並完成本發明之硬質合金的第3實施例。於第3實施例之中,本案發明人係以碳化鎢(WC)粉末作為本發明之硬質合金的碳化物,並以莫耳組成上包含Al10
Co19
Cr5
Cu10
Fe19
Ni37
之高熵合金(High Entropy Alloy, HEA)粉末作為黏結相金屬之製程原料。下表(5)係整理了所述黏結相金屬之每一個成分的重量比例。 表(5)
同時,又添加了微量的矽元素於該高熵合金之中,以於硬質合金的組成中提供微量的矽(Si)成分。該碳化鎢粉末、該高熵合金粉末與用以提供矽元素的矽(Si)粉末的配方係整理於下表(6)之中。進一步地,本案發明人將碳化鎢與高熵合金之混粉執行雷射燒結製程,進以獲得本發明之硬質合金的第5樣品。 表(6)
藉由比較第2樣品與第5樣品的差熱分析(Differential Thermal Analysis,DTA)量測數據,可以發現添加有微量矽元素的硬質合金的熔點係低於未添加微量矽元素的硬質合金的熔點。同時,維氏硬度試驗的相關數據亦顯示,添加有微量矽元素的硬質合金的硬度係高於未添加微量矽元素的硬質合金的硬度。因此,矽元素被認為是一種強化元素。並且,除了矽元素以外,其他適合的強化元素也可以是鈧(Sc)、鈮(Nb)、鉬(Mo)、釔(Y)、釕(Ru)、鉿(Hf)、錸(Re)、鈀(Pd)、鉭(Ta)、鋯(Zr)、硼(B)、氮(N)、或氧(O)。By comparing the differential thermal analysis (DTA) measurement data of the second sample and the fifth sample, it can be found that the melting point of the cemented carbide to which the trace amount of lanthanum is added is lower than the melting point of the cemented carbide to which no trace amount of lanthanum is added. . At the same time, the data of the Vickers hardness test also showed that the hardness of the cemented carbide added with trace amounts of lanthanum was higher than that of the cemented carbide without the addition of trace lanthanum. Therefore, the yttrium element is considered to be a strengthening element. Further, in addition to the lanthanum element, other suitable strengthening elements may be cerium (Sc), cerium (Nb), molybdenum (Mo), yttrium (Y), yttrium (Ru), yttrium (Hf), yttrium (Re), Palladium (Pd), cerium (Ta), zirconium (Zr), boron (B), nitrogen (N), or oxygen (O).
第First 44 實施例:Example:
進一步地,本案發明人又完成本發明之硬質合金的第4實施例。於第4實施例之中,本案發明人係以六方密集結構(Hexagonal close-packed structure)之碳化鎢(W2
C)粉末作為本發明之硬質合金的碳化物,並以莫耳組成上包含Al10
Co19
Cr5
Cu10
Fe9
Ni3
之高熵合金粉末作為黏結相金屬之製程原料;其中,鋁(Al)、鈷(Co)、鉻(Cr)、銅(Cu)、鐵(Fe)、與鎳(Ni)之間的莫耳比為10:19:5:10:9:3。值得說明的是,莫耳組成上包含Al10
Co19
Cr5
Cu10
Fe9
Ni3
之高熵合金係以簡易符號CHK3表示。此外,該碳化鎢與該高熵合金的配方係整理於下表(7)之中。進一步地,本案發明人將碳化鎢與高熵合金之混粉執行雷射燒結製程,進以獲得本發明之硬質合金的第6樣品;並且,利用維氏硬度試驗機可以測得第6樣品的硬度為HV1370。請參閱圖5,係顯示該硬質合金之第6樣品的剖面電子顯微影像圖。觀察圖5之後,吾人可輕易地發現利用雷射燒結製程所製得之第6樣品並無具有明顯的裂痕(crack)或孔洞(voids, pores)等缺陷。 表(7)
第First 55 實施例:Example:
進一步地,本案發明人又完成本發明之硬質合金的第5實施例。於第5實施例之中,本案發明人係以立方晶系的碳化鈦(TiC)粉末作為本發明之硬質合金的碳化物,並以莫耳組成上包含Ni3
FeCrTi0.5
之合金粉末作為黏結相金屬之製程原料;其中,鎳(Ni)、鐵(Fe)、鉻(Cr)、與鈦(Ti)之間的莫耳比為3:1:1:0.5。此外,該碳化鈦粉末與該合金粉末的配方係整理於下表(8)之中。進一步地,本案發明人將碳化鈦與合金之混粉執行雷射燒結製程,進以獲得本發明之硬質合金的第7樣品;並且,利用維氏硬度試驗機可以測得第7樣品的硬度為HV1100。 表(8)
如此,上述係已完整且清楚地說明本發明之適於積層製程的硬質合金,經由上述,可以得知本發明係具有下列之優點:Thus, the above-mentioned series has completely and clearly explained the cemented carbide suitable for the lamination process of the present invention, and it can be understood from the above that the present invention has the following advantages:
(1)習知的硬質合金通常包含質硬的碳化物與質軟的黏結相金屬(binding phase metal)等黏結相金屬,其中,鈷為常用的黏結相金屬,但降低了純碳化鎢的硬度與耐磨性。不同於習知的硬質合金的組成,本發明特別以至少四種金屬元素組成一合金材料,並以至少一種碳化物及該合金材料構成一種適於積層製程的硬質合金。並且,實驗資料係證實,本發明之硬質合金係能夠利用例如雷射燒結之積層製程或者傳統真空燒結製程對於上述碳化物粉末與合金材料粉末進行加工之後而製得。同時,所製得的硬質合金係具有至少HV1100以上的維氏硬度值。(1) Conventional cemented carbides usually contain a hard phase carbide and a soft phase phase metal such as a binding phase metal. Among them, cobalt is a commonly used binder phase metal, but the hardness of pure tungsten carbide is lowered. With wear resistance. Unlike the conventional composition of cemented carbide, the present invention particularly comprises an alloy material of at least four metal elements, and at least one carbide and the alloy material constitute a cemented carbide suitable for a lamination process. Further, the experimental data confirmed that the cemented carbide of the present invention can be obtained by processing the above-described carbide powder and alloy material powder by, for example, a laminate process of laser sintering or a conventional vacuum sintering process. At the same time, the obtained cemented carbide has a Vickers hardness value of at least HV1100 or more.
(2)另一方面,本發明之硬質合金的成品或半成品的型態可為下列任一種:粉末、線材、焊條、或塊材。並且,本發明之硬質合金的成品或半成品係可透過以下任一種製程方式而被加工披覆至一目標工件的表面上:鑄造、電弧焊、熱噴塗、熱燒結、或雷射燒結。(2) On the other hand, the form of the finished or semi-finished product of the cemented carbide of the present invention may be any of the following: a powder, a wire, an electrode, or a block. Moreover, the finished or semi-finished product of the cemented carbide of the present invention can be processed and coated onto the surface of a target workpiece by any of the following processes: casting, arc welding, thermal spraying, thermal sintering, or laser sintering.
必須加以強調的是,上述之詳細說明係針對本發明可行實施例之具體說明,惟該實施例並非用以限制本發明之專利範圍,凡未脫離本發明技藝精神所為之等效實施或變更,均應包含於本案之專利範圍中。It is to be understood that the foregoing detailed description of the embodiments of the present invention is not intended to Both should be included in the scope of the patent in this case.
<本發明>
11‧‧‧硬質合金結構
12‧‧‧黏結金屬相
13‧‧‧第1種缺碳相
13’‧‧‧第2種缺碳相<present invention>
11‧‧‧Carbide structure
12‧‧‧ Bonded metal phase
13‧‧‧1st carbon-deficient phase
13'‧‧‧The second carbon-deficient phase
<習知>無<知知> none
圖1係顯示碳化鎢、高熵合金與碳元素之混粉的背向散射電子顯微影 像圖; 圖2係顯示本發明之一種適於積層製造的硬質合金之第1樣品與第2樣 品電子顯微影像圖; 圖3係顯示硬質合金之第3樣品的電子顯微影像圖; 圖4係顯示硬質合金之第3樣品的剖面電子顯微影像圖; 圖5係顯示該硬質合金之第6樣品的剖面電子顯微影像圖。1 is a backscattered electron micrograph showing a mixture of tungsten carbide, a high entropy alloy and a carbon element; and FIG. 2 is a view showing a first sample and a second sample electron of a cemented carbide suitable for lamination manufacturing of the present invention. FIG. 3 is an electron micrograph of the third sample of the cemented carbide; FIG. 4 is a cross-sectional electron micrograph of the third sample of the cemented carbide; FIG. 5 shows the sixth of the cemented carbide. A cross-sectional electron micrograph of the sample.
Claims (8)
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