TWI748676B - Cemented carbide and cutting tools equipped with it - Google Patents
Cemented carbide and cutting tools equipped with it Download PDFInfo
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- TWI748676B TWI748676B TW109134615A TW109134615A TWI748676B TW I748676 B TWI748676 B TW I748676B TW 109134615 A TW109134615 A TW 109134615A TW 109134615 A TW109134615 A TW 109134615A TW I748676 B TWI748676 B TW I748676B
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23B—TURNING; BORING
- B23B27/00—Tools for turning or boring machines; Tools of a similar kind in general; Accessories therefor
- B23B27/14—Cutting tools of which the bits or tips or cutting inserts are of special material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23B—TURNING; BORING
- B23B41/00—Boring or drilling machines or devices specially adapted for particular work; Accessories specially adapted therefor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23B—TURNING; BORING
- B23B51/00—Tools for drilling machines
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- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
- C22C29/06—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds
- C22C29/08—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds based on tungsten carbide
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Abstract
本發明之超硬合金具備包含複數個碳化鎢粒子之第1相、以及包含鈷之第2相,且於藉由對利用掃描式電子顯微鏡拍攝超硬合金之圖像進行圖像處理,而算出碳化鎢粒子各者之圓相當徑之情形時,圓相當徑為0.3 μm以上1.0 μm以下之碳化鎢粒子之個數基準之比率為50%以上,於藉由以頻數為縱軸、以等級為橫軸之柱狀圖表示碳化鎢粒子之圓相當徑之分佈之情形時,頻數為碳化鎢粒子之個數,等級係上述圓相當徑以升序方式間隔0.1 μm分隔而成,於橫軸中,將超過0.3 μm且為0.6 μm以下之範圍規定為第1範圍,將超過0.6 μm且為1.0 μm以下之範圍規定為第2範圍,第1範圍及第2範圍分別具有至少一個極大頻數,第1範圍內存在之極大頻數中最大之第1極大頻數相對於碳化鎢粒子總數之比率為10%以上,第2範圍內存在之極大頻數中最大之第2極大頻數相對於碳化鎢粒子總數之比率為10%以上。The cemented carbide of the present invention has a first phase containing a plurality of tungsten carbide particles and a second phase containing cobalt. In the case of tungsten carbide particles with a circle equivalent diameter, the ratio of the number of tungsten carbide particles with a circle equivalent diameter of 0.3 μm or more and 1.0 μm or less is 50% or more. When the histogram on the horizontal axis shows the distribution of the circle-equivalent diameters of tungsten carbide particles, the frequency is the number of tungsten carbide particles, and the grade is the above-mentioned circle-equivalent diameter separated by 0.1 μm in ascending order. In the horizontal axis, The range exceeding 0.3 μm and less than 0.6 μm is defined as the first range, and the range exceeding 0.6 μm and less than 1.0 μm is defined as the second range. The first range and the second range have at least one maximum frequency. The first The ratio of the first maximum frequency in the maximum frequency in the range to the total number of tungsten carbide particles is more than 10%, and the ratio of the second maximum frequency in the maximum frequency in the second range to the total number of tungsten carbide particles is More than 10%.
Description
本發明係關於一種超硬合金及具備其之切削工具。The present invention relates to a super hard alloy and a cutting tool provided with it.
印刷電路基板之開孔中,ϕ1 mm以下之小徑開孔成為主流。因此,作為小徑鑽頭等工具所使用之超硬合金,使用硬質相包含平均粒徑1 μm以下之碳化鎢粒子之所謂之微粒超硬合金(例如日本專利特開2007-92090號公報(專利文獻1)、日本專利特開2012-52237號公報(專利文獻2)、日本專利特開2012-117100號公報(專利文獻3))。 [先前技術文獻] [專利文獻] Among the openings of printed circuit boards, small-diameter openings below ϕ1 mm have become the mainstream. Therefore, as a cemented carbide used in tools such as small-diameter drills, a so-called fine-grained cemented carbide in which the hard phase contains tungsten carbide particles with an average particle diameter of 1 μm or less is used (for example, Japanese Patent Laid-Open No. 2007-92090 (Patent Document) 1), Japanese Patent Laid-Open No. 2012-52237 (Patent Document 2), and Japanese Patent Laid-Open No. 2012-117100 (Patent Document 3)). [Prior Technical Literature] [Patent Literature]
[專利文獻1]日本專利特開2007-92090號公報 [專利文獻2]日本專利特開2012-52237號公報 [專利文獻3]日本專利特開2012-117100號公報 [Patent Document 1] Japanese Patent Laid-Open No. 2007-92090 [Patent Document 2] Japanese Patent Laid-Open No. 2012-52237 [Patent Document 3] Japanese Patent Laid-Open No. 2012-117100
本發明之超硬合金具備包含複數個碳化鎢粒子之第1相、以及包含鈷之第2相,且 於藉由對利用掃描式電子顯微鏡拍攝之上述超硬合金之圖像進行圖像處理,而算出上述碳化鎢粒子各者之圓相當徑之情形時,上述圓相當徑為0.3 μm以上1.0 μm以下之上述碳化鎢粒子之個數基準之比率為50%以上, 於藉由以頻數為縱軸、以等級為橫軸之柱狀圖表示上述碳化鎢粒子之圓相當徑之分佈之情形時, 上述頻數為上述碳化鎢粒子之個數, 上述等級係上述圓相當徑以升序方式間隔0.1 μm分隔而成, 於上述橫軸中,將超過0.3 μm且為0.6 μm以下之範圍規定為第1範圍,將超過0.6 μm且為1.0 μm以下之範圍規定為第2範圍, 上述第1範圍及上述第2範圍分別具有至少一個極大頻數, 上述第1範圍內存在之極大頻數中最大之第1極大頻數相對於上述碳化鎢粒子總數之比率為10%以上, 上述第2範圍內存在之極大頻數中最大之第2極大頻數相對於上述碳化鎢粒子總數之比率為10%以上。 The cemented carbide of the present invention has a first phase containing a plurality of tungsten carbide particles and a second phase containing cobalt, and When calculating the circle equivalent diameter of each of the tungsten carbide particles by performing image processing on the image of the cemented carbide taken with a scanning electron microscope, the circle equivalent diameter is 0.3 μm or more and 1.0 μm or less The ratio of the number of tungsten carbide particles mentioned above is more than 50%, When the distribution of the circle-equivalent diameter of the tungsten carbide particles mentioned above is represented by a histogram with frequency as the vertical axis and grade as the horizontal axis, The above frequency is the number of the above tungsten carbide particles, The above grades are separated by the equivalent diameters of the above circles in ascending order at intervals of 0.1 μm, In the above horizontal axis, the range exceeding 0.3 μm and less than 0.6 μm is defined as the first range, and the range exceeding 0.6 μm and less than 1.0 μm is defined as the second range. The first range and the second range each have at least one maximum frequency, The ratio of the largest first maximum frequency among the maximum frequencies existing in the first range to the total number of tungsten carbide particles is 10% or more, The ratio of the largest second maximum frequency among the maximum frequencies existing in the second range to the total number of tungsten carbide particles is 10% or more.
本發明之切削工具具備包含上述超硬合金之刀尖。The cutting tool of the present invention is provided with a cutting edge containing the above-mentioned cemented carbide.
[本發明所欲解決之問題] 近年來,隨著5G(第5代移動通信系統)之擴大,資訊之高容量化進一步發展。因此,要求印刷電路基板具有更佳之耐熱性。為了提高印刷電路基板之耐熱性,對提高構成印刷電路基板之樹脂或玻璃填料之耐熱性的技術進行了開發。另一方面,印刷電路基板之難削程度由此變大。 [Problems to be solved by the present invention] In recent years, with the expansion of 5G (fifth generation mobile communication system), high-capacity information has been further developed. Therefore, the printed circuit board is required to have better heat resistance. In order to improve the heat resistance of the printed circuit board, technology has been developed to improve the heat resistance of the resin or glass filler constituting the printed circuit board. On the other hand, the degree of difficulty of the printed circuit board becomes greater.
因此,本發明之目的在於提供一種超硬合金及具備其之切削工具,上述超硬合金於用作工具材料之情形時,尤其是於印刷電路基板之微細加工時,亦能夠延長工具之壽命。Therefore, the object of the present invention is to provide a cemented carbide and a cutting tool provided with the cemented carbide. When the cemented carbide is used as a tool material, especially in the microfabrication of printed circuit boards, the life of the tool can be extended.
[本發明之效果] 本發明之超硬合金於用作工具材料之情形時,尤其是於印刷電路基板之微細加工時,亦能夠延長工具之壽命。 [Effects of the invention] When the cemented carbide of the present invention is used as a tool material, especially in the microfabrication of printed circuit boards, it can also extend the life of the tool.
[本發明之實施方式之說明] 首先,列舉本發明之實施方式加以說明。 (1)本發明之超硬合金具備包含複數個碳化鎢粒子之第1相、以及包含鈷之第2相,且 於藉由對利用掃描式電子顯微鏡拍攝之上述超硬合金之圖像進行圖像處理,而算出上述碳化鎢粒子各者之圓相當徑之情形時,上述圓相當徑為0.3 μm以上1.0 μm以下之上述碳化鎢粒子之個數基準之比率為50%以上, 於藉由以頻數為縱軸、以等級為橫軸之柱狀圖表示上述碳化鎢粒子之圓相當徑之分佈之情形時, 上述頻數為上述碳化鎢粒子之個數, 上述等級係上述圓相當徑以升序方式間隔0.1 μm分隔而成, 於上述橫軸中,將超過0.3 μm且為0.6 μm以下之範圍規定為第1範圍,將超過0.6 μm且為1.0 μm以下之範圍規定為第2範圍, 上述第1範圍及上述第2範圍分別具有至少一個極大頻數, 上述第1範圍內存在之極大頻數中最大之第1極大頻數相對於上述碳化鎢粒子總數之比率為10%以上, 上述第2範圍內存在之極大頻數中最大之第2極大頻數相對於上述碳化鎢粒子總數之比率為10%以上。 [Description of the embodiment of the present invention] First, the embodiments of the present invention will be described. (1) The cemented carbide of the present invention has a first phase containing a plurality of tungsten carbide particles and a second phase containing cobalt, and When calculating the circle equivalent diameter of each of the tungsten carbide particles by performing image processing on the image of the cemented carbide taken with a scanning electron microscope, the circle equivalent diameter is 0.3 μm or more and 1.0 μm or less The ratio of the number of tungsten carbide particles mentioned above is more than 50%, When the distribution of the circle-equivalent diameter of the tungsten carbide particles mentioned above is represented by a histogram with frequency as the vertical axis and grade as the horizontal axis, The above frequency is the number of the above tungsten carbide particles, The above grades are separated by the equivalent diameters of the above circles in ascending order at intervals of 0.1 μm, In the above horizontal axis, the range exceeding 0.3 μm and less than 0.6 μm is defined as the first range, and the range exceeding 0.6 μm and less than 1.0 μm is defined as the second range. The first range and the second range each have at least one maximum frequency, The ratio of the largest first maximum frequency among the maximum frequencies existing in the first range to the total number of tungsten carbide particles is 10% or more, The ratio of the largest second maximum frequency among the maximum frequencies existing in the second range to the total number of tungsten carbide particles is 10% or more.
本發明之超硬合金於用作工具材料之情形時,尤其是於印刷電路基板之微細加工時,亦能夠延長工具之壽命。When the cemented carbide of the present invention is used as a tool material, especially in the microfabrication of printed circuit boards, it can also extend the life of the tool.
(2)上述超硬合金較佳為於利用掃描式電子顯微鏡拍攝之圖像中,包含75面積%以上且未達100面積%之上述第1相,且包含超過0體積%且為20面積%以下之上述第2相。藉此,工具壽命進一步延長。(2) The above-mentioned cemented carbide preferably contains 75 area% or more and less than 100 area% of the first phase in an image taken by a scanning electron microscope, and includes more than 0 volume% and 20 area% The second phase mentioned below. As a result, the tool life is further extended.
(3)上述超硬合金較佳為於利用掃描式電子顯微鏡拍攝之圖像中,包含5面積%以上12面積%以下之上述第2相。藉此,工具壽命進一步延長。(3) The above-mentioned cemented carbide preferably includes 5 area% or more and 12 area% or less of the second phase in an image taken with a scanning electron microscope. As a result, the tool life is further extended.
(4)上述超硬合金較佳為包含鉻,且 上述鉻相對於上述鈷之質量基準之比率為5%以上10%以下。藉此,超硬合金之耐破損性提高,工具壽命進一步延長。 (4) The above-mentioned cemented carbide preferably contains chromium, and The ratio of the chromium to the mass standard of the cobalt is 5% or more and 10% or less. As a result, the damage resistance of the cemented carbide is improved, and the tool life is further extended.
(5)於上述超硬合金包含釩之情形時,上述超硬合金之上述釩之質量基準之含有率較佳為未達100 ppm。藉此,超硬合金之強度提高。(5) When the cemented carbide contains vanadium, the content of vanadium in the cemented carbide is preferably less than 100 ppm on a mass basis. As a result, the strength of the cemented carbide is improved.
(6)上述圓相當徑未達0.3 μm之上述碳化鎢粒子之個數基準之比率較佳為7%以下。藉此,工具壽命進一步延長。(6) The ratio of the number of tungsten carbide particles whose circle equivalent diameter is less than 0.3 μm is preferably 7% or less. As a result, the tool life is further extended.
(7)上述第2極大頻數相對於上述第1極大頻數之比率較佳為0.8以上1.2以下。藉此,工具壽命進一步延長。(7) The ratio of the second maximum frequency to the first maximum frequency is preferably 0.8 or more and 1.2 or less. As a result, the tool life is further extended.
(8)於在上述橫軸中將超過0.4 μm且為0.6 μm以下之範圍規定為第3範圍,將超過0.6 μm且為0.8 μm以下之範圍規定為第4範圍之情形時, 較佳為上述第3範圍具有上述第1極大頻數,且 上述第4範圍具有上述第2極大頻數。藉此,工具壽命進一步延長。 (8) When the above horizontal axis defines the range exceeding 0.4 μm and less than 0.6 μm as the third range and the range exceeding 0.6 μm and less than 0.8 μm as the fourth range, Preferably, the third range has the first maximum frequency, and The above-mentioned fourth range has the above-mentioned second maximum frequency. As a result, the tool life is further extended.
(9)本發明之切削工具具備包含上述超硬合金之刀尖。本發明之切削工具具有較長之工具壽命。(9) The cutting tool of the present invention is provided with a cutting edge containing the above-mentioned cemented carbide. The cutting tool of the present invention has a longer tool life.
(10)上述切削工具較佳為印刷電路基板加工用旋轉工具。本發明之切削工具適合用於印刷電路基板之微細加工。(10) The cutting tool is preferably a rotating tool for processing a printed circuit board. The cutting tool of the present invention is suitable for the micro processing of printed circuit boards.
[本發明之實施方式之詳情] 以下,一面參照圖式一面對本發明之超硬合金及切削工具之具體例進行說明。於本發明之圖式中,相同之參照符號表示同一部分或相當部分。又,為了使圖式清晰簡單,長度、寬度、厚度、深度等尺寸關係進行了適當變更,未必表示實際之尺寸關係。 [Details of the embodiment of the present invention] Hereinafter, specific examples of the cemented carbide and cutting tool of the present invention will be described with reference to the drawings. In the drawings of the present invention, the same reference signs indicate the same part or a corresponding part. In addition, in order to make the drawings clear and simple, the dimensional relationships such as length, width, thickness, and depth have been appropriately changed, and they do not necessarily represent the actual dimensional relationships.
於本說明書中,「A~B」之形式之記載於無特殊定義之情形時意指範圍之上限下限(即A以上B以下),於僅B記載了單位而A未記載單位之情形時,A之單位與B之單位相同。In this specification, when the form of "A~B" is described in the absence of a special definition, it means the upper and lower limits of the range (that is, above A and below B). When only B describes the unit but A does not describe the unit, The unit of A is the same as the unit of B.
於本說明書中,於藉由化學式表示化合物等之情形時,若未特別限定原子比,則視為包括先前公知之所有原子比,未必應僅限定於化學計量範圍內之原子比。例如,於記為「WC」之情形時,構成WC之原子數之比包括先前公知之所有原子比。In this specification, when a compound or the like is represented by a chemical formula, if the atomic ratio is not particularly limited, it is deemed to include all previously known atomic ratios, and it is not necessarily limited to the atomic ratio within the stoichiometric range. For example, in the case of "WC", the ratio of the number of atoms constituting WC includes all previously known atomic ratios.
本發明人等為了獲得能夠延長工具之壽命之超硬合金,對使用包含先前之微粒超硬合金之工具對印刷電路基板進行微細加工之情形時之工具的損傷形態進行了研究,結果獲得下述見解。In order to obtain a cemented carbide that can extend the life of the tool, the inventors studied the damage pattern of the tool when a tool containing the previous particulate cemented carbide is used to microfabricate a printed circuit board, and the result is as follows opinion.
使用令將玻璃纖維編織成布狀而成之玻璃織布含浸環氧樹脂而成之玻璃環氧基板、或令玻璃織布含浸聚醯亞胺樹脂而成之玻璃聚醯亞胺基板等作為印刷電路基板中使用之基板。Use glass epoxy substrates made by weaving glass fibers into cloth and impregnated with epoxy resin, or glass polyimide substrates made by impregnating glass fabrics with polyimide resin as printing The substrate used in the circuit substrate.
使用包含先前之微粒超硬合金之工具對印刷電路基板進行微細加工,結果確認到作為超硬合金之結合相之鈷因印刷電路基板中之樹脂或玻璃纖維而出現局部磨耗,碳化鎢粒子(以下亦記為「WC粒子」)露出,導致該WC粒子脫落。The printed circuit board was micro-processed with a tool containing the previous particulate cemented carbide. As a result, it was confirmed that the cobalt, which is the bonding phase of the cemented carbide, was locally worn due to the resin or glass fiber in the printed circuit board. Tungsten carbide particles (below Also recorded as "WC particles") exposed, causing the WC particles to fall off.
因此,本發明人等推測為了實現較長之工具壽命,減少加工中工具表面露出之鈷(Co)之量、以及提高WC粒子彼此之結合力較為重要。又,本發明人等基於超硬合金中之WC粒子直接參與印刷電路基板之切削之情況,推測為了維持微細加工之精度,WC粒子連續且緻密地出現於工具表面亦較為重要。Therefore, the inventors of the present invention speculate that in order to achieve a longer tool life, it is important to reduce the amount of cobalt (Co) exposed on the surface of the tool during processing and to increase the bonding force of the WC particles with each other. In addition, based on the fact that the WC particles in the cemented carbide directly participate in the cutting of the printed circuit board, the inventors speculate that it is also important for the WC particles to continuously and densely appear on the surface of the tool in order to maintain the precision of the microfabrication.
為了減少存在Co之WC彼此之界面,減少加工中工具表面露出之鈷之量,考慮增大超硬合金中之WC粒子之粒徑,減少鈷量。然而,若增大WC粒子之粒徑,減少鈷量,則強度容易降低,從而容易於加工中產生破損。In order to reduce the interface between WC with Co and reduce the amount of cobalt exposed on the surface of the tool during processing, it is considered to increase the particle size of the WC particles in the cemented carbide and reduce the amount of cobalt. However, if the particle size of the WC particles is increased and the amount of cobalt is reduced, the strength is likely to decrease, and damage is likely to occur during processing.
基於上述見解,本發明人等進行了銳意研究,結果新發現藉由控制WC粒子之粒徑,可提高WC粒子間之結合力,從而完成了本發明之超硬合金。於下文對本發明之超硬合金及具備其之切削工具之詳情作出說明。Based on the above insights, the inventors conducted intensive research, and as a result, they newly discovered that by controlling the particle size of the WC particles, the binding force between the WC particles can be increased, thereby completing the cemented carbide of the present invention. The details of the cemented carbide of the present invention and the cutting tool provided with it are described below.
[實施方式1:超硬合金] 本發明之超硬合金具備包含複數個碳化鎢粒子之第1相、以及包含鈷之第2相,且 於藉由對利用掃描式電子顯微鏡拍攝超硬合金之圖像進行圖像處理,而算出碳化鎢粒子各者之圓相當徑之情形時,圓相當徑為0.3 μm以上1.0 μm以下之碳化鎢粒子之個數基準之比率為50%以上,於藉由以頻數為縱軸、以等級為橫軸之柱狀圖表示碳化鎢粒子之圓相當徑之分佈之情形時,頻數為碳化鎢粒子之個數,等級係上述圓相當徑以升序方式間隔0.1 μm分隔而成,於橫軸中,將超過0.3 μm且為0.6 μm以下之範圍規定為第1範圍,將超過0.6 μm且為1.0 μm以下之範圍規定為第2範圍,第1範圍及第2範圍分別具有至少一個極大頻數,第1範圍內存在之極大頻數中最大之第1極大頻數相對於碳化鎢粒子總數之比率為10%以上,第2範圍內存在之極大頻數中最大之第2極大頻數相對於碳化鎢粒子總數之比率為10%以上。 [Embodiment 1: Cemented carbide] The cemented carbide of the present invention has a first phase containing a plurality of tungsten carbide particles and a second phase containing cobalt, and In the case of calculating the circle equivalent diameter of each tungsten carbide particle by image processing on the image of the cemented carbide taken with a scanning electron microscope, the circle equivalent diameter of tungsten carbide particles is 0.3 μm or more and 1.0 μm or less The ratio of the number basis is more than 50%. When the bar graph with frequency as the vertical axis and grade as the horizontal axis shows the distribution of the circle-equivalent diameter of tungsten carbide particles, the frequency is the number of tungsten carbide particles. The number, the grade is the above-mentioned circle equivalent diameter divided by 0.1 μm in ascending order. In the horizontal axis, the range exceeding 0.3 μm and less than 0.6 μm is defined as the first range, and the range exceeding 0.6 μm and less than 1.0 μm is defined as the first range. The range is defined as the second range. The first range and the second range each have at least one maximum frequency. The ratio of the largest first maximum frequency to the total number of tungsten carbide particles in the first range is 10% or more. 2 The ratio of the largest second largest frequency among the largest frequencies present in the range to the total number of tungsten carbide particles is more than 10%.
本發明之超硬合金於用作工具材料之情形時,尤其是於印刷電路基板之微細加工時,亦能夠延長工具之壽命。其原因尚不明確,但可作如下述(i)及(ii)之推測。When the cemented carbide of the present invention is used as a tool material, especially in the microfabrication of printed circuit boards, it can also extend the life of the tool. The reason is not clear, but it can be inferred as follows (i) and (ii).
(i)本發明之超硬合金中,圓相當徑為0.3 μm以上1.0 μm以下之碳化鎢粒子之個數基準之比率為50%以上。藉此,超硬合金組織變得均質,可抑制微細加工之精度隨著使用而降低,從而使工具壽命變長。(i) In the cemented carbide of the present invention, the ratio of the number of tungsten carbide particles having a circle equivalent diameter of 0.3 μm or more and 1.0 μm or less is 50% or more. As a result, the structure of the cemented carbide becomes homogeneous, which can prevent the precision of micro-machining from decreasing with use, thereby prolonging the life of the tool.
(ii)本發明之超硬合金中,WC粒子之圓相當徑之分佈於粒徑超過0.3 μm且為0.6 μm以下之範圍(第1範圍)及超過0.6 μm且為1.0 μm以下之範圍(第2範圍)中分別具有至少一個極大頻數。第1範圍內最大之極大頻數(第1極大頻數)及第2範圍內最大之極大頻數(第2極大頻數)相對於超硬合金中之碳化鎢粒子總數之比率分別為10%以上。(ii) In the cemented carbide of the present invention, the circle-equivalent diameter of the WC particles is distributed in the range where the particle size exceeds 0.3 μm and is 0.6 μm or less (the first range) and the range where the particle size exceeds 0.6 μm and is 1.0 μm or less (the first range) 2) each has at least one maximum frequency. The ratio of the largest maximum frequency in the first range (first maximum frequency) and the largest maximum frequency in the second range (second maximum frequency) to the total number of tungsten carbide particles in the cemented carbide is 10% or more.
藉此,超硬合金具有如下形態之組織:圓相當徑較大之WC粒子成為骨架,於該WC粒子間,圓相當徑較小之WC粒子填充間隙。由於該超硬合金中WC粒子彼此結合,故WC粒子之脫落得到抑制,藉此使耐磨性提高。進而,藉由磨耗得到抑制,而切削阻力之增加得到抑制,從而耐破損性提高。因此工具壽命變長。As a result, the cemented carbide has a structure in which the WC particles with a larger circle equivalent diameter become a skeleton, and the WC particles with a smaller circle equivalent diameter fill the gaps between the WC particles. Since the WC particles in the cemented carbide are bonded to each other, the shedding of the WC particles is suppressed, thereby improving the wear resistance. Furthermore, by suppressing abrasion, the increase in cutting resistance is suppressed, and the breakage resistance is improved. Therefore, the tool life becomes longer.
進而,該超硬合金中,加工中工具表面露出之鈷量低於先前之微粒超硬合金。因此,加工中不易產生鈷之磨耗,可抑制WC粒子之脫落,從而使工具壽命變長。Furthermore, in this cemented carbide, the amount of cobalt exposed on the surface of the tool during processing is lower than that of the previous particulate cemented carbide. Therefore, cobalt abrasion is less likely to occur during processing, and WC particles can be prevented from falling off, thereby prolonging the tool life.
<第1相> (第1相之組成) 第1相包含碳化鎢粒子。此處,碳化鎢不僅包括「純粹之WC(為不含任何雜質元素之WC,亦包括雜質元素未達檢測極限之WC)」,亦包括「在不損害本發明之效果之範圍內於其內部刻意或不可避免地含有其他雜質元素之WC」。碳化鎢中所含雜質之濃度(於構成雜質之元素為兩種以上之情形時,為其等之合計濃度)相對於上述碳化鎢及上述雜質之總量未達0.1質量%。第1相中之雜質元素之含量藉由ICP(Inductively Coupled Plasma,感應耦合電漿)發射光譜法(Emission Spectroscopy)(測定裝置:島津製作所製造之「ICPS-8100」(商標))進行測定。 <Phase 1> (Composition of Phase 1) The first phase contains tungsten carbide particles. Here, tungsten carbide not only includes "pure WC (which does not contain any impurity elements, and also includes WC whose impurity elements do not reach the detection limit)", but also includes "within the scope of not impairing the effects of the present invention. Deliberately or inevitably, WC containing other impurity elements". The concentration of impurities contained in tungsten carbide (when there are two or more elements constituting the impurities, the total concentration of the same) is less than 0.1% by mass relative to the total amount of the tungsten carbide and the impurities. The content of impurity elements in the first phase was measured by ICP (Inductively Coupled Plasma) emission spectroscopy (measurement device: "ICPS-8100" (trademark) manufactured by Shimadzu Corporation).
(碳化鎢粒子之圓相當徑之分佈) 碳化鎢粒子中,圓相當徑為0.3 μm以上1.0 μm以下之碳化鎢粒子之個數基準之比率為50%以上。藉此,超硬合金組織變得均質,可抑制微細加工之精度隨著使用而降低,從而使工具壽命變長。 (Distribution of circle equivalent diameter of tungsten carbide particles) Among tungsten carbide particles, the ratio of tungsten carbide particles with a circle equivalent diameter of 0.3 μm or more and 1.0 μm or less based on the number of tungsten carbide particles is 50% or more. As a result, the structure of the cemented carbide becomes homogeneous, which can prevent the precision of micro-machining from decreasing with use, thereby prolonging the life of the tool.
於超硬合金中之鈷量一定之情形時,若圓相當徑超過1 μm之粗粒碳化鎢粒子之比率增加,則有硬度降低而耐磨性降低之傾向,若圓相當徑未達0.3 μm之微粒碳化鎢粒子之比率增加,則有碳化鎢粒子之脫落變嚴重而耐磨性降低之傾向。本發明之超硬合金中,圓相當徑為0.3 μm以上1.0 μm以下之碳化鎢粒子之個數基準之比率為50%以上,因此能夠具有優異之耐磨性。When the amount of cobalt in the cemented carbide is constant, if the ratio of coarse-grained tungsten carbide particles with a circle equivalent diameter of more than 1 μm increases, the hardness will decrease and the wear resistance tends to decrease. If the circle equivalent diameter does not reach 0.3 μm As the ratio of fine tungsten carbide particles increases, the shedding of tungsten carbide particles becomes serious and the wear resistance tends to decrease. In the cemented carbide of the present invention, the ratio of the number of tungsten carbide particles with a circle equivalent diameter of 0.3 μm or more and 1.0 μm or less is 50% or more, so it can have excellent wear resistance.
就提高超硬合金組織之均質性之觀點而言,圓相當徑為0.3 μm以上1.0 μm以下之碳化鎢粒子之個數基準之比率為50%以上,較佳為70%以上。圓相當徑為0.3 μm以上1.0 μm以下之碳化鎢粒子之個數基準之比率的上限並無特別限定,例如可設為100%以下、90%以下、80%以下。圓相當徑為0.3 μm以上1.0 μm以下之碳化鎢粒子之個數基準之比率可設為50%以上100%以下、60%以上90%以下、70%以上80%以下。From the viewpoint of improving the homogeneity of the cemented carbide structure, the ratio of the number of tungsten carbide particles with a circle equivalent diameter of 0.3 μm or more and 1.0 μm or less is 50% or more, preferably 70% or more. The upper limit of the number-based ratio of tungsten carbide particles having a circle equivalent diameter of 0.3 μm or more and 1.0 μm or less is not particularly limited. For example, it may be 100% or less, 90% or less, or 80% or less. The ratio of the number of tungsten carbide particles whose circle equivalent diameter is 0.3 μm or more and 1.0 μm or less can be set to 50% or more and 100% or less, 60% or more and 90% or less, and 70% or more and 80% or less.
圓相當徑未達0.3 μm之碳化鎢粒子之個數基準之比率較佳為7%以下。圓相當徑未達0.3 μm之碳化鎢粒子對於提高超硬合金之強度、或減少加工中工具表面露出之鈷量的作用較小。因此,藉由降低圓相當徑未達0.3 μm之碳化鎢粒子之個數基準之比率,而使工具壽命變得更長。The ratio of tungsten carbide particles whose circle equivalent diameter is less than 0.3 μm is preferably 7% or less. Tungsten carbide particles with a circle equivalent diameter of less than 0.3 μm have little effect on increasing the strength of the cemented carbide or reducing the amount of cobalt exposed on the surface of the tool during processing. Therefore, by reducing the ratio of the number of tungsten carbide particles whose circle equivalent diameter is less than 0.3 μm, the tool life becomes longer.
圓相當徑未達0.3 μm之碳化鎢粒子之個數基準之比率較佳為0%以上7%以下,進而較佳為0%以上5%以下。又,圓相當徑未達0.2 μm之碳化鎢粒子之個數基準之比率較佳為0%以上3%以下。The ratio of tungsten carbide particles whose circle equivalent diameter is less than 0.3 μm is preferably 0% or more and 7% or less, and more preferably 0% or more and 5% or less. In addition, the ratio of the number of tungsten carbide particles whose circle equivalent diameter is less than 0.2 μm is preferably from 0% to 3%.
按照下述(A1)~(C1)之步序測定碳化鎢粒子之圓相當徑。 (A1)對超硬合金之任意表面或任意截面進行鏡面加工。作為鏡面加工之方法,例如可列舉:利用鑽石膏進行研磨之方法、使用聚焦離子束裝置(FIB裝置)之方法、使用截面拋光儀裝置(CP裝置)之方法、及將該等方法加以組合之方法等。 Measure the circle equivalent diameter of tungsten carbide particles according to the following steps (A1) to (C1). (A1) Mirror processing any surface or any cross section of the cemented carbide. As a method of mirror surface processing, for example, a method using diamond paste for polishing, a method using a focused ion beam device (FIB device), a method using a cross-section polisher device (CP device), and a combination of these methods Methods etc.
(B1)利用掃描式電子顯微鏡拍攝超硬合金之加工面。觀察倍率設為5000倍。將利用掃描式電子顯微鏡拍攝本發明之超硬合金之圖像的一例示於圖1。於圖1右下方之標度中,1刻度表示1 μm。(B1) Use a scanning electron microscope to photograph the processed surface of the cemented carbide. The observation magnification is set to 5000 times. An example of an image of the cemented carbide of the present invention taken by a scanning electron microscope is shown in FIG. 1. In the scale at the bottom right of Figure 1, 1 scale means 1 μm.
(C1)將上述(B1)中所得之拍攝圖像輸入至電腦中,使用圖像解析軟體(ImageJ:https://imagej.nih.gov/ij/)進行圖像處理,算出碳化鎢粒子之圓相當徑(Heywood直徑:等面積圓直徑)。包含碳化鎢粒子之第1相及包含鈷之第2相可藉由上述拍攝圖像中之顏色深淺進行識別。將對圖1之拍攝圖像進行圖像處理所得之圖像示於圖2。圖2中,黑色區域為第1相,白色區域為第2相。白色之線表示晶界。於圖2右下方之標度中,1刻度表示1 μm。(C1) Input the captured image obtained in (B1) above into the computer, and use the image analysis software (ImageJ: https://imagej.nih.gov/ij/) for image processing to calculate the tungsten carbide particles Circle equivalent diameter (Heywood diameter: equal area circle diameter). The first phase containing tungsten carbide particles and the second phase containing cobalt can be identified by the color shade in the above-mentioned captured image. The image obtained by performing image processing on the captured image of FIG. 1 is shown in FIG. 2. In Figure 2, the black area is the first phase, and the white area is the second phase. The white line represents the grain boundary. In the scale at the bottom right of Figure 2, 1 scale means 1 μm.
於本說明書中,按照下述(D1)及(E1)之步序算出超硬合金中之圓相當徑為0.3 μm以上1.0 μm以下之碳化鎢粒子之個數基準的比率。 (D1)於三個測定視野中進行上述(C1)之圖像處理。一個測定視野之大小設為縱25.3 μm×寬17.6 μm之矩形。 In this manual, the following steps (D1) and (E1) are used to calculate the ratio based on the number of tungsten carbide particles with a circle equivalent diameter of 0.3 μm to 1.0 μm in cemented carbide. (D1) Perform the above-mentioned (C1) image processing in three measurement fields of view. The size of a measurement field is a rectangle with a length of 25.3 μm × a width of 17.6 μm.
(E1)於三個測定視野中分別算出圓相當徑為0.3 μm以上1.0 μm以下之碳化鎢粒子相對於測定視野中所有碳化鎢粒子之個數基準的比率。將其等之平均值作為超硬合金中之圓相當徑為0.3 μm以上1.0 μm以下之碳化鎢粒子之個數基準的比率。(E1) Calculate the ratio of tungsten carbide particles with a circle equivalent diameter of 0.3 μm or more and 1.0 μm or less to the number basis of all tungsten carbide particles in the measurement field in the three measurement fields. The average value of these is regarded as the ratio based on the number of tungsten carbide particles with a circle-equivalent diameter of 0.3 μm or more and 1.0 μm or less in the cemented carbide.
根據申請人所進行之測定,確認到於同一試樣中進行測定之情形時,即便變更測定視野之選擇位置而測定複數次超硬合金中之圓相當徑為0.3 μm以上1.0 μm以下之碳化鎢粒子之個數基準的比率,測定結果之偏差亦較少,即便任意設定測定視野,結果亦不會變得隨意。According to the measurement performed by the applicant, when it is confirmed that the measurement is performed on the same sample, even if the selected position of the measurement field is changed and the circle equivalent diameter in the cemented carbide is measured multiple times, the tungsten carbide whose diameter is 0.3 μm or more and 1.0 μm or less Based on the ratio of the number of particles, the deviation of the measurement result is also less. Even if the measurement field of view is set arbitrarily, the result will not become random.
本發明之超硬合金所含之碳化鎢粒子之圓相當徑的分佈滿足下述(a)。進而,於藉由以頻數為縱軸、以等級為橫軸之柱狀圖表示本發明之超硬合金所含之碳化鎢粒子之圓相當徑之分佈的情形時,滿足下述(b)及(c)。此處,頻數為碳化鎢粒子之個數,等級係上述圓相當徑以升序方式間隔0.1 μm分隔而成。The distribution of the circle-equivalent diameter of the tungsten carbide particles contained in the cemented carbide of the present invention satisfies the following (a). Furthermore, when the distribution of the circle-equivalent diameter of the tungsten carbide particles contained in the cemented carbide of the present invention is represented by a histogram with frequency on the vertical axis and grade on the horizontal axis, the following (b) and (c). Here, the frequency is the number of tungsten carbide particles, and the grade is the above-mentioned circle equivalent diameter separated by 0.1 μm in ascending order.
(a)圓相當徑為0.3 μm以上1.0 μm以下之碳化鎢粒子之個數基準之比率為50%以上。(a) The ratio of tungsten carbide particles with a circle equivalent diameter of 0.3 μm or more and 1.0 μm or less is 50% or more.
(b)於在橫軸中將超過0.3 μm且為0.6 μm以下之範圍規定為第1範圍,將超過0.6 μm且為1.0 μm以下之範圍規定為第2範圍之情形時,第1範圍及第2範圍分別具有至少一個極大頻數。(b) When the range exceeding 0.3 μm and less than 0.6 μm is defined as the first range on the horizontal axis, and the range exceeding 0.6 μm and less than 1.0 μm is defined as the second range, the first range and the second range The 2 ranges each have at least one maximum frequency.
(c)第1範圍內存在之極大頻數中最大之第1極大頻數相對於碳化鎢粒子總數之比率為10%以上,第2範圍內存在之極大頻數中最大之第2極大頻數相對於碳化鎢粒子總數之比率為10%以上。(c) The ratio of the largest first largest frequency in the first range to the total number of tungsten carbide particles is 10% or more, and the largest second largest frequency in the second range is relative to tungsten carbide The ratio of the total number of particles is more than 10%.
於本說明書中,按照下述(A2)及(B2)之步序製作柱狀圖。In this manual, follow the steps (A2) and (B2) below to make a histogram.
(A2)藉由上述碳化鎢粒子之圓相當徑之測定方法中記載之(A1)~(C1)之步序算出碳化鎢粒子之圓相當徑。於三個測定視野中進行碳化鎢粒子之圓相當徑之測定。(A2) Calculate the circle-equivalent diameter of tungsten carbide particles according to the steps (A1) to (C1) described in the above-mentioned method for measuring the circle-equivalent diameter of tungsten carbide particles. The circle equivalent diameter of tungsten carbide particles was measured in three measurement fields.
(B2)基於三個測定視野中測得之所有碳化鎢粒子之圓相當徑,製作以頻數為縱軸、以等級為橫軸之柱狀圖。頻數為碳化鎢粒子之個數,等級係圓相當徑以升序方式間隔0.1 μm分隔而成。(B2) Based on the circle-equivalent diameters of all tungsten carbide particles measured in the three measurement fields, a histogram with frequency as the vertical axis and grade as the horizontal axis is created. The frequency is the number of tungsten carbide particles, and the grade is the circle equivalent diameter separated by 0.1 μm in ascending order.
於本說明書中,極大頻數意指該頻數大於該頻數所屬等級之下一(圓相當徑較小之側)等級之頻數、以及該頻數所屬等級之上一(圓相當徑較大之側)等級之頻數之任一者。In this specification, the maximum frequency means that the frequency is greater than the level one below the level of the frequency (the side with the smaller diameter of the circle), and the level above the level (the side with the larger the circle is the larger diameter) above the level to which the frequency belongs Any one of the frequency.
再者,極大頻數所屬等級之下一等級、以及極大頻數所屬等級之上一等級亦可為第1範圍外或第2範圍外之等級。具體而言,於第1範圍內之極大頻數所屬之等級為超過0.3 μm且為0.4 μm以下之情形時,下一等級為超過0.2 μm且為0.3 μm以下,其處於第1範圍外。於第2範圍內之極大頻數所屬之等級為超過0.9 μm且為1.0 μm以下之情形時,上一等級為超過1.0 μm且為1.1 μm以下,其處於第2範圍外。Furthermore, the level below the level to which the extreme frequency belongs and the level above the level to which the extreme frequency belongs can also be a level outside the first range or outside the second range. Specifically, when the class to which the maximum frequency in the first range belongs is more than 0.3 μm and less than 0.4 μm, the next class is more than 0.2 μm and less than 0.3 μm, which is outside the first range. When the maximum frequency in the second range belongs to a level exceeding 0.9 μm and less than 1.0 μm, the previous level is more than 1.0 μm and less than 1.1 μm, which is outside the second range.
藉由滿足上述(a)~(c),可抑制微細加工之精度隨著使用而降低,使強度、耐破損性提高,可抑制WC粒子之脫落,從而使工具壽命變長。By satisfying the above (a) to (c), the precision of microfabrication can be suppressed from decreasing with use, the strength and breakage resistance can be improved, the falling of WC particles can be suppressed, and the tool life can be prolonged.
使用圖3~圖6對上述(a)~(c)加以說明。圖3~圖6分別為表示本發明之超硬合金中之碳化鎢粒子之圓相當徑之分佈之圖的一例。圖3~圖6中,橫軸表示以升序方式間隔0.1 μm將圓相當徑分隔而成之等級,縱軸表示屬於各等級之鎢粒子相對於全部鎢粒子之個數基準之比率(%)。The above (a) to (c) will be described with reference to Figs. 3 to 6. FIGS. 3 to 6 are respectively an example of a diagram showing the distribution of the circle-equivalent diameter of tungsten carbide particles in the cemented carbide of the present invention. In Figures 3 to 6, the horizontal axis represents the grades divided by the circle equivalent diameters in ascending order at intervals of 0.1 μm, and the vertical axis represents the ratio (%) of tungsten particles belonging to each grade to the number basis of all tungsten particles.
圖3~圖6中,「C~D」之形式之記載意指超過C且為D以下。具體而言,圖3~圖6之橫軸之「0~0.1」之記載意指超過0 μm且為0.1 μm以下,「0.1~0.2」之記載意指超過0.1 μm且為0.2 μm以下。In FIGS. 3 to 6, the description of the form of "C to D" means that it exceeds C and is less than D. Specifically, the description of "0 to 0.1" on the horizontal axis of FIGS. 3 to 6 means more than 0 μm and 0.1 μm or less, and the description of "0.1 to 0.2" means more than 0.1 μm and 0.2 μm or less.
圖3~圖6之形狀可視為橫軸之等級之規定相同,且將縱軸之頻數設為碳化鎢粒子之個數之情形時之柱狀圖的形狀。因此,可使用圖3~圖6之形狀對上述(a)~(c)進行說明。圖3~圖6中,縱軸表示屬於各等級之鎢粒子相對於全部鎢粒子之個數基準之比率(%),以下,為了便於說明,有時將圖3~圖6之縱軸記為頻數。The shape of Fig. 3 to Fig. 6 can be regarded as the shape of the histogram when the horizontal axis has the same level and the frequency on the vertical axis is set as the number of tungsten carbide particles. Therefore, the above-mentioned (a) to (c) can be described using the shapes of FIGS. 3 to 6. In Figures 3 to 6, the vertical axis represents the ratio (%) of tungsten particles belonging to each grade to the number basis of all tungsten particles. In the following, for convenience of explanation, the vertical axis of Figures 3 to 6 may be denoted as Frequency.
(圖3) 圖3中,圓相當徑為0.3 μm以上1.0 μm以下之碳化鎢粒子之個數基準之比率為50%以上(約72%)。因此,圖3所示之碳化鎢粒子之圓相當徑之分佈滿足上述(a)。 (image 3) In Figure 3, the ratio of tungsten carbide particles with a circle equivalent diameter of 0.3 μm or more and 1.0 μm or less is 50% or more (about 72%). Therefore, the circle-equivalent diameter distribution of the tungsten carbide particles shown in FIG. 3 satisfies the above (a).
圖3中,圓相當徑超過0.4 μm且為0.5 μm以下之等級之頻數大於該頻數所屬等級之下一等級(圓相當徑超過0.3 μm且為0.4 μm以下)之頻數、以及該頻數所屬等級之上一等級(圓相當徑超過0.5 μm且為0.6 μm以下)之頻數。即,圖3中,第1範圍(圓相當徑超過0.3 μm且為0.6 μm以下)具有一個極大頻數。In Figure 3, the frequency of the class with a circle equivalent diameter exceeding 0.4 μm and less than 0.5 μm is greater than the frequency of the class below the class (circle equivalent diameter exceeding 0.3 μm and less than 0.4 μm), and the frequency of the class to which the frequency belongs The frequency of the previous level (the circle equivalent diameter exceeds 0.5 μm and is less than 0.6 μm). That is, in FIG. 3, the first range (the circle equivalent diameter exceeds 0.3 μm and is 0.6 μm or less) has a maximum frequency.
圖3中,圓相當徑超過0.7 μm且為0.8 μm以下之等級之頻數大於該頻數所屬等級之下一等級(圓相當徑超過0.6 μm且為0.7 μm以下)之頻數、以及該頻數所屬等級之上一等級(圓相當徑超過0.8 μm且為0.9 μm以下)之頻數。即,圖3中,第2範圍(圓相當徑超過0.6 μm且為1.0 μm以下)具有一個極大頻數。In Figure 3, the frequency of the class with a circle equivalent diameter exceeding 0.7 μm and below 0.8 μm is greater than the frequency of the class below that frequency (the circle equivalent diameter exceeds 0.6 μm and is less than 0.7 μm), and the frequency of the class to which the frequency belongs The frequency of the previous level (the circle equivalent diameter exceeds 0.8 μm and is less than 0.9 μm). That is, in FIG. 3, the second range (the circle equivalent diameter exceeds 0.6 μm and is 1.0 μm or less) has a maximum frequency.
由此可知,圖3所示之碳化鎢粒子之圓相當徑之分佈滿足上述(b)。From this, it can be seen that the circle-equivalent diameter distribution of the tungsten carbide particles shown in FIG. 3 satisfies the above (b).
圖3中,作為第1範圍內存在之最大之極大頻數之第1極大頻數為圓相當徑超過0.4 μm且為0.5 μm以下之等級之頻數。該第1極大頻數相對於碳化鎢粒子總數之比率為10%以上(約14.3%)。In Fig. 3, the first maximum frequency, which is the largest maximum frequency existing in the first range, is the frequency of the level whose circle equivalent diameter exceeds 0.4 μm and is 0.5 μm or less. The ratio of the first maximum frequency to the total number of tungsten carbide particles is 10% or more (approximately 14.3%).
圖3中,作為第2範圍內存在之最大之極大頻數之第2極大頻數為圓相當徑超過0.7 μm且為0.8 μm以下之等級之頻數。該第2極大頻數相對於碳化鎢粒子總數之比率為10%以上(約12.6%)。In Fig. 3, the second maximum frequency, which is the largest maximum frequency existing in the second range, is the frequency at the level where the circle equivalent diameter exceeds 0.7 μm and is below 0.8 μm. The ratio of the second maximum frequency to the total number of tungsten carbide particles is 10% or more (about 12.6%).
由此可知,圖3所示之碳化鎢粒子之圓相當徑之分佈滿足上述(c)。From this, it can be seen that the circle-equivalent diameter distribution of the tungsten carbide particles shown in Fig. 3 satisfies the above (c).
(圖4) 圖4中,圓相當徑為0.3 μm以上1.0 μm以下之碳化鎢粒子之個數基準之比率為50%以上(約72.1%)。因此,圖4所示之碳化鎢粒子之圓相當徑之分佈滿足上述(a)。 (Figure 4) In Figure 4, the ratio of tungsten carbide particles with a circle equivalent diameter of 0.3 μm or more and 1.0 μm or less is 50% or more (approximately 72.1%). Therefore, the circle-equivalent diameter distribution of the tungsten carbide particles shown in FIG. 4 satisfies the above (a).
圖4中,圓相當徑超過0.5 μm且為0.6 μm以下之等級之頻數大於該頻數所屬等級之下一等級(圓相當徑超過0.4 μm且為0.5 μm以下)之頻數、以及該頻數所屬等級之上一等級(圓相當徑超過0.6 μm且為0.7 μm以下)之頻數。即,圖4中,第1範圍(圓相當徑超過0.3 μm且為0.6 μm以下)具有一個極大頻數。In Figure 4, the frequency of a class with a circle equivalent diameter exceeding 0.5 μm and below 0.6 μm is greater than the frequency of a class below the class of the frequency (circle equivalent diameter exceeding 0.4 μm and less than 0.5 μm), and the frequency of the class to which the frequency belongs The frequency of the previous level (the circle equivalent diameter exceeds 0.6 μm and is less than 0.7 μm). That is, in FIG. 4, the first range (the circle equivalent diameter exceeds 0.3 μm and is 0.6 μm or less) has a maximum frequency.
圖4中,圓相當徑超過0.7 μm且為0.8 μm以下之等級之頻數大於該頻數所屬等級之下一等級(圓相當徑超過0.6 μm且為0.7 μm以下)之頻數、以及該頻數所屬等級之上一等級(圓相當徑超過0.8 μm且為0.9 μm以下)之頻數。又,圖4中,圓相當徑超過0.9 μm且為1.0 μm以下之等級之頻數大於該頻數所屬等級之下一等級(圓相當徑超過0.8 μm且為0.9 μm以下)之頻數、以及該頻數所屬等級之上一等級(圓相當徑超過1.0 μm且為1.1 μm以下)之頻數。即,圖4中,第2範圍(圓相當徑超過0.6 μm且為1.0 μm以下)具有兩個極大頻數。In Figure 4, the frequency of the class with a circle equivalent diameter exceeding 0.7 μm and below 0.8 μm is greater than the frequency of the class below the class of the frequency (the circle equivalent diameter exceeds 0.6 μm and is less than 0.7 μm), and the frequency of the class to which the frequency belongs The frequency of the previous level (the circle equivalent diameter exceeds 0.8 μm and is less than 0.9 μm). In addition, in Figure 4, the frequency of a class with a circle equivalent diameter exceeding 0.9 μm and below 1.0 μm is greater than the frequency of a class below the class to which the frequency belongs (circle equivalent diameter exceeding 0.8 μm and less than 0.9 μm), and the frequency to which the frequency belongs The frequency of one level above the level (the equivalent diameter of a circle exceeds 1.0 μm and is less than 1.1 μm). That is, in FIG. 4, the second range (the circle equivalent diameter exceeds 0.6 μm and is 1.0 μm or less) has two maximum frequencies.
由此可知,圖4所示之碳化鎢粒子之圓相當徑之分佈滿足上述(b)。From this, it can be seen that the distribution of the circle-equivalent diameter of the tungsten carbide particles shown in Fig. 4 satisfies the above (b).
圖4中,作為第1範圍內存在之最大之極大頻數之第1極大頻數為圓相當徑超過0.5 μm且為0.6 μm以下之等級之頻數。該第1極大頻數相對於碳化鎢粒子總數之比率為10%以上(約13.4%)。In Fig. 4, the first maximum frequency, which is the largest maximum frequency existing in the first range, is the frequency at the level where the circle equivalent diameter exceeds 0.5 μm and is less than 0.6 μm. The ratio of the first maximum frequency to the total number of tungsten carbide particles is 10% or more (about 13.4%).
圖4中,作為第2範圍內存在之最大之極大頻數之第2極大頻數為圓相當徑超過0.7 μm且為0.8 μm以下之等級之頻數。該第2極大頻數相對於碳化鎢粒子總數之比率為10%以上(約12.7%)。In Fig. 4, the second maximum frequency, which is the largest maximum frequency existing in the second range, is a frequency of a level where the circle equivalent diameter exceeds 0.7 μm and is below 0.8 μm. The ratio of the second maximum frequency to the total number of tungsten carbide particles is 10% or more (about 12.7%).
由此可知,圖4所示之碳化鎢粒子之圓相當徑之分佈滿足上述(c)。It can be seen that the distribution of the circle-equivalent diameter of the tungsten carbide particles shown in Fig. 4 satisfies the above (c).
(圖5) 圖5中,圓相當徑為0.3 μm以上1.0 μm以下之碳化鎢粒子之個數基準之比率為50%以上(約73.5%)。因此,圖5所示之碳化鎢粒子之圓相當徑之分佈滿足上述(a)。 (Figure 5) In Figure 5, the ratio of tungsten carbide particles with a circle equivalent diameter of 0.3 μm or more and 1.0 μm or less is 50% or more (about 73.5%). Therefore, the circle-equivalent diameter distribution of the tungsten carbide particles shown in FIG. 5 satisfies the above (a).
圖5中,圓相當徑超過0.3 μm且為0.4 μm以下之等級之頻數大於該頻數所屬等級之下一等級(圓相當徑超過0.2 μm且為0.3 μm以下)之頻數、以及該頻數所屬等級之上一等級(圓相當徑超過0.4 μm且為0.5 μm以下)之頻數。即,圖5中,第1範圍(圓相當徑超過0.3 μm且為0.6 μm以下)具有一個極大頻數。In Figure 5, the frequency of a class with a circle equivalent diameter exceeding 0.3 μm and below 0.4 μm is greater than the frequency of a class below the class of the frequency (circle equivalent diameter exceeding 0.2 μm and less than 0.3 μm), and the frequency of the class to which the frequency belongs The frequency of the previous level (the equivalent diameter of a circle exceeds 0.4 μm and is less than 0.5 μm). That is, in FIG. 5, the first range (the circle equivalent diameter exceeds 0.3 μm and is 0.6 μm or less) has a maximum frequency.
圖5中,圓相當徑超過0.7 μm且為0.8 μm以下之等級之頻數大於該頻數所屬等級之下一等級(圓相當徑超過0.6 μm且為0.7 μm以下)之頻數、以及該頻數所屬等級之上一等級(圓相當徑超過0.8 μm且為0.9 μm以下)之頻數。又,圖5中,圓相當徑超過0.9 μm且為1.0 μm以下之等級之頻數大於該頻數所屬等級之下一等級(圓相當徑超過0.8 μm且為0.9 μm以下)之頻數、以及該頻數所屬等級之上一等級(圓相當徑超過1.0 μm且為1.1 μm以下)之頻數。即,圖5中,第2範圍(圓相當徑超過0.6 μm且為1.0 μm以下)具有兩個極大頻數。In Figure 5, the frequency of a class with a circle equivalent diameter exceeding 0.7 μm and below 0.8 μm is greater than the frequency of a class below the class to which the frequency belongs (the circle equivalent diameter exceeds 0.6 μm and is less than 0.7 μm), and the frequency of the class to which the frequency belongs The frequency of the previous level (the circle equivalent diameter exceeds 0.8 μm and is less than 0.9 μm). In addition, in Fig. 5, the frequency of a class with a circle equivalent diameter exceeding 0.9 μm and less than 1.0 μm is greater than the frequency of a class below the class to which the frequency belongs (circle equivalent diameter exceeding 0.8 μm and less than 0.9 μm), and the frequency to which the frequency belongs The frequency of one level above the level (the equivalent diameter of a circle exceeds 1.0 μm and is less than 1.1 μm). That is, in FIG. 5, the second range (the circle equivalent diameter exceeds 0.6 μm and is 1.0 μm or less) has two maximum frequencies.
由此可知,圖5所示之碳化鎢粒子之圓相當徑之分佈滿足上述(b)。From this, it can be seen that the circle-equivalent diameter distribution of the tungsten carbide particles shown in FIG. 5 satisfies the above (b).
圖5中,作為第1範圍內存在之最大之極大頻數之第1極大頻數為圓相當徑超過0.3 μm且為0.4 μm以下之等級之頻數。該第1極大頻數相對於碳化鎢粒子總數之比率為10%以上(約11.8%)。In Fig. 5, the first maximum frequency, which is the largest maximum frequency existing in the first range, is the frequency at the level where the circle equivalent diameter exceeds 0.3 μm and is less than 0.4 μm. The ratio of the first maximum frequency to the total number of tungsten carbide particles is 10% or more (about 11.8%).
圖5中,作為第2範圍內存在之最大之極大頻數之第2極大頻數為圓相當徑超過0.7 μm且為0.8 μm以下之等級之頻數。該第2極大頻數相對於碳化鎢粒子總數之比率為10%以上(約12.2%)。In Fig. 5, the second maximum frequency, which is the largest maximum frequency existing in the second range, is the frequency at the level where the circle equivalent diameter exceeds 0.7 μm and is below 0.8 μm. The ratio of the second maximum frequency to the total number of tungsten carbide particles is 10% or more (about 12.2%).
由此可知,圖5所示之碳化鎢粒子之圓相當徑之分佈滿足上述(c)。It can be seen that the distribution of the circle-equivalent diameter of the tungsten carbide particles shown in FIG. 5 satisfies the above (c).
(圖6) 圖6中,圓相當徑為0.3 μm以上1.0 μm以下之碳化鎢粒子之個數基準之比率為50%以上(約72.6%)。因此,圖6所示之碳化鎢粒子之圓相當徑之分佈滿足上述(a)。 (Image 6) In Figure 6, the ratio of tungsten carbide particles with a circle equivalent diameter of 0.3 μm or more and 1.0 μm or less is 50% or more (about 72.6%). Therefore, the circle-equivalent diameter distribution of the tungsten carbide particles shown in FIG. 6 satisfies the above (a).
圖6中,圓相當徑超過0.4 μm且為0.5 μm以下之等級之頻數大於該頻數所屬等級之下一等級(圓相當徑超過0.3 μm且為0.4 μm以下)之頻數、以及該頻數所屬等級之上一等級(圓相當徑超過0.5 μm且為0.6 μm以下)之頻數。即,圖6中,第1範圍(圓相當徑超過0.3 μm且為0.6 μm以下)具有一個極大頻數。In Figure 6, the frequency of a class with a circle equivalent diameter exceeding 0.4 μm and less than 0.5 μm is greater than the frequency of a class below the class of the frequency (circle equivalent diameter exceeding 0.3 μm and less than 0.4 μm), and the frequency of the class to which the frequency belongs The frequency of the previous level (the circle equivalent diameter exceeds 0.5 μm and is less than 0.6 μm). That is, in FIG. 6, the first range (the circle equivalent diameter exceeds 0.3 μm and is 0.6 μm or less) has a maximum frequency.
圖6中,圓相當徑超過0.6 μm且為0.7 μm以下之等級之頻數大於該頻數所屬等級之下一等級(圓相當徑超過0.5 μm且為0.6 μm以下)之頻數、以及該頻數所屬等級之上一等級(圓相當徑超過0.7 μm且為0.8 μm以下)之頻數。即,圖6中,第2範圍(圓相當徑超過0.6 μm且為1.0 μm以下)具有一個極大頻數。In Figure 6, the frequency of a class with a circle equivalent diameter exceeding 0.6 μm and less than 0.7 μm is greater than the frequency of a class below the class of the frequency (circle equivalent diameter exceeding 0.5 μm and less than 0.6 μm), and the frequency of the class to which the frequency belongs The frequency of the previous level (the circle equivalent diameter exceeds 0.7 μm and is less than 0.8 μm). That is, in FIG. 6, the second range (the circle equivalent diameter exceeds 0.6 μm and is 1.0 μm or less) has a maximum frequency.
由此可知,圖6所示之碳化鎢粒子之圓相當徑之分佈滿足上述(b)。From this, it can be seen that the distribution of the circle-equivalent diameter of the tungsten carbide particles shown in FIG. 6 satisfies the above (b).
圖6中,作為第1範圍內存在之最大之極大頻數之第1極大頻數為圓相當徑超過0.4 μm且為0.5 μm以下之等級之頻數。該第1極大頻數相對於碳化鎢粒子總數之比率為10%以上(約14.2%)。In Fig. 6, the first maximum frequency, which is the largest maximum frequency existing in the first range, is a frequency of a level whose circle equivalent diameter exceeds 0.4 μm and is 0.5 μm or less. The ratio of the first maximum frequency to the total number of tungsten carbide particles is 10% or more (about 14.2%).
圖6中,作為第2範圍內存在之最大之極大頻數之第2極大頻數為圓相當徑超過0.6 μm且為0.7 μm以下之等級之頻數。該第2極大頻數相對於碳化鎢粒子總數之比率為10%以上(約12.4%)。In Fig. 6, the second maximum frequency, which is the largest maximum frequency existing in the second range, is the frequency at the level where the circle equivalent diameter exceeds 0.6 μm and is less than 0.7 μm. The ratio of the second maximum frequency to the total number of tungsten carbide particles is 10% or more (about 12.4%).
由此可知,圖6所示之碳化鎢粒子之圓相當徑之分佈滿足上述(c)。From this, it can be seen that the circle-equivalent diameter distribution of the tungsten carbide particles shown in FIG. 6 satisfies the above (c).
於在表示本發明之碳化鎢粒子之圓相當徑之分佈之柱狀圖的橫軸中,將超過0.4 μm且為0.6 μm以下之範圍規定為第3範圍,將超過0.6 μm且為0.8 μm以下之範圍規定為第4範圍之情形時,較佳為第3範圍具有第1極大頻數,第4範圍具有第2極大頻數。藉此,工具壽命進一步延長。In the horizontal axis of the histogram representing the distribution of the circle-equivalent diameter of the tungsten carbide particles of the present invention, the range exceeding 0.4 μm and less than 0.6 μm is defined as the third range, and the range exceeding 0.6 μm and less than 0.8 μm is defined When the range is defined as the fourth range, it is preferable that the third range has the first maximum frequency and the fourth range has the second maximum frequency. As a result, the tool life is further extended.
第2極大頻數相對於第1極大頻數之比率較佳為0.8以上1.2以下。藉此,工具壽命進一步延長。推測其原因在於:藉由碳化鎢粒子彼此之接觸之結合較為重要,若第1範圍內存在之極大頻數與第2範圍內存在之極大頻數的差變大,則結果超硬合金中之碳化鎢粒子彼此之接觸變少。The ratio of the second maximum frequency to the first maximum frequency is preferably 0.8 or more and 1.2 or less. As a result, the tool life is further extended. It is speculated that the reason is that the combination of tungsten carbide particles is more important in contact with each other. If the difference between the maximum frequency in the first range and the maximum frequency in the second range becomes larger, the result is the tungsten carbide in the cemented carbide The particles have less contact with each other.
<第2相> 第2相包含鈷。第2相係使構成第1相之碳化鎢粒子彼此結合之結合相。 <Phase 2> The second phase contains cobalt. The second phase is a bonding phase in which tungsten carbide particles constituting the first phase are bonded to each other.
此處,「第2相包含鈷(Co)」意指第2相之主成分為Co。「第2相之主成分為Co」意指第2相中之鈷之質量比率為90質量%以上100質量%以下。第2相中之鈷之質量比率可藉由ICP發射光譜分析法(所用機器:島津製作所製造之「ICPS-8100」(商標))進行測定。Here, "the second phase contains cobalt (Co)" means that the main component of the second phase is Co. "The main component of the second phase is Co" means that the mass ratio of cobalt in the second phase is 90% by mass to 100% by mass. The mass ratio of cobalt in the second phase can be measured by ICP emission spectrometry (machine used: "ICPS-8100" (trademark) manufactured by Shimadzu Corporation).
第2相除鈷外亦可包含鎳等鐵族元素、合金中之溶解物(Cr、W等)。In addition to cobalt, the second phase may also contain iron group elements such as nickel, and dissolved substances in alloys (Cr, W, etc.).
<超硬合金之組成> (組成) 超硬合金具備包含複數個碳化鎢粒子之第1相、以及包含鈷之第2相。超硬合金較佳為於利用掃描式電子顯微鏡拍攝之圖像中,包含75面積%以上且未達100面積%之第1相,且包含超過0面積%且為20面積%以下之第2相。 <The composition of cemented carbide> (composition) The cemented carbide has a first phase containing a plurality of tungsten carbide particles and a second phase containing cobalt. The cemented carbide preferably includes the first phase with 75 area% or more and less than 100 area% in the image taken by the scanning electron microscope, and the second phase with more than 0 area% and 20 area% or less. .
若超硬合金中之第2相之比率為20面積%以下,則可抑制圓相當徑為0.6 μm以下之微粒碳化鎢粒子溶解於第2相之鈷中,可抑制圓相當徑超過0.3 μm且為0.6 μm以下之碳化鎢粒子之減少。又,加工中工具表面露出之鈷量進一步減少。因此,工具壽命進一步延長。If the ratio of the second phase in the cemented carbide is 20 area% or less, it is possible to suppress the dissolution of fine tungsten carbide particles with a circle-equivalent diameter of 0.6 μm or less in the cobalt of the second phase, and it can prevent the circle-equivalent diameter from exceeding 0.3 μm and It is the reduction of tungsten carbide particles below 0.6 μm. In addition, the amount of cobalt exposed on the surface of the tool during processing is further reduced. Therefore, the tool life is further extended.
超硬合金較佳為於利用掃描式電子顯微鏡拍攝之圖像中,包含5面積%以上12面積%以下之第2相。藉此,能夠發揮印刷電路基板之加工所必需之硬度及耐磨性,抑制工具壽命產生偏差。The cemented carbide preferably contains the second phase of 5 area% or more and 12 area% or less in an image taken by a scanning electron microscope. Thereby, the hardness and wear resistance necessary for the processing of the printed circuit board can be exerted, and the deviation of the tool life can be suppressed.
超硬合金中之第1相之比率之下限可設為75面積%以上、85面積%以上。超硬合金中之第1相之比率之上限可設為未達100面積%、95面積%以下。超硬合金中之第1相之比率可設為75面積%以上且未達100面積%、85面積%以上95面積%以下。The lower limit of the ratio of the first phase in the cemented carbide can be set to 75 area% or more and 85% area or more. The upper limit of the ratio of the first phase in the cemented carbide can be set to less than 100 area% and 95 area% or less. The ratio of the first phase in the cemented carbide can be set to 75 area% or more and less than 100 area%, and 85 area% or more and 95 area% or less.
超硬合金中之第2相之比率之下限可設為超過0面積%、5面積%以上。超硬合金中之第2相之比率之上限可設為20面積%以下、12面積%以下。超硬合金中之第2相之比率可設為超過0面積%且為20面積%以下、5面積%以上12面積%以下。The lower limit of the ratio of the second phase in the cemented carbide can be set to be more than 0 area% or more than 5 area%. The upper limit of the ratio of the second phase in the cemented carbide can be set to 20 area% or less and 12 area% or less. The ratio of the second phase in the cemented carbide can be set to exceed 0 area% and be 20 area% or less, 5 area% or more and 12 area% or less.
按照下述(A3)~(C3)之步序測定超硬合金中之第1相及第2相各者之面積比率。Measure the area ratio of each of the first phase and the second phase in the cemented carbide according to the following steps (A3) to (C3).
(A3)按照與上述碳化鎢粒子之圓相當徑之測定方法中記載之(A1)及(B1)相同之步序,獲得超硬合金之截面之拍攝圖像。(A3) Follow the same steps as (A1) and (B1) described in the above-mentioned method for measuring the circle-equivalent diameter of tungsten carbide particles to obtain a photographed image of the cross section of the cemented carbide.
(B3)將上述(A3)中所得之拍攝圖像輸入至電腦中,使用圖像解析軟體(ImageJ:https://imagej.nih.gov/ij/)進行圖像處理,將整個測定視野(縱25.3 μm×寬17.6 μm之矩形)作為分母而測定第1相及第2相各者之面積比率。第1相與第2相可藉由上述拍攝圖像中之顏色深淺進行識別。(B3) Input the captured image obtained in (A3) above into the computer, and use the image analysis software (ImageJ: https://imagej.nih.gov/ij/) to perform image processing, and the entire measurement field of view ( A rectangle with a length of 25.3 μm × a width of 17.6 μm) was used as the denominator to measure the area ratio of the first phase and the second phase. The first phase and the second phase can be identified by the color shade in the above-mentioned captured image.
(C3)於五個測定視野中進行上述(B3)之圖像處理。將五個測定視野中獲得之第1相之面積比率之平均值作為超硬合金中之第1相之面積比率。將五個測定視野中獲得之第2相之面積比率之平均值作為超硬合金中之第2相之面積比率。(C3) Perform the image processing of (B3) above in five measurement fields. The average value of the area ratio of the first phase obtained in the five measurement fields is taken as the area ratio of the first phase in the cemented carbide. The average value of the area ratio of the second phase obtained in the five measurement fields is taken as the area ratio of the second phase in the cemented carbide.
(鉻含量) 超硬合金較佳為包含鉻(Cr),且鉻相對於鈷之質量基準之比率為5%以上10%以下。鉻具有碳化鎢粒子之晶粒生長抑制作用。進而,藉由固溶於鈷中,而促進鈷產生晶格應變。因此,若超硬合金以上述比率包含鉻,則耐破損性進一步提高。 (Chromium content) The cemented carbide preferably contains chromium (Cr), and the ratio of chromium to cobalt on a mass basis is 5% or more and 10% or less. Chromium has the effect of inhibiting the grain growth of tungsten carbide particles. Furthermore, by solid-dissolving in cobalt, cobalt is promoted to generate lattice strain. Therefore, if the cemented carbide contains chromium in the above-mentioned ratio, the breakage resistance is further improved.
另一方面,若鉻之量過剩,則存在鉻以碳化物之形式析出而成為破損之源頭之情形。若鉻相對於鈷之質量基準之比率為5%以上10%以下,則不易發生鉻之碳化物之析出,可獲得提高耐破損性之效果。On the other hand, if the amount of chromium is excessive, chromium may precipitate in the form of carbides and become the source of damage. If the ratio of chromium to the mass standard of cobalt is 5% or more and 10% or less, the precipitation of chromium carbides is unlikely to occur, and the effect of improving the damage resistance can be obtained.
又,若鉻相對於鈷之質量基準之比率為10%以下,則晶粒生長抑制作用之程度變得適度,可抑制超硬合金中之圓相當徑超過1.0 μm之碳化鎢粒子之量過剩。In addition, if the ratio of chromium to cobalt is 10% or less on the basis of mass, the degree of the grain growth inhibitory effect becomes moderate, and it is possible to suppress the excessive amount of tungsten carbide particles whose circle equivalent diameter exceeds 1.0 μm in the cemented carbide.
鉻相對於鈷之質量基準之比率之下限較佳為5%以上,更佳為7%以上。鉻相對於鈷之質量基準之比率較佳為10%以下,更佳為9%以下。鉻相對於鈷之質量基準可設為5%以上10%以下、7%以上9%以下。The lower limit of the mass standard ratio of chromium to cobalt is preferably 5% or more, more preferably 7% or more. The ratio of chromium to the mass basis of cobalt is preferably 10% or less, more preferably 9% or less. The quality standard of chromium relative to cobalt can be set at 5% or more and 10% or less, and 7% or more and 9% or less.
超硬合金中之鈷及鉻之含量藉由ICP發射光譜分析法進行測定。The content of cobalt and chromium in the cemented carbide is determined by ICP emission spectrometry.
(釩) 於超硬合金包含釩之情形時,超硬合金之釩之質量基準之含有率較佳為未達100 ppm。 (vanadium) When the cemented carbide contains vanadium, the content of vanadium on the basis of mass of the cemented carbide is preferably less than 100 ppm.
由於釩具有晶粒生長抑制作用,故而於先前之超微粒超硬合金之製造時使用釩。認為若碳化鎢粒子之晶粒生長時存在釩,則碳化鎢粒子之表面會析出釩,或碳化鎢粒子之生長面於短期內介存有釩,藉此抑制碳化鎢粒子之生長。Because vanadium has a grain growth inhibitory effect, vanadium was used in the manufacture of the previous ultrafine super-hard alloy. It is believed that if vanadium is present when the grains of tungsten carbide particles grow, vanadium will be precipitated on the surface of tungsten carbide particles, or vanadium will be interspersed on the growth surface of tungsten carbide particles in a short period of time, thereby inhibiting the growth of tungsten carbide particles.
因此,若添加釩,則可獲得晶粒生長抑制作用,但由於碳化鎢粒子與鈷之界面、或碳化鎢粒子彼此之界面上存在碳化鎢,故而有出現濕潤性降低或強度降低之傾向。因此,碳化鎢中之釩之含量越少,越可將碳化鎢粒子與鈷之親和性、或碳化鎢粒子彼此之親和性維持得較高,從而使超硬合金之強度提高。Therefore, if vanadium is added, the grain growth inhibitory effect can be obtained. However, since tungsten carbide exists on the interface between tungsten carbide particles and cobalt or the interface between tungsten carbide particles, the wettability or strength tends to decrease. Therefore, the lower the content of vanadium in tungsten carbide, the higher the affinity between tungsten carbide particles and cobalt, or the affinity between tungsten carbide particles, can be maintained higher, thereby increasing the strength of the cemented carbide.
超硬合金中之釩之含量較佳為100 ppm以下,更佳為10 ppm以下。超硬合金中之釩之含量越少越佳,因此其下限較佳為0 ppm。再者,存在非刻意地因製造步驟而檢測出數ppm之釩之情形。超硬合金中之釩之含量可設為0 ppm以上100 ppm以下、0 ppm以上10 ppm以下。The content of vanadium in the cemented carbide is preferably 100 ppm or less, more preferably 10 ppm or less. The lower the content of vanadium in the cemented carbide, the better, so the lower limit is preferably 0 ppm. Furthermore, there are cases where several ppm of vanadium is detected inadvertently due to manufacturing steps. The content of vanadium in the cemented carbide can be set from 0 ppm to 100 ppm, 0 ppm to 10 ppm.
超硬合金中之釩之含量藉由ICP發射光譜分析法進行測定。The content of vanadium in the cemented carbide is determined by ICP emission spectrometry.
<超硬合金之製造方法> 就代表性而言,本實施方式之超硬合金可藉由依序進行原料粉末之準備步驟、混合步驟、成形步驟、燒結步驟、冷卻步驟而製造。以下,對各步驟進行說明。 <Manufacturing method of cemented carbide> Representatively, the cemented carbide of the present embodiment can be manufactured by sequentially performing the preparation step, mixing step, forming step, sintering step, and cooling step of the raw material powder. Hereinafter, each step will be described.
《準備步驟》 準備步驟係準備構成超硬合金之材料之所有原料粉末之步驟。作為原料粉末,可列舉作為第1相之原料之碳化鎢粉末、作為第2相之原料之鈷(Co)粉末作為必需之原料粉末。又,視需要可準備碳化鉻(Cr 3C 2)粉末作為晶粒生長抑制劑。又,只要發揮本發明之效果,則亦可準備碳化釩(VC)粉末。碳化鎢粉末、鈷粉末、碳化鉻粉末、碳化釩粉末可使用市售品。 "Preparation Steps" The preparation step is the step of preparing all the raw material powders that constitute the material of the cemented carbide. As the raw material powder, tungsten carbide powder, which is the raw material of the first phase, and cobalt (Co) powder, which is the raw material of the second phase, can be cited as essential raw material powders. In addition, if necessary, chromium carbide (Cr 3 C 2 ) powder can be prepared as a grain growth inhibitor. In addition, as long as the effects of the present invention are exhibited, vanadium carbide (VC) powder may be prepared. Commercially available products can be used for tungsten carbide powder, cobalt powder, chromium carbide powder, and vanadium carbide powder.
關於碳化鎢粉末,準備(a)平均粒徑為0.4 μm以上1.2 μm以下之碳化鎢粉末(以下亦記為「第1碳化鎢粉末」)、以及(b)平均粒徑為0.8 μm以上1.2 μm以下之碳化鎢粉末(以下亦記為「第2碳化鎢粉末」)。關於第1碳化鎢粉末,準備平均粒徑小於第2碳化鎢粉末之平均粒徑者。於本說明書中,原料粉末之平均粒徑意指圓相當徑之中值粒徑d50。該平均粒徑使用Microtrac公司製造之粒度分佈測定裝置(商品名:MT3300EX)進行測定。For tungsten carbide powder, prepare (a) tungsten carbide powder with an average particle diameter of 0.4 μm or more and 1.2 μm or less (hereinafter also referred to as "the first tungsten carbide powder"), and (b) an average particle diameter of 0.8 μm or more and 1.2 μm The following tungsten carbide powder (hereinafter also referred to as "second tungsten carbide powder"). Regarding the first tungsten carbide powder, an average particle size smaller than that of the second tungsten carbide powder is prepared. In this specification, the average particle diameter of the raw material powder means the median diameter d50 of the circle equivalent diameter. The average particle size is measured using a particle size distribution measuring device (trade name: MT3300EX) manufactured by Microtrac.
鈷粉末之平均粒徑可設為0.8 μm以上1.2 μm以下。碳化鉻粉末之平均粒徑可設為1.0 μm以上2.0 μm以下。碳化釩粉末之平均粒徑可設為0.5 μm以上1.0 μm以下。The average particle size of the cobalt powder can be set to 0.8 μm or more and 1.2 μm or less. The average particle size of the chromium carbide powder can be set to 1.0 μm or more and 2.0 μm or less. The average particle size of vanadium carbide powder can be set to 0.5 μm or more and 1.0 μm or less.
《混合步驟》 混合步驟係將準備步驟中準備之各原料粉末加以混合之步驟。藉由混合步驟獲得各原料粉末混合而成之混合粉末。 "Mixed Steps" The mixing step is a step of mixing the raw material powders prepared in the preparation step. Through the mixing step, a mixed powder obtained by mixing each raw material powder is obtained.
混合粉末中之第1碳化鎢粉末之比率例如可設為30質量%以上94.6質量%以下。The ratio of the first tungsten carbide powder in the mixed powder can be set to 30% by mass or more and 94.6% by mass or less, for example.
混合粉末中之第2碳化鎢粉末之比率例如可設為30質量%以上64.6質量%以下。The ratio of the second tungsten carbide powder in the mixed powder can be set to 30% by mass or more and 64.6% by mass or less, for example.
第1碳化鎢粉末與第2碳化鎢粉末之混合比例如以質量基準計可設為第1碳化鎢粉末:第2碳化鎢粉末=2:1~1:2。The mixing ratio of the first tungsten carbide powder and the second tungsten carbide powder can be set to, for example, the first tungsten carbide powder: the second tungsten carbide powder=2:1 to 1:2 on a mass basis.
混合粉末中之鈷粉末之比率例如可設為2.8質量%以上10質量%以下。The ratio of the cobalt powder in the mixed powder can be set to, for example, 2.8% by mass or more and 10% by mass or less.
混合粉末中之碳化鉻粉末之比率例如可設為0.2質量%以上1.2質量%以下。The ratio of the chromium carbide powder in the mixed powder can be set to, for example, 0.2% by mass or more and 1.2% by mass or less.
混合粉末中之碳化釩粉末之比率例如可設為0質量%以上0.2質量%以下。The ratio of the vanadium carbide powder in the mixed powder can be set to, for example, 0% by mass or more and 0.2% by mass or less.
使用球磨機將混合粉末加以混合。混合時間可設為20小時以上48小時以下。Use a ball mill to mix the mixed powders. The mixing time can be set to 20 hours or more and 48 hours or less.
混合步驟後,視需要亦可對混合粉末進行造粒。藉由對混合粉末進行造粒,於下述成形步驟時容易將混合粉末填充至模嘴或模具中。造粒時可應用公知之造粒方法,例如可使用噴霧乾燥器等市售之造粒機。After the mixing step, the mixed powder can also be granulated if necessary. By granulating the mixed powder, it is easy to fill the mixed powder into the die nozzle or mold during the following forming steps. For granulation, a known granulation method can be applied. For example, a commercially available granulator such as a spray dryer can be used.
《成形步驟》 成形步驟係使藉由混合步驟所獲得之混合粉末成形為特定之形狀而獲得成形體之步驟。成形步驟中之成形方法及成形條件採用通常之方法及條件即可,並無特別限定。作為特定之形狀,例如可列舉切削工具形狀(例如小徑鑽頭之形狀)。 "Forming Steps" The forming step is a step of forming the mixed powder obtained by the mixing step into a specific shape to obtain a formed body. The forming method and forming conditions in the forming step may be general methods and conditions, and are not particularly limited. As the specific shape, for example, the shape of a cutting tool (for example, the shape of a small-diameter drill) can be cited.
《燒結步驟》 燒結步驟係對藉由成形步驟所獲得之成形體進行燒結而獲得超硬合金之步驟。於本發明之超硬合金之製造方法中,燒結溫度可設為通常之超硬合金之燒結溫度(1350~1500℃)。 "Sintering Steps" The sintering step is a step of sintering the formed body obtained by the forming step to obtain a cemented carbide. In the manufacturing method of the cemented carbide of the present invention, the sintering temperature can be set to the sintering temperature of the usual cemented carbide (1350-1500°C).
超硬合金通常於1350~1500℃下進行燒結,微粒碳化鎢粒子由於表面積較大,容易溶解於鈷,故而容易因溶解再析出而產生異常組織。因此,於微粒碳化鎢粒子之燒結中,為了抑制溶解再析出,於碳化鎢對鈷之固溶限較低之1350~1380℃之低溫度區域下進行燒結。然而,於低溫度區域下進行燒結而獲得之超硬合金中,碳化鎢粒子未進行晶粒生長,因此,碳化鎢粒子表面成為因之前步驟中之粉碎或混合而破碎之狀態。因此,成為碳化鎢粒子與鈷之界面、或碳化鎢粒子彼此之界面之結合力較低之狀態,有耐磨性及耐破損性降低之傾向。Cemented carbide is usually sintered at 1350 to 1500°C. Because of its large surface area, the particulate tungsten carbide particles are easy to dissolve in cobalt, so they are likely to produce abnormal structures due to dissolution and precipitation. Therefore, in the sintering of fine tungsten carbide particles, in order to suppress dissolution and re-precipitation, sintering is performed in a low temperature region of 1350 to 1380°C where the solid solubility limit of tungsten carbide to cobalt is relatively low. However, in the cemented carbide obtained by sintering in a low temperature region, the tungsten carbide particles have not undergone grain growth. Therefore, the surface of the tungsten carbide particles is broken due to the pulverization or mixing in the previous step. Therefore, the interface between the tungsten carbide particles and the cobalt or the interface between the tungsten carbide particles has a low binding force, and there is a tendency for wear resistance and breakage resistance to decrease.
另一方面,於本發明之超硬合金之製造方法中,抑制因原料之粉碎或混合而產生之超微細碳化鎢粒子之碎片的產生,並且最大限度地發揮鉻之晶粒生長抑制效果。進而發現,藉由使微細組織中具有粒度相近且具有波峰之粗粒子與微粒子之分佈,即便於通常會發生晶粒生長之溫度區域下,亦可抑制異常晶粒生長。因此,於本發明之超硬合金之製造方法中,即便於高於先前之溫度下對碳化鎢粒子進行燒結,亦能夠抑制異常組織之產生,藉由使碳化鎢粒子與鈷之界面、或碳化鎢粒子彼此之界面之結合力提高,可使超硬合金之耐磨性及耐破損性提高。此為本發明人等進行銳意研究後獲得之新發現。On the other hand, in the manufacturing method of the cemented carbide of the present invention, the generation of the fragments of the ultrafine tungsten carbide particles generated by the crushing or mixing of the raw materials is suppressed, and the chromium grain growth suppressing effect is maximized. Furthermore, it was found that the distribution of coarse particles and fine particles with similar grain sizes and peaks in the fine structure can suppress abnormal grain growth even in a temperature region where grain growth usually occurs. Therefore, in the manufacturing method of the cemented carbide of the present invention, even if the tungsten carbide particles are sintered at a higher temperature than the previous temperature, the generation of abnormal structures can be suppressed, by making the interface between the tungsten carbide particles and the cobalt, or carbonizing The improvement of the bonding force of the interface between the tungsten particles can improve the wear resistance and breakage resistance of the cemented carbide. This is a new discovery obtained by the inventors after intensive research.
《冷卻步驟》 冷卻步驟係使燒結完成後之超硬合金冷卻之步驟。冷卻條件採用通常之條件即可,並無特別限定。 "Cooling Steps" The cooling step is a step of cooling the cemented carbide after sintering. The cooling conditions may be ordinary conditions, and are not particularly limited.
[實施方式2:切削工具] 本發明之切削工具包括包含上述超硬合金之刀尖。於本說明書中,刀尖意指參與切削之部分,意指於超硬合金中,由刀尖稜線、以及自該刀尖稜線向超硬合金側沿該刀尖稜線之切線之垂線之距離為2 mm之假想面所包圍之區域。 [Embodiment 2: Cutting tool] The cutting tool of the present invention includes a tip including the above-mentioned cemented carbide. In this specification, the tip of the tool refers to the part involved in cutting, which means that in the cemented carbide, the distance from the edge of the tool and the perpendicular from the edge of the tool to the side of the cemented carbide along the tangent of the edge of the tool is The area enclosed by an imaginary surface of 2 mm.
作為切削工具,例如可例示:切削刀具、鑽頭、端銑刀、銑削加工用刀尖交換式切削刀片、車削加工用刀尖交換式切削刀片、金屬用鋸、齒輪切製工具、鉸刀或螺絲攻等。本發明之切削工具於為印刷電路基板加工用小徑鑽頭之情形時,尤其可發揮優異之效果。Examples of cutting tools include: cutting tools, drills, end mills, tip-changing cutting inserts for milling processing, tip-changing cutting inserts for turning processing, metal saws, gear cutting tools, reamers, or screws Attack and wait. When the cutting tool of the present invention is a small-diameter drill for processing a printed circuit board, it can particularly exhibit excellent effects.
本實施方式之超硬合金可構成該等工具整體,亦可構成其一部分。此處,「構成其一部分」表示將本實施方式之超硬合金硬焊於任意基材之特定位置而製成刀尖部之態樣等。The cemented carbide of this embodiment can constitute the whole or a part of these tools. Here, “constitute a part of it” means that the cemented carbide of the present embodiment is brazed to a specific position of an arbitrary base material to form a cutting edge.
《硬質膜》 本實施方式之切削工具進而可具備被覆包含超硬合金之基材之表面之至少一部分的硬質膜。作為硬質膜,例如可使用類鑽碳或鑽石。 [實施例] "Hard Film" The cutting tool of this embodiment may further include a hard film that coats at least a part of the surface of the base material containing cemented carbide. As the hard film, for example, diamond-like carbon or diamond can be used. [Example]
藉由實施例更加具體地對本實施方式進行說明。但是,並不藉由該等實施例限定本實施方式。This embodiment will be described in more detail with examples. However, this embodiment is not limited by these examples.
[實施例1] 於實施例1中,變更原料粉末之種類及調配比而製作試樣1~試樣24之超硬合金。製作具備包含該超硬合金之刀尖之小徑鑽頭,對其進行評估。 [Example 1] In Example 1, the types and blending ratios of the raw material powders were changed to produce cemented carbides of sample 1 to sample 24. Produce a small diameter drill with a tip containing the cemented carbide, and evaluate it.
《試樣之製作》 (準備步驟) 準備表1之「原料」欄所示之組成之粉末作為原料粉末。關於碳化鎢(WC)粉末,準備複數種平均粒徑不同者。碳化WC粉末之平均粒徑如表1之「第1WC粉末」之「平均粒徑(μm)」欄所示。 "Production of Samples" (Preparatory steps) Prepare the powder of the composition shown in the "Raw Material" column of Table 1 as the raw material powder. Regarding tungsten carbide (WC) powder, a plurality of types with different average particle diameters are prepared. The average particle size of the carbonized WC powder is shown in the "average particle size (μm)" column of the "1st WC powder" in Table 1.
鈷(Co)粉末之平均粒徑為1 μm,碳化釩(VC)粉末之平均粒徑為0.8 μm,碳化鉻(Cr 3C 2)粉末之平均粒徑為1 μm。Co粉末、VC粉末及Cr 3C 2粉末為市售品。原料粉末之平均粒徑為使用Microtrac公司製造之粒度分佈測定裝置(商品名:MT3300EX)測得之值。 The average particle size of cobalt (Co) powder is 1 μm, the average particle size of vanadium carbide (VC) powder is 0.8 μm, and the average particle size of chromium carbide (Cr 3 C 2 ) powder is 1 μm. Co powder, VC powder, and Cr 3 C 2 powder are commercially available products. The average particle size of the raw material powder is a value measured using a particle size distribution measuring device (trade name: MT3300EX) manufactured by Microtrac.
(混合步驟) 按照表1所示之調配量將各原料粉末加以混合而製作混合粉末。表1之「原料」欄之「質量%」表示各原料粉末相對於原料粉末之合計質量之比率。混合係利用球磨機進行20小時。對所得之混合粉末進行噴霧乾燥而製成造粒粉末。 (Mixing step) The raw material powders were mixed according to the blending amounts shown in Table 1 to produce mixed powders. The "mass%" in the "raw material" column of Table 1 represents the ratio of each raw material powder to the total mass of the raw material powder. The mixing system uses a ball mill for 20 hours. The resultant mixed powder is spray-dried to prepare granulated powder.
(成形步驟) 對所得之造粒粉末進行加壓成形而製作ϕ3.4 mm之圓桿形狀之成形體。 (Forming step) The obtained granulated powder is press-molded to produce a molded body in the shape of a ϕ3.4 mm round rod.
(燒結步驟) 將成形體放至燒結爐中,於真空中、1400℃下維持1小時而進行燒結。 (Sintering step) The compact was placed in a sintering furnace and maintained at 1400° C. for 1 hour in a vacuum to perform sintering.
(冷卻步驟) 燒結完成後,於氬氣(Ar)氛圍中緩慢冷卻而獲得超硬合金。 (Cooling step) After the sintering is completed, it is slowly cooled in an argon (Ar) atmosphere to obtain a cemented carbide.
[表1]
表1
<評估> 對於各試樣之超硬合金,測定碳化鎢粒子之圓相當徑之分佈、第1相及第2相之面積比率、鉻相對於鈷之質量基準之比率、釩之質量基準之含量。 <Evaluation> For the cemented carbide of each sample, the distribution of the circle-equivalent diameter of tungsten carbide particles, the area ratio of the first phase and the second phase, the ratio of chromium to cobalt on the basis of mass, and the content of vanadium on the basis of mass were measured.
(碳化鎢粒子之圓相當徑之分佈) 對於各試樣之超硬合金,測定碳化鎢粒子之圓相當徑之分佈,算出圓相當徑為0.3 μm以上1.0 μm以下之碳化鎢粒子之個數基準之比率、存在第1極大頻數之等級、第1極大頻數相對於碳化鎢粒子總數之比率、存在第2極大頻數之等級、第2極大頻數相對於碳化鎢粒子總數之比率、第2極大頻數相對於第1極大頻數之比率。具體之測定方法及算出方法記載於實施方式1中,因此不重複進行其說明。 (Distribution of circle equivalent diameter of tungsten carbide particles) For the cemented carbide of each sample, the distribution of the circle-equivalent diameter of the tungsten carbide particles was measured, and the ratio of the number of tungsten carbide particles with the circle-equivalent diameter of 0.3 μm to 1.0 μm was calculated, and the level with the first maximum frequency was calculated. The ratio of the first maximum frequency to the total number of tungsten carbide particles, the level where the second maximum frequency exists, the ratio of the second maximum frequency to the total number of tungsten carbide particles, and the ratio of the second maximum frequency to the first maximum frequency. The specific measurement method and calculation method are described in the first embodiment, so the description thereof will not be repeated.
將結果分別示於表1之「圓相當徑0.3-1.0 μm比率(%)」、「第1極大頻數」之「等級(μm)」及「比率(%)」、「第2極大頻數」之「等級(μm)」及「比率(%)」、「第2極大頻數/第1極大頻數」欄。The results are shown in Table 1 "Ratio of circle equivalent diameter 0.3-1.0 μm (%)", "Level (μm)" and "Ratio (%)" of "First maximum frequency", and "Second maximum frequency" "Level (μm)" and "Ratio (%)", "2nd maximum frequency / 1st maximum frequency" column.
於極大頻數不存在於第1範圍(超過0.3 μm且為0.6 μm以下)內、或第2範圍(超過0.6 μm且為1.0 μm以下)內之情形時,記為「-」。又,於極大頻數存在於第1範圍(超過0.3 μm且為0.6 μm以下)外、或第2範圍(超過0.6 μm且為1.0 μm以下)外之情形時,將該極大頻數之等級示於括號()內。When the maximum frequency does not exist in the first range (over 0.3 μm and less than 0.6 μm) or the second range (over 0.6 μm and less than 1.0 μm), it is recorded as "-". Also, when the maximum frequency exists outside the first range (over 0.3 μm and less than 0.6 μm) or the second range (over 0.6 μm and less than 1.0 μm), the level of the maximum frequency is shown in parentheses ()Inside.
(第1相及第2相之體積比率) 對於各試樣之超硬合金,測定利用掃描式電子顯微鏡拍攝之圖像中之第1相及第2相之面積比率。具體之測定方法記載於實施方式1中,因此不重複進行其說明。將結果示於表1之「第1相(面積%)」及「第2相(面積%)」欄。 (Volume ratio of phase 1 and phase 2) For the cemented carbide of each sample, the area ratio of the first phase and the second phase in the image taken by the scanning electron microscope was measured. The specific measurement method is described in the first embodiment, so the description will not be repeated. The results are shown in Table 1 in the "Phase 1 (Area %)" and "Phase 2 (Area %)" columns.
(鉻相對於鈷之質量基準之比率、釩之質量基準之含量) 對於各試樣之超硬合金,測定鉻相對於鈷之質量基準之比率、及釩之質量基準之含量。具體之測定方法記載於實施方式1中,因此不重複進行其說明。將結果示於表1之「Cr/Co(%)」及「V(ppm)」欄。 (The ratio of chromium to the quality standard of cobalt, the content of the quality standard of vanadium) For the cemented carbide of each sample, the ratio of chromium to cobalt and the content of vanadium were measured. The specific measurement method is described in the first embodiment, so the description will not be repeated. The results are shown in the "Cr/Co (%)" and "V (ppm)" columns of Table 1.
<切削試驗> 對各試樣之圓桿進行加工而製作刃徑ϕ0.35 mm之小徑鑽頭。目前的主流為僅將刃部壓入至不鏽鋼柄中而形成鑽頭,為了進行評估,藉由對ϕ3.4 mm之圓桿之前端進行開刃加工而製作鑽頭。使用該鑽頭進行市售之車輛用印刷電路基板之開孔加工。開孔加工之條件設為轉速155 krpm、進給速度2.5 m/min。根據鑽頭直徑之減少量算出開10000個孔後之鑽頭之磨耗量。利用3根鑽頭進行開孔加工。將3根鑽頭之磨耗量之平均值示於表1之「磨耗量(μm)」欄。又,觀察開孔加工後之刀尖狀態。將其結果示於表1之「刀尖狀態」欄。 <Cutting test> Process the round rods of each sample to produce small-diameter drills with a blade diameter of ϕ0.35 mm. The current mainstream is to press the blade into the stainless steel shank to form a drill bit. For evaluation, the drill bit is manufactured by cutting the front end of a φ 3.4 mm round rod. Use this drill to drill holes for printed circuit boards for vehicles on the market. The conditions for drilling holes are set at a speed of 155 krpm and a feed speed of 2.5 m/min. Calculate the wear amount of the drill bit after 10,000 holes are opened according to the decrease in the diameter of the drill bit. Use 3 drills to drill holes. The average value of the abrasion of the three drill bits is shown in the "Abrasion Amount (μm)" column of Table 1. Also, observe the state of the tool tip after drilling. The results are shown in Table 1 in the "Tool Point State" column.
磨耗量越小,表示鑽頭之工具壽命越長。於「磨耗量(μm)」欄記為「-」之情形時,表示3根鑽頭均於剛開始加工後產生破損,而無法測定磨耗量。又,於「刀尖狀態」欄記為「1根破損」之情形時,將未破損之2根鑽頭之磨耗量之平均值示於表1之「磨耗量(μm)」欄。於「刀尖狀態」欄記為「微小碎屑」之情形時,表示刀尖產生微小碎屑。The smaller the wear, the longer the tool life of the drill. When the column of "Abrasion Amount (μm)" is marked as "-", it means that the 3 drills are damaged just after the start of processing, and the amount of abrasion cannot be measured. In addition, in the case where the "tool tip state" column is recorded as "1 broken", the average value of the abrasion of the two undamaged drill bits is shown in the "abrasion (μm)" column of Table 1. When it is marked as "micro chip" in the "tool tip status" column, it means that the tool tip produces small chips.
<探討> 試樣3、5~9、13~24相當於實施例。 <Discussion> Samples 3, 5-9, and 13-24 correspond to Examples.
試樣1、4、12於第2範圍內不存在極大頻數(第2極大頻數),相當於比較例。再者,試樣12中,於超過1.0 μm且為1.1 μm以下之等級中存在極大頻數。Samples 1, 4, and 12 have no maximum frequency (second maximum frequency) in the second range, which corresponds to a comparative example. In addition, in the sample 12, there is an extremely high frequency in the level exceeding 1.0 μm and less than 1.1 μm.
試樣2、10、11於第1範圍內不存在極大頻數(第1極大頻數),相當於比較例。試樣2於超過0.2 μm且為0.3 μm以下之等級中存在極大頻數,該極大頻數之個數基準之比率為10.1%。Samples 2, 10, and 11 have no maximum frequency (first maximum frequency) in the first range, which corresponds to a comparative example. Sample 2 has a maximum frequency in the level exceeding 0.2 μm and less than 0.3 μm, and the ratio of the number basis of the maximum frequency is 10.1%.
確認到試樣3、5~9、13~24(實施例)之磨耗量小於試樣1、2、4、10、12(比較例),而工具壽命較長。再者,試樣11(比較例)中,3根鑽頭均於剛開始後產生破損,而無法測定磨耗量。It was confirmed that the wear amount of samples 3, 5-9, and 13-24 (examples) was smaller than that of samples 1, 2, 4, 10, and 12 (comparative examples), and the tool life was longer. In addition, in sample 11 (comparative example), all three drills were damaged immediately after the start, and the amount of wear could not be measured.
如上所述,對本發明之實施方式及實施例進行了說明,但起初亦規定可將上述各實施方式及實施例之構成進行適當組合或各種變形。As described above, the embodiments and examples of the present invention have been described, but it is also stipulated at the beginning that the configurations of the above-mentioned embodiments and examples can be appropriately combined or variously modified.
應當認為文中揭示之實施方式及實施例於所有方面均為例示,並非限制性者。本發明之範圍由申請專利範圍揭示,而非由上述實施方式及實施例揭示,且意欲包含與申請專利範圍均等之含義、及範圍內之所有變更。It should be considered that the embodiments and examples disclosed in the text are illustrative in all aspects and not restrictive. The scope of the present invention is disclosed by the scope of the patent application, rather than the above-mentioned embodiments and examples, and is intended to include the meaning equivalent to the scope of the patent application, and all changes within the scope.
圖1係利用掃描式電子顯微鏡拍攝之本發明之超硬合金之圖像之一例。 圖2係對圖1之拍攝圖像進行圖像處理所得之圖像。 圖3係表示本發明之超硬合金中之碳化鎢粒子之圓相當徑之分佈之一例的圖。 圖4係表示本發明之超硬合金中之碳化鎢粒子之圓相當徑之分佈之另一例的圖。 圖5係表示本發明之超硬合金中之碳化鎢粒子之圓相當徑之分佈之另一例的圖。 圖6係表示本發明之超硬合金中之碳化鎢粒子之圓相當徑之分佈之另一例的圖。 Fig. 1 is an example of an image of the cemented carbide of the present invention taken with a scanning electron microscope. Figure 2 is an image obtained by performing image processing on the captured image of Figure 1. Fig. 3 is a diagram showing an example of the distribution of the circle-equivalent diameter of tungsten carbide particles in the cemented carbide of the present invention. 4 is a diagram showing another example of the distribution of the circle-equivalent diameter of tungsten carbide particles in the cemented carbide of the present invention. Fig. 5 is a diagram showing another example of the distribution of the circle-equivalent diameter of tungsten carbide particles in the cemented carbide of the present invention. Fig. 6 is a diagram showing another example of the distribution of the circle-equivalent diameter of the tungsten carbide particles in the cemented carbide of the present invention.
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JPH09227981A (en) * | 1996-02-20 | 1997-09-02 | Tokyo Tungsten Co Ltd | Cemented carbide |
JP3353522B2 (en) * | 1995-02-09 | 2002-12-03 | 住友電気工業株式会社 | Cemented carbide for tools processing wood-based hard materials |
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CN102808096A (en) * | 2012-08-13 | 2012-12-05 | 厦门钨业股份有限公司 | Preparation method for super coarse crystal WC-Co hard alloy |
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JP3127708B2 (en) * | 1994-03-11 | 2001-01-29 | 住友電気工業株式会社 | Coated cemented carbide for cutting tools |
DE112006000769C5 (en) * | 2005-03-28 | 2022-08-18 | Kyocera Corporation | Carbide and cutting tool |
JP5393004B2 (en) * | 2007-06-27 | 2014-01-22 | 京セラ株式会社 | Cemented carbide small diameter rod and cutting tool and miniature drill |
CN101845579B (en) * | 2010-06-28 | 2013-03-13 | 株洲钻石切削刀具股份有限公司 | Inhomogeneous hard alloy and preparation method thereof |
JP5835306B2 (en) * | 2013-11-22 | 2015-12-24 | 住友電気工業株式会社 | Cemented carbide and surface-coated cutting tool using the same |
EP3309268B1 (en) * | 2015-06-15 | 2020-07-29 | Sumitomo Electric Industries, Ltd. | Cemented carbide and cutting tool |
JP7021528B2 (en) * | 2017-03-17 | 2022-02-17 | 株式会社Moldino | Cemented carbide and its manufacturing method, and cutting tools using it |
US11458545B2 (en) * | 2017-03-30 | 2022-10-04 | Kyocera Corporation | Cutting insert and cutting tool |
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JP3353522B2 (en) * | 1995-02-09 | 2002-12-03 | 住友電気工業株式会社 | Cemented carbide for tools processing wood-based hard materials |
JPH09227981A (en) * | 1996-02-20 | 1997-09-02 | Tokyo Tungsten Co Ltd | Cemented carbide |
TW200909592A (en) * | 2007-06-27 | 2009-03-01 | Kyocera Corp | Cemented carbide, cutting tool, and cutting device |
CN102808096A (en) * | 2012-08-13 | 2012-12-05 | 厦门钨业股份有限公司 | Preparation method for super coarse crystal WC-Co hard alloy |
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TW202138580A (en) | 2021-10-16 |
JP2021161539A (en) | 2021-10-11 |
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