JP7605491B2 - A method for selective etching of the metallic bonding phase on the surface of cemented carbide. - Google Patents
A method for selective etching of the metallic bonding phase on the surface of cemented carbide. Download PDFInfo
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Description
本発明は、超硬工具を構成する超硬合金に含まれる硬質粒子相と金属結合相のうち、金属結合相のみを選択腐食するにあたって、必要な選択腐食深さを選定した際、その腐食時間を決定して、超硬合金表面の金属結合相を選択的に腐食する方法に関する。 The present invention relates to a method for selectively corroding only the metallic bond phase of the cemented carbide surface by determining the required selective corrosion depth and the corrosion time when selectively corroding only the metallic bond phase of the cemented carbide of a cemented carbide tool.
切断工具として用いられる超硬工具の特性の向上に関して、近年、硬質粒子相と金属結合相からなる超硬合金のうち、金属結合相を工具表面から除去し、硬質粒子相のみをその表面に残して工具として使用することによって、その特性が向上することが、特許文献１において報告されている。 Regarding the improvement of the characteristics of cemented carbide tools used as cutting tools, it has been reported in recent years in Patent Document 1 that the characteristics can be improved by removing the metallic bonding phase from the tool surface of cemented carbide alloys consisting of a hard particle phase and a metallic bonding phase, leaving only the hard particle phase on the surface and using the tool as such.
この金属結合相の除去に際して、化学エッチングや物理エッチングがその手段として用いられる。例えば特許文献２では、王水や硝酸溶液での表面金属結合相の除去プロセスが開示されている。
Chemical etching and physical etching are used to remove this metallic bonding phase. For example,
上述したように、金属結合相を化学エッチングや物理エッチングの方法で選択除去すると、その表面は、特定の使用環境において、耐摩耗性、耐電圧性、潤滑性等が改善することがわかっている。しかし、金属結合相の欠乏深さは、切断工具、切削工具、プレス工具、引き抜きダイス、摺動放電工具等、それぞれの用途に応じた品種の超硬合金にそれぞれ最適な深さが存在するため、腐食条件をあらかじめ定めておくことは困難である。 As mentioned above, it is known that when the metallic bonding phase is selectively removed by chemical or physical etching, the surface has improved wear resistance, voltage resistance, lubricity, etc. in certain usage environments. However, the depth of deficiency in the metallic bonding phase varies depending on the type of cemented carbide used for each application, such as cutting tools, cutting tools, press tools, drawing dies, and sliding discharge tools, and it is difficult to determine the corrosion conditions in advance.
従来は、顧客仕様に応じて、超硬合金の品種と選択腐食深さを定めると、都度選択腐食の予備検討を実施した上で、最適腐食時間を決定し製品に適用していた。しかし、このプロセスは工程が煩雑であることから、選択腐食された表面を持つ工具の量産採用を顧客が行うにあたって、品質、コスト、納期の観点から大きな障害となっていた。 Previously, once the type of cemented carbide and the selective corrosion depth were determined according to customer specifications, a preliminary study of selective corrosion was carried out each time, and the optimal corrosion time was then determined and applied to the product. However, this process was complicated, and was a major obstacle in terms of quality, cost, and delivery time for customers to mass-produce tools with selectively etched surfaces.
本発明は、このような事情を考慮してなされたもので、新規の用途、新規の超硬合金の品種、ならびに新規の選択腐食深さに対して都度の予備実験を実施しなくても、選択腐食条件を精度良く決定し、目的とする腐食深さに必要な腐食時間を定めて、その腐食時間で超硬合金中に含まれる金属結合相の選択腐食を行うことが可能な、金属結合相の選択腐食方法を提供することを目的とする。 The present invention was made in consideration of these circumstances, and aims to provide a method for selectively corroding metallic bonding phases that can accurately determine selective corrosion conditions, determine the corrosion time required for the target corrosion depth, and selectively corrode the metallic bonding phases contained in the cemented carbide for that corrosion time, without having to conduct preliminary experiments each time for a new application, a new type of cemented carbide, or a new selective corrosion depth.
以上の課題を解決するために、本発明は、超硬工具を構成する超硬合金に含まれる硬質粒子相と金属結合相のうち、超硬合金の表面において金属結合相のみを選択腐食する際に、必要な腐食深さを選定し、その狙い深さで腐食する金属結合相の選択腐食方法であって、腐食深さに影響を与える制御変数をあらかじめ重回帰分析を用いてその影響度を数値化し、重回帰分析における重回帰式によって目的とする腐食深さに必要な腐食時間を定めて、その腐食時間で超硬合金中に含まれる金属結合相の選択腐食を行うことを特徴とする金属結合相の選択腐食方法である。 In order to solve the above problems, the present invention is a method for selectively corroding only the metallic bond phase on the surface of a cemented carbide tool, by selecting the required corrosion depth and corroding it at the target depth, among the hard particle phase and metallic bond phase contained in the cemented carbide that constitutes the cemented carbide tool, characterized in that the influence of the control variables that affect the corrosion depth is quantified in advance using multiple regression analysis, the corrosion time required for the target corrosion depth is determined by the multiple regression equation in the multiple regression analysis, and the selective corrosion of the metallic bond phase contained in the cemented carbide is performed for that corrosion time.
また、本発明においては、前記腐食深さを重回帰分析で数式化する際、その制御変数として、硬質粒子相と金属結合相の質量比、超硬合金の硬質粒子径、腐食液組成、腐食液濃度、腐食液温度、腐食時間、腐食液の流速、または腐食時の振動条件の少なくとも１つ以上を含むことができる。 In addition, in the present invention, when the corrosion depth is mathematically expressed by multiple regression analysis, the control variables can include at least one of the mass ratio of the hard particle phase to the metallic bond phase, the hard particle diameter of the cemented carbide, the etching solution composition, the etching solution concentration, the etching solution temperature, the corrosion time, the flow rate of the etching solution, or the vibration conditions during corrosion.
また、本発明においては、前記重回帰式により求められる腐食時間から、使用目的とする工具に最適な腐食深さを定め、その他の制御変数を入力することにより、腐食深さに対応する腐食時間を算出することができる。 In addition, in the present invention, the optimal corrosion depth for the tool to be used is determined from the corrosion time obtained by the multiple regression equation, and the corrosion time corresponding to the corrosion depth can be calculated by inputting other control variables.
これにより、新規の用途、新規の超硬合金の品種、ならびに新規の選択腐食深さに対して都度の予備実験を実施しなくても、選択腐食条件を精度良く決定し、目的とする腐食深さに必要な腐食時間を定めて、その腐食時間で超硬合金中に含まれる金属結合相の選択腐食を行うことが可能となる。なお、選択腐食の深さは、強度保持の観点から、硬質粒子の平均粒径と同程度の深さとすることを前提としている。 This makes it possible to accurately determine the selective corrosion conditions, determine the corrosion time required for the desired corrosion depth, and selectively corrode the metallic bonding phase contained in the cemented carbide for that corrosion time without having to conduct preliminary experiments for each new application, new cemented carbide variety, and new selective corrosion depth. Note that, from the perspective of strength retention, it is assumed that the selective corrosion depth is approximately the same as the average grain size of the hard particles.
そのため、新たな顧客要求を伴う製品用途に対して、選択腐食の最適深さが決定され、この最適深さを得るための腐食時間が一義的に決定されることにより、顧客要求を満たす製品設計が属人化されることなく、最短、最適に決定され、良好な品質の超硬工具の量産が可能となる。 Therefore, for product applications that involve new customer requirements, the optimal depth of selective corrosion is determined, and the corrosion time required to obtain this optimal depth is uniquely determined. This allows product designs that satisfy customer requirements to be determined in the shortest possible time and in the most optimal way, without being dependent on individual factors, enabling the mass production of high-quality carbide tools.
本発明によると、新規の用途、新規の超硬合金の品種、ならびに新規の選択腐食深さに対して都度の予備実験を実施しなくても、新たな顧客要求を伴う製品用途に対して、選択腐食の最適深さが決定され、この最適深さを得るための腐食時間が一義的に決定されることにより、顧客要求を満たす製品設計が属人化されることなく、最短、最適に決定され、良好な品質の超硬工具の量産が可能となる。 According to the present invention, the optimal depth of selective corrosion is determined for product applications that entail new customer requirements, without the need to conduct preliminary experiments for each new application, new cemented carbide variety, and new selective corrosion depth, and the corrosion time required to obtain this optimal depth is uniquely determined. This allows product designs that satisfy customer requirements to be determined in the shortest and most optimal way, without being dependent on individual people, and enables the mass production of high-quality cemented carbide tools.
以下に、本発明に係る超硬合金表面の金属結合相の選択腐食方法を、その実施形態に基づいて説明する。 The following describes the method for selectively corroding the metallic bonding phase on the surface of a cemented carbide alloy according to the present invention, based on an embodiment of the method.
最初に、本発明の基盤技術となる、金属結合相の選択腐食の欠乏深さを算出する方法について説明する。 First, we will explain the method for calculating the depletion depth of selective corrosion of metallic bonding phases, which is the basic technology of the present invention.
図１は、超硬合金製工具の表面の金属結合相の選択腐食後の断面と、その際の金属結合相の主成分であるＣＯ量の変化を模式的に示したものである。選択腐食がなされた後の欠乏層内では、硬質粒子１間にわずかに金属結合相２が残存するために、ＣＯ量は完全にゼロとはならない値で変動を持って推移する。金属結合相２が腐食によって除去された領域から、未反応の領域ではなだらかなＣＯ量の遷移が起きており、この領域で欠乏深さを定義する必要がある。
Fig. 1 shows a schematic diagram of a cross section of the metallic bonding phase on the surface of a cemented carbide tool after selective corrosion and the change in the amount of CO, the main component of the metallic bonding phase, during the selective corrosion. In the depletion layer after selective corrosion, a small amount of
そこで本発明者は、図２に示す直線的な成分変化を仮定し、金属結合相の欠乏深さを定義することとした。母体のＣＯ量をｍ１、硬質粒子間に残る少量のＣＯ量をｍ２とし、ｍ２、ｍ１はそれぞれ一定値、ｍ２からｍ１への遷移は、図２に示すように、直線的な変化が起きるものと仮定する。 Therefore, the inventors have decided to define the depletion depth of the metallic bonding phase by assuming a linear change in components as shown in Figure 2. The amount of CO in the matrix is m1, and the small amount of CO remaining between the hard particles is m2. It is assumed that m2 and m1 are both constant values, and that the transition from m2 to m1 occurs linearly as shown in Figure 2.
この直線的な変化が起きるＣＯ量の遷移位置を、金属結合相の欠乏深さｄと定義する。これらの定義と、特性Ｘ線分析で照射するＸ線が計測する分析深さＤ、実際に特性Ｘ線分析で測定したＣｏ量ｍｘを用いて、Ｃｏ量の質量保存で等式を作ると、以下の式（１）が得られる。 The transition position of the CO amount where this linear change occurs is defined as the depletion depth d of the metallic bonding phase. Using these definitions, the analysis depth D measured by the X-rays irradiated in the characteristic X-ray analysis, and the amount of Co mx actually measured by the characteristic X-ray analysis, an equation is created based on the conservation of mass of the amount of Co, and the following equation (1) is obtained.
式（１）を欠乏深さｄで解けば、式（２）が得られる。 By solving equation (1) with respect to the deficiency depth d, we obtain equation (2).
ここで、硬質粒子間に残る金属結合相の濃度は、あらかじめ、走査型電子顕微鏡に付属する分析方法等でその残分を推定しておく必要がある。また分析深さは、使用する特性Ｘ線分析装置のＸ線強度と、分析される超硬合金の組成で定まる。 Here, the concentration of the metallic bonding phase remaining between the hard particles must be estimated in advance using an analysis method attached to the scanning electron microscope. The analysis depth is determined by the X-ray intensity of the characteristic X-ray analyzer used and the composition of the cemented carbide being analyzed.
特性Ｘ線分析装置とは、エネルギー分散型特性Ｘ線分析装置（ＥＤＳ）や、波長分散型特性Ｘ線分析装置（ＷＤＳ）などを指す。いずれの装置も、試料表面から放出される特性Ｘ線を検出することにより、試料の化学組成を測定する装置であり、ＥＤＳは特性Ｘ線のエネルギーを測定するものであり、ＷＤＳは特性Ｘ線の波長を測定するものである。 Characteristic X-ray analyzers include energy dispersive X-ray analyzers (EDS) and wavelength dispersive X-ray analyzers (WDS). Both instruments measure the chemical composition of a sample by detecting characteristic X-rays emitted from the sample surface, with EDS measuring the energy of characteristic X-rays and WDS measuring the wavelength of characteristic X-rays.
ＥＤＳは、特性Ｘ線の反応領域が、深さ方向に数μｍと比較的浅い一方、ＷＤＳは１０μｍを超える分析深さを有している。本発明においては、被分析素材が数μｍ程度の硬質粒子径を持つことを考えると、複数粒子分の深さが測定できる波長分散型特性Ｘ線分析装置（ＷＤＳ）の方が、より望ましい分析装置であると言える。 In EDS, the reaction region of characteristic X-rays is relatively shallow at a depth of a few μm, while WDS has an analysis depth of more than 10 μm. In the present invention, considering that the material to be analyzed has hard particle diameters of about a few μm, it can be said that a wavelength dispersive characteristic X-ray analyzer (WDS), which can measure the depth of multiple particles, is a more desirable analytical device.
このような単純化された定義の欠乏深さではあるが、この欠乏深さは算術上、一義的に定まるものであり、またＣｏ量の遷移領域と必ず交わるために、取り決めとして仕様書などにうたう場合に、大変扱いやすい定義となる。またこの測定方法は非破壊であるために、直接的に出荷検査に用いることが可能になり、同時に異常時の原因分析に用いることもできる。 Although this is a simplified definition of the deficiency depth, it is arithmetically uniquely determined and always intersects with the transition region of the Co content, making it a very easy definition to use when specifying it as an agreement in specifications. Furthermore, because this measurement method is non-destructive, it can be used directly for shipping inspections, and at the same time, it can also be used to analyze the cause of abnormalities.
上述したように、超硬合金母体の組成ｍ１、これと同一の母体を工具に加工し、金属結合相を選択腐食した後で上面から特性Ｘ線分析で計測した組成ｍｘ、選択腐食された金属結合相の欠乏領域で硬質粒子間にわずかに残存する金属結合相の組成ｍ２、および特性Ｘ線分析で特性Ｘ線が放出されることにより計測する分析深さＤの４つの情報から、金属結合相の欠乏深さｄを算出することが可能となる。 As described above, it is possible to calculate the depletion depth d of the metallic bonding phase from four pieces of information: the composition m1 of the cemented carbide base body, the composition mx measured from the top surface by characteristic X-ray analysis after processing the same base body into a tool and selectively etching the metallic bonding phase, the composition m2 of the metallic bonding phase remaining in small amounts between the hard particles in the depleted area of the selectively etched metallic bonding phase, and the analysis depth D measured by the emission of characteristic X-rays in the characteristic X-ray analysis.
図３に、以上説明した、超硬合金中の表面金属結合相の欠乏深さ測定方法のフローチャートを示す。この処理を行うことにより、計算された腐食深さは、実際には境界があいまいな腐食前面の深さを非破壊で一義的に定義できる。 Figure 3 shows a flowchart of the method for measuring the depth of deficiency in the surface metal bonding phase in cemented carbide, as described above. By performing this process, the calculated corrosion depth can nondestructively and unambiguously define the depth of the corrosion front, the boundary of which is actually ambiguous.
上述した、金属結合相の欠乏深さの算出方法を用いて、以下に、本発明の実施形態に係る超硬合金表面の金属結合相の選択腐食方法について説明する。
本発明は、新規の用途、新規の超硬合金の品種、新規の選択腐食深さに対して、都度の予備実験を実施しなくても、選択腐食条件を精度高く決定するための方法に関するものである。
A method for selectively corroding a metallic bonding phase on a surface of a cemented carbide according to an embodiment of the present invention will be described below using the above-mentioned method for calculating the depletion depth of the metallic bonding phase.
The present invention relates to a method for determining selective corrosion conditions with high accuracy for a new application, a new type of cemented carbide, or a new selective corrosion depth, without the need to carry out preliminary experiments each time.
その方法は、超硬工具を構成する超硬合金に含まれる硬質粒子相と金属結合相のうち、超硬合金の表面において金属結合相のみを選択腐食する際に、必要な腐食深さを選定し、その狙い深さで腐食する金属結合相の選択腐食方法であって、腐食深さに影響を与える制御変数をあらかじめ重回帰分析を用いてその影響度を数値化し、重回帰分析における重回帰式によって目的とする腐食深さに必要な腐食時間を定めて、その腐食時間で超硬合金中に含まれる金属結合相の選択腐食を行う選択腐食方法である。 This method is a selective corrosion method for the metallic bond phase, which is selectively corroded at the target depth when selectively corroding only the metallic bond phase on the surface of the cemented carbide out of the hard particle phase and metallic bond phase contained in the cemented carbide that constitutes the cemented carbide tool, by selecting the required corrosion depth and selectively corroding the metallic bond phase at the target depth, in which the degree of influence of the control variables that affect the corrosion depth is quantified in advance using multiple regression analysis, the corrosion time required for the target corrosion depth is determined by the multiple regression equation in the multiple regression analysis, and the metallic bond phase contained in the cemented carbide is selectively corroded for that corrosion time.
腐食深さを重回帰分析で数式化する際、その制御変数として、硬質粒子相と金属結合相の質量比、超硬合金の硬質粒子径、腐食液組成、腐食液濃度、腐食液温度、腐食時間、腐食液の流速、または腐食時の振動条件の少なくとも１つ以上を含むようにし、重回帰式を腐食時間について解き、目的とする工具に最適な腐食深さを定め、その他の制御変数を入力することにより、腐食深さに対応する腐食時間を算出するものである。 When the corrosion depth is expressed as a mathematical expression using multiple regression analysis, the control variables include at least one of the mass ratio of the hard particle phase to the metallic bond phase, the hard particle diameter of the cemented carbide, the corrosion solution composition, the corrosion solution concentration, the corrosion solution temperature, the corrosion time, the flow rate of the corrosion solution, or the vibration conditions during corrosion. The multiple regression equation is then solved for the corrosion time, the optimum corrosion depth for the target tool is determined, and the corrosion time corresponding to the corrosion depth is calculated by inputting the other control variables.
上述した、選択腐食深さに必要な腐食時間を一義的に求める方法を、製品の製造プロセスに適用した処理のフローチャートを、図４に示す。 Figure 4 shows a flowchart of the process in which the above-mentioned method for uniquely determining the corrosion time required for a selected corrosion depth is applied to a product manufacturing process.
以下に、金属結合相の欠乏深さｄについて、狙い値と計算値と実測値との比較についての試験内容と、その結果について説明する。
図５に、重回帰分析による欠乏深さ算出のためのフローチャートを示す。
The following describes the test content and results of the comparison of the target value, the calculated value, and the actually measured value for the depletion depth d of the metallic bonding phase.
FIG. 5 shows a flow chart for calculating the deficiency depth by multiple regression analysis.
硬質粒子の粒径や金属結合相量が異なる材種を用いて、サンプルを製作し、エッチング処理前のサンプルについて、波長分散型特性Ｘ線分析装置（ＷＤＳ）またはエネルギー分散型特性Ｘ線分析装置（ＥＤＳ）により成分分析して、母相の金属結合相量を同定し、これを未処理の計算基準値として用いる。ここでは、粒子径が異なる３つの材種（細粒、中粒、粗粒）を対象とし、それぞれの平均粒径は、細粒が０．６～１．０μｍ、中粒が２．０～４．０μｍ、粗粒が５．０μｍ以上である。 Samples are made using materials with different hard particle diameters and metallic bond phase amounts, and the samples before etching are subjected to component analysis using a wavelength dispersive X-ray analyzer (WDS) or energy dispersive X-ray analyzer (EDS) to identify the amount of metallic bond phase in the parent phase, which is used as the unprocessed calculation reference value. Here, three materials with different particle diameters (fine, medium, coarse) are targeted, with the average particle diameters of fine grains being 0.6 to 1.0 μm, medium grains being 2.0 to 4.0 μm, and coarse grains being 5.0 μm or more.
その後、サンプルをエッチング処理して、エッチング処理されたサンプルの成分分析を行い、処理後の金属結合相量を同定する。これらのデータと分析深さＤから、式（２）により、各サンプルの金属結合相の欠乏深さを計算する。 The samples are then etched, and the components of the etched samples are analyzed to identify the amount of metallic bonding phase after the process. From these data and the analysis depth D, the metallic bonding phase deficiency depth of each sample is calculated using formula (2).
サンプルを粒子径が異なる材種系統ごとに分類し、金属結合相の欠乏深さについて重回帰分析を行い、回帰直線を算出し、回帰直線の方程式から、処理時間について解を求める式（処理条件決定式）を算出する。 The samples are classified into material types with different particle sizes, and multiple regression analysis is performed on the depth of deficiency in the metal bonding phase to calculate a regression line. From the equation for the regression line, a formula (treatment condition determination formula) is calculated to find the solution for the treatment time.
それぞれの材種系統のサンプルを製作し、エッチング処理前のサンプルの成分分析を行い、母相の金属結合相量を同定する。処理条件決定式より、金属結合相欠乏深さの狙い値と処理時間を決定し、エッチング処理を行う。 Samples of each material type are produced, and the components of the samples are analyzed before etching to identify the amount of metallic bond phase in the parent phase. The target metallic bond phase deficiency depth and processing time are determined using the processing condition determination formula, and the etching process is then performed.
上述した処理を行った具体的な実施例について、以下に説明する。
図６から図８に、粒子径が異なる材種系統ごとに重回帰分析を行った例を示しており、図６は、細粒についての回帰直線を示し、図７は、中粒についての回帰直線を示し、図８は、粗粒についての回帰直線を示している。
A specific example in which the above-mentioned processing is carried out will be described below.
6 to 8 show examples of multiple regression analysis for each material type with different particle sizes. FIG. 6 shows the regression line for fine grains, FIG. 7 shows the regression line for medium grains, and FIG. 8 shows the regression line for coarse grains.
図９に、この重回帰分析の処理条件決定の詳細を示しており、図９（ａ）は、重回帰分析における係数を、細粒、中粒、粗粒のそれぞれについて示している。また、図９（ｂ）は、これにより求めた処理時間計算値を示しており、図９（ｃ）は、欠乏深さ計算値を示している。なお、図９における処理深さは、欠乏深さと同意である。 Figure 9 shows the details of the determination of processing conditions in this multiple regression analysis, with Figure 9(a) showing the coefficients in the multiple regression analysis for fine, medium, and coarse grains. Figure 9(b) shows the calculated processing time obtained from this, and Figure 9(c) shows the calculated deficiency depth. Note that the processing depth in Figure 9 is the same as the deficiency depth.
図９（ｃ）により決定された狙い処理時間は、細粒で６０秒、中粒で６５秒、粗粒で１００秒であり、欠乏深さの狙い値は、細粒で０．１６μｍ、中粒で０．７６μｍ、粗粒で１．０４μｍであった。結合相量は１２．０ｗｔ％、処理液濃度は１０．０ｗｔ％である。 The target processing time determined from Figure 9 (c) was 60 seconds for fine grains, 65 seconds for medium grains, and 100 seconds for coarse grains, and the target values for the deficiency depth were 0.16 μm for fine grains, 0.76 μm for medium grains, and 1.04 μm for coarse grains. The amount of the binder phase was 12.0 wt%, and the concentration of the processing solution was 10.0 wt%.
この狙い値と対比するために、サンプルの金属結合相の欠乏深さの計算値を、式（２）により求めるとともに、金属結合相の欠乏深さの実測値を、ＳＥＭにより実測した。
サンプルの断面をイオンビームミリングで加工し、金属結合相が欠乏している深さをＳＥＭで実測して欠乏深さ分析を行ったところ、その平均値は、細粒で０．１４μｍ、中粒で０．８１μｍ、粗粒で１．２９μｍであった。欠乏深さの測定は、数か所について実測を行い、その平均値とした。図１１は、細粒についてＳＥＭにより欠乏深さの実測を行った図である。図１２は、中粒についてＳＥＭにより欠乏深さの実測を行った図である。図１３は、粗粒についてＳＥＭにより欠乏深さの実測を行った図である。
To compare with this target value, the calculated value of the depletion depth of the metallic bonding phase of the sample was obtained using formula (2), and the actual measured value of the depletion depth of the metallic bonding phase was measured using a SEM.
The cross section of the sample was processed by ion beam milling, and the depth of the metallic bonding phase was measured by SEM to perform a deficiency depth analysis. The average values were 0.14 μm for fine grains, 0.81 μm for medium grains, and 1.29 μm for coarse grains. Measurements of the deficiency depth were performed at several locations, and the average values were used. Figure 11 is a diagram showing the actual measurement of the deficiency depth for fine grains by SEM. Figure 12 is a diagram showing the actual measurement of the deficiency depth for medium grains by SEM. Figure 13 is a diagram showing the actual measurement of the deficiency depth for coarse grains by SEM.
一方、計算による欠乏深さは、細粒については、０．１４μｍであり、中粒については、０．８７μｍであり、粗粒については、１．３２μｍであった。 On the other hand, the calculated deficiency depth was 0.14 μm for fine grains, 0.87 μm for medium grains, and 1.32 μm for coarse grains.
狙い欠乏深さと計算深さと実測深さの対比を図１０に示す。図１０（ａ）は、細粒についてのものであり、図１０（ｂ）は、中粒についてのものであり、図１０（ｃ）は、粗粒についてのものである。 The comparison of the target deficiency depth, the calculated depth, and the measured depth is shown in Figure 10. Figure 10(a) is for fine grains, Figure 10(b) is for medium grains, and Figure 10(c) is for coarse grains.
図１０（ａ）、（ｂ）、（ｃ）において、欠乏深さの適正範囲の上限値と下限値は、回帰直線式の値とプロットされている解析用データとの差異のばらつきより決定しており、図１０（ｄ）に、最大差異絶対値と、差異の標準偏差σと、３σを示している。その結果、いずれのケースについても、±３σの範囲内にあり、回帰直線から外れていないことが確認された。 In Figures 10(a), (b), and (c), the upper and lower limits of the appropriate range of deficiency depth are determined from the variation in the difference between the value of the regression line and the plotted analysis data, and Figure 10(d) shows the maximum absolute difference, the standard deviation of the difference, σ, and 3σ. As a result, it was confirmed that in all cases, the values were within the range of ±3σ and did not deviate from the regression line.
上記の実施例における制御変数は一例を示したものであり、腐食深さに影響を与える制御変数には様々なものがあり得る。例えば、腐食液温度については、温度を上げると化学的に腐食反応を促進することがわかっており、反応を制御する因子である。また、腐食液の流速は、腐食液中反応イオンの物質移動を促進し、反応速度に影響を与えるため、反応を制御する因子である。さらに、腐食時の振動は、ミクロな凹部の間隙の反応物の除去と反応イオンの補充を促進し、反応速度に影響を与えるため、反応を制御する因子である。
これらの因子を制御変数として用いて、水準を変化させ、重回帰分析を行うことによって、上記の実施例と同様に、影響度を数値化することができる。
The control variables in the above embodiment are merely examples, and there may be various control variables that affect the corrosion depth. For example, the temperature of the etching solution is a factor that controls the reaction, since it is known that increasing the temperature chemically accelerates the corrosion reaction. In addition, the flow rate of the etching solution is a factor that controls the reaction, since it accelerates the mass transfer of reactive ions in the etching solution and affects the reaction rate. Furthermore, vibration during corrosion is a factor that controls the reaction, since it accelerates the removal of reactants in the gaps of micro recesses and the replenishment of reactive ions, and affects the reaction rate.
By using these factors as control variables, varying the levels, and performing multiple regression analysis, the degree of influence can be quantified in the same manner as in the above embodiment.
このように、腐食深さに影響を与える様々な制御変数を用いて同様の重回帰分析を行うことが可能であり、重回帰分析で数式化する際の制御変数として、硬質粒子相と金属結合相の質量比、超硬合金の硬質粒子径、腐食液組成、腐食液濃度、腐食液温度、腐食時間、腐食液の流速、または腐食時の振動条件等を用いることができる。 In this way, it is possible to perform a similar multiple regression analysis using various control variables that affect the corrosion depth. The control variables that can be used to formulate the equation in the multiple regression analysis include the mass ratio of the hard particle phase to the metallic bond phase, the hard particle diameter of the cemented carbide, the etching solution composition, the etching solution concentration, the etching solution temperature, the corrosion time, the flow rate of the etching solution, or the vibration conditions during corrosion.
上述したプロセスを確立することにより、新たな顧客要求を伴う製品用途に対して、最適深さを決定すると、この最適深さを得るための腐食時間は一義的に決定される。これにより顧客要求を満たす製品設計が属人化されることなく最短、最適に決定されるため、良好な品質の超硬工具の量産が可能となる。 By establishing the above-mentioned process, once the optimal depth is determined for a product application that involves new customer requirements, the corrosion time required to achieve this optimal depth is uniquely determined. This allows product designs that meet customer requirements to be determined in the shortest and most optimal way possible without being dependent on individual skills, making it possible to mass-produce high-quality carbide tools.
本発明は、新規の用途、新規の超硬合金の品種、ならびに新規の選択腐食深さに対して都度の予備実験を実施しなくても、選択腐食条件を精度良く決定し、目的とする腐食深さに必要な腐食時間を定めて、その腐食時間で超硬合金中に含まれる金属結合相の選択腐食を行うことが可能な、金属結合相の選択腐食方法として、広く利用することができる。 The present invention can be widely used as a method for selectively corroding metallic bonding phases, which can accurately determine selective corrosion conditions, determine the corrosion time required for the desired corrosion depth, and selectively corrode the metallic bonding phases contained in the cemented carbide for that corrosion time, without having to conduct preliminary experiments for each new application, new type of cemented carbide, and new selective corrosion depth.
１ 硬質粒子
２ 金属結合相
1
Claims (3)
必要な腐食深さの選定は、超硬合金母体の組成と、これと同一の母体を工具に加工し、金属結合相を選択腐食した後で上面から特性Ｘ線分析で計測した組成と、選択腐食された金属結合相の欠乏領域で硬質粒子間にわずかに残存する金属結合相の組成と、特性Ｘ線分析で特性Ｘ線が放出されることにより計測する分析深さの４つの情報から、金属結合相の欠乏深さを算出することを用いることによってなされることを特徴とする超硬合金表面の金属結合相の選択腐食方法。 A method for selectively corroding only the metallic binder phase on the surface of a cemented carbide tool, comprising: selecting a required corrosion depth; and selectively corroding the metallic binder phase at the target depth, comprising: selecting a control variable that affects the corrosion depth using multiple regression analysis to quantify the degree of influence of the control variable; determining a corrosion time required for the target corrosion depth using a multiple regression equation in the multiple regression analysis; and selectively corroding the metallic binder phase contained in the cemented carbide for the corrosion time ;
a composition of the metallic bonding phase measured from the top surface by characteristic X-ray analysis after machining the same substrate into a tool and selectively etching the metallic bonding phase; a composition of the metallic bonding phase remaining slightly between hard particles in a depleted region of the selectively etched metallic bonding phase; and an analysis depth measured by emission of characteristic X-rays in characteristic X-ray analysis .
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