WO2009131175A1 - 金属材料中微粒子の粒度分布測定方法 - Google Patents
金属材料中微粒子の粒度分布測定方法 Download PDFInfo
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- WO2009131175A1 WO2009131175A1 PCT/JP2009/058072 JP2009058072W WO2009131175A1 WO 2009131175 A1 WO2009131175 A1 WO 2009131175A1 JP 2009058072 W JP2009058072 W JP 2009058072W WO 2009131175 A1 WO2009131175 A1 WO 2009131175A1
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- fine particles
- particle size
- metal material
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- size distribution
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Images
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N15/00—Investigating characteristics of particles; Investigating permeability, pore-volume or surface-area of porous materials
- G01N15/02—Investigating particle size or size distribution
- G01N15/0205—Investigating particle size or size distribution by optical means
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/0005—Field flow fractionation
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/20—Metals
- G01N33/202—Constituents thereof
- G01N33/2022—Non-metallic constituents
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/47—Scattering, i.e. diffuse reflection
- G01N2021/4704—Angular selective
Definitions
- the present invention provides field flow fractionation (FFF).
- FFF field flow fractionation
- the present invention relates to a method for measuring the particle size of fine particles (precipitates and non-metallic inclusions) in a metal material using a Flow Fractionation method.
- Patent Document 1 describes a method aiming to compensate for such a low number density in microscopic observation.
- this conventional method first, steel is electrolyzed, and the extracted residue is dropped and dried on a support film to prepare a sample having an extremely large number of residue particles. Next, this sample is subjected to optical microscope analysis, scanning electron microscope (SEM) analysis, transmission electron microscope (TEM) analysis, and the like.
- SEM scanning electron microscope
- TEM transmission electron microscope
- Patent Document 2 Another evaluation method different from the microscope test method is described in Patent Document 2 and Non-Patent Document 2.
- a spark discharge emission analysis of about 2000 pulses is performed on a metal sample, and the oxide particle size is obtained from discharge data obtained by removing preliminary discharge data of initial several hundred pulses.
- a very strong light emission (abnormal light emission) intensity of an oxide-forming element emits light from one oxide.
- Non-Patent Document 3 describes another method for obtaining the size and frequency of alumina inclusions.
- a spark discharge emission analysis is performed on a metal sample, and in the obtained emission analysis data, it is assumed that only pulse data exceeding a certain threshold is inclusions, etc. I'm looking for size and frequency.
- compositional analysis utilizing simultaneous multi-element light emission can be performed because optical information such as light emission intensity is processed as data.
- the solid solution component contained in the matrix since the fine particles such as inclusions that contribute to light emission are in principle larger than several ⁇ m, the solid solution component contained in the matrix must be a fine particle of such a size. Cannot be compared with the pulse intensity. That is, the emission analysis method cannot be applied to fine particles smaller than several ⁇ m, and accurate analysis cannot be performed.
- JP 2004-317203 A Japanese Patent Laid-Open No. 10-300659 Japanese Patent Laid-Open No. 2005-62166
- the present invention is capable of quickly and accurately quantitatively analyzing the size and number density of fine particles contained in a metal material, and preferably capable of quickly and accurately quantitatively analyzing the composition and crystal structure of the fine particles. It is an object of the present invention to provide a method for measuring the particle size distribution of medium fine particles.
- the present invention has been made to solve the above-mentioned problems, and the gist thereof is as follows.
- Process A method for measuring the particle size distribution of fine particles in a metal material.
- the size and number density of fine particles contained in a metal material can be quantified quickly and with good reproducibility. For this reason, the particle size distribution can be accurately measured.
- FIG. 1 is a flowchart showing a basic flow of a particle size distribution measuring method for fine particles in a metal material according to an embodiment of the present invention.
- FIG. 2 is a diagram illustrating an example of the in-steel particle extraction device 1.
- FIG. 3 is a diagram illustrating an example of a method for preparing a solution used in the particle fine dispersion device 2.
- FIG. 4 is a diagram showing the size separation principle of the FFF method.
- FIG. 5 is a graph showing the measurement results of the relationship between the particle size and the number density distribution.
- FIG. 6 is a graph showing a comparison result of the number of days required for the number density analysis between the embodiment of the present invention and the conventional method.
- FIG. 7 is a graph showing the composition analysis results of fine particles sieved for each nanosize.
- An important matter in the present invention is to enable quick and accurate quantitative analysis of the particle size and number density of fine particles contained in a metal material to be measured. In addition to overcoming the problems inherent in sensory tests, such as errors and time, and providing a method for clearly grasping the number density of fine particles of several ⁇ m or less that cannot be detected by the estimation method using emission spectrometry. It is important to be able to measure size and number density with high reproducibility.
- the inventors examined sieving for each particle size before photographing.
- a minimum size of about 20 ⁇ m is the smallest currently available, and it is difficult to divide a smaller size by size. Therefore, the present inventors have repeated research specialized in a method of sieving fine particles of 20 ⁇ m or less for each size.
- the size and amount can be determined by ionizing them as they are and subjecting them to mass spectrometry or separating and extracting them by ion chromatography.
- the fine particles in steel are much larger than biological samples and are difficult to soft ionize.
- dissolves for ionization the information regarding a size will disappear. For this reason, it cannot be dissolved.
- positive ions and negative ions are not clearly charged in the solution, and therefore cannot be separated by ion chromatography or the like.
- a size separation method by GPC gel permeation chromatography was also examined, but it is unsuitable for high-precision separation of minute amounts.
- the measurable molecular weight range is as wide as several hundred to several tens of millions, the fine particles in actual metal materials range from several nanometers to several tens of micrometers, so the molecular weight is low at tens of millions of orders. This is because it is impossible to separate the sample and a large amount of sample is required.
- FFF Field Flow Fractionation
- the fine particles are sieved in advance for each size.
- FIG. 1 shows a basic flow of a method for measuring the particle size distribution of fine particles in a metal material according to an embodiment of the present invention.
- the fine particle analyzer used for carrying out the present embodiment mainly includes a steel particle extracting device 1, a particle fine dispersing device 2, and an FFF device 3.
- the fine particle size distribution measuring method according to the present embodiment first, the fine particles contained in the metal material are stably extracted using the in-steel particle extracting device 1. Next, the fine particle in the above-described metal material is finely dispersed in the solution by the fine particle dispersion device 2 without being aggregated in the solution. Then, the fine particles in the metal material finely dispersed in the solution are put into the FFF device 3 and the fine particles are classified by size, measured for size, and measured for number density. An example of the operation of the FFF device 3 is shown below.
- the particles are divided into the sizes by focusing, and then the small particles are sequentially separated from the large particles. Let it flow out in order.
- Laser light is applied to the obtained solution, the absolute value of the size is determined from the angle dependence of the reflection intensity, and the absolute value of the number density is determined from the intensity of the reflection intensity.
- the steel particle extraction apparatus 1 is an apparatus that stably extracts fine particles from metal.
- FIG. 2 is a diagram illustrating an example of the in-steel particle extraction device 1.
- the extraction method of fine particles in a metal sample in this embodiment is, for example, an acid decomposition method in which an iron matrix of a steel sample is dissolved in an acid solution, an iron matrix of a steel sample is dissolved in an iodine methanol mixed solution or a bromine methanol mixed solution.
- SPEED Selective-potentiostatic-Etching-by-Electrolytic-Dissolution-Method
- the SPEED method is preferable because the composition and size hardly change when the fine particles are dispersed in the solvent, and even unstable fine particles can be stably extracted.
- the content of the SPEED method is described in Non-Patent Document 4, for example.
- the present embodiment will be described by taking as an example a method for evaluating fine particles in a steel material by a non-aqueous solvent system constant potential electrolysis method (SPEED method), but the extraction method in the present invention is limited to the SPEED method.
- the metal material is not limited to the steel material.
- the metal sample 4 is processed into a size of, for example, 20 mm ⁇ 40 mm ⁇ 2 mm, and the oxide film such as the scale of the surface layer is removed by chemical polishing or mechanical polishing, and the metal layer is taken out. deep. Conversely, when analyzing the fine particles contained in the oxide film layer, it is left as it is.
- this metal sample 4 is electrolyzed using the SPEED method.
- the electrolytic bath 9 is filled with the electrolytic solution 9, the metal sample 4 is immersed therein, and the reference electrode 7 is brought into contact with the metal sample 4.
- the platinum electrode 6 and the metal sample 4 are connected to the electrolysis device 8.
- the electrolytic potential of fine particles in steel such as precipitates has a higher electrolytic potential than the electrolytic potential of the metal portion serving as the matrix of the metal sample 4. Therefore, it is possible to selectively dissolve only the matrix by setting a voltage between the electrolysis potential that dissolves the matrix of the metal sample 4 using the electrolysis apparatus 8 and does not dissolve fine particles such as precipitates. It becomes.
- the electrolytically extracted particles 5 are dispersed in the surface layer portion of the metal sample 4 and the electrolytic solution 9.
- the solvent may be an aqueous solvent or an organic solvent, but an organic solvent is preferable in order to stably retain the electrolytic extraction particles 5 such as inclusions without dissolving them.
- organic solvents alcohol solvents such as methanol and ethanol are easily available and have high stability.
- TMAC tetramethylammonium chloride
- a 2% by mass TMAC-methanol solution is used as the electrolytic solution.
- a chelating reagent that forms a chelate complex with a metal ion such as methyl salicylate and an electrolyte for passing an electric current such as tetramethylammonium chloride (TMAC) are used as an electrolytic solution dissolved in a methanol solvent that is a non-aqueous solvent.
- TMAC tetramethylammonium chloride
- the present inventors further stabilize the electrolytic extraction particles 5 such as inclusions by using, as the electrolytic solution 9, a solution obtained by further adding a dispersant mainly composed of a surfactant, which will be described later, to these electrolytic solutions. Newly found that it can be captured. When the surfactant is added, the surfactant stably wraps around the electrolytic extraction particles 5 immediately after being separated from the metal matrix and released into the electrolytic solution 9.
- the electrolytic extraction particles 5 such as inclusions away from the metal material 9 such as steel come into contact with air. It is stably incorporated in the dispersant before and the extraction effect is improved. Furthermore, when the electrolytically extracted particles 5 such as inclusions are subsequently redispersed in a solvent, the effect of being easily dispersed into single particles can be obtained. For this purpose, it is important to carry out the processes from the extraction of the electrolytically extracted particles 5 to the separation into the particle sizes described later in the liquid so that the electrolytically extracted particles 5 do not come into contact with air.
- the concentration of the surfactant to be added is preferably 0.0001% by mass to 10% by mass. If the concentration is less than 0.0001% by mass, the action is too weak. Moreover, since it will become easy to produce
- FIG. 3 is a diagram showing an example of a method for preparing a solution used in the particle fine dispersion device 2.
- the particle extraction solution 13 produced through ultrasonic irradiation or the like that is, the particle extraction solution 13 including the electrolytic extraction particles 5 extracted from the metal sample 4 using the in-steel particle extraction apparatus 1 is used as a solution holding container.
- a dispersant 12 is added to finely disperse the electrolytically extracted particles 5.
- the dispersant for example, a surfactant is used.
- the surface potential of the electrolytically extracted particles 5 can be increased and dispersed by adjusting the zeta potential with PH. However, it is more effective to mainly use a surfactant as the dispersant.
- the surfactant has in its molecule a part that is easy to adjust to water (hydrophilic group) and a part that is easy to adjust to oil (lipophilic group / hydrophobic group).
- hydrophilic group a surfactant is added to the surface of the particles to change the periphery of the particles into a positive or negative charge.
- the particles obtain repulsive forces having the same polarity, and the individual particles are dispersed.
- Surfactants are roughly classified into those having a hydrophilic portion that is ionic (cationic / anionic) and nonionic (nonionic).
- Anionic surfactants dissociate in water to become anions, and the structure of the hydrophilic group is typically a carboxylic acid structure, a sulfonic acid structure, or a phosphoric acid structure.
- carboxylic acid surfactants include fatty acid salts and cholate salts, which are the main components of soap, and typical sulfonic acid surfactants include sodium linear alkylbenzene sulfonate and sodium lauryl sulfate. It is.
- Typical cationic surfactants are those that dissociate in water to become cations and have tetraalkylammonium as their hydrophilic groups.
- alkyltrimethylammonium salt, dialkyldimethylammonium salt, alkylbenzyldimethylammonium salt and the like are representative.
- both the anionic surfactant and the cationic surfactant are effective as the dispersant 12.
- sodium salts of sulfuric acid mono-long-chain alkyl esters such as sodium lauryl sulfate (C 12 H 25 NaO 4 S: SDS (sodium dodecyl sulfate)) that are relatively easily available and are used in the field of biochemistry, etc. preferable. This is because it is also used as daily necessities such as toothpaste and shampoo, and is safe and inexpensive for the human body.
- an amphoteric surfactant having both an anionic portion and a cationic portion in the molecule, a nonionic surfactant having a hydrophilic portion that does not ionize the hydrophilic portion, and the like may be used as the dispersant 12. it can.
- a particle extraction solution 13 containing electrolytically extracted particles 5 such as inclusions extracted from a metal material 4 such as steel is collected in a solution holding container 11 such as a test tube and the concentration of SDS. Is added in an amount of 0.0001 mass% to 10 mass%, preferably 0.05 mass% or less of dispersion liquid 12 and dispersed by irradiating with ultrasonic waves for 1 to 10 minutes, preferably 3 minutes.
- the particle extraction solution 13 may have a very dense density or a very thin density, and it may be overloaded to the measuring apparatus. For this reason, it is preferable to accommodate at least 1 ml and at most 20 ml.
- the concentration of SDS may be within a range in which the ability to disperse the electrolytically extracted particles 5 can be maintained, but is preferably as thin as possible. However, if it is thinner than 0.0001% by mass, the dispersion effect is low, and if it is too thick, there is a problem that costs are increased and bubbles are easily generated.
- the ultrasonic irradiation time varies depending on the output and the amount of liquid, but if left for more than 10 minutes, it is heated and the content of the mixture of the particle extraction solution 13 and the dispersant 12 is likely to change. On the other hand, if it is less than 1 minute, dispersion may be insufficient.
- the size of the electrolytic extraction particles 5 contained in the solution is wide, and depending on the measurement method, the coarse electrolytic extraction particles 5 may be dispersed inside the FFF device 3. There is a possibility of blocking small holes and filters. For this reason, it is preferable to remove the coarse electrolytically extracted particles 5 in advance. For example, it may be pre-filtered with a filter of several ⁇ m mesh. Alternatively, coarse particles having a size of 1 ⁇ m or more are allowed to settle downward by taking a few minutes or more with a centrifugal separator, and an upper supernatant liquid of the obtained liquid may be collected and applied to the FFF device 3.
- the size separation principle of the FFF method will be described with reference to FIG.
- a separation solution containing a surfactant is used, and a liquid flow called a cross flow 14 is first generated from the upper side of the cell toward the lower cell, while the left side of the separation cell 16 is left.
- the liquid is also flowed from the right side, and the sample solution 15 containing fine particles is added therebetween.
- the large particles 20 having a large size are pressed and stuck to the lower separation membrane 21 by the flow of the cross flow 14, while the medium particles 19 and the small particles 18 having a relatively large size are flown by the cross flow 14.
- the liquid separated for each size is directly guided to a laser light irradiation detection unit disposed inside the FFF device 3, and the light intensity scattered by the laser light is obtained from photodetectors installed at a plurality of angles.
- the angle dependency is very small and an omnidirectional scattering phenomenon is exhibited.
- the size of the electrolytic extraction particles 5 can be uniquely determined by taking the inclination of the angle dependency.
- the size of the electrolytically extracted particles 5 can be calculated from the angle dependency using the Zim plot method.
- the Zimm plot method is demonstrated easily.
- the relationship between the scattering angle, the concentration, the molecular weight, and the second virial coefficient indicating the dispersion state of the particles is expressed by the following Rayleigh equation.
- This formula has variables related to concentration and angle as described above, and becomes a proportional formula when the concentration is fixed.
- the values of the angle 0 degree and the concentration 0 indicate the molecular weight, and the plot of these values is called a Zim-Berry plot.
- the point where the concentration is constant and the angle ⁇ is extrapolated to 0 is the reciprocal of the molecular weight
- the slope of the plot represents the root mean square radius of inertia. From this, by taking the inclination of the angle dependency, the size of the electrolytically extracted particles 5, that is, the fine particles in the metal material 4 can be uniquely determined.
- the scattering intensity reflected is higher in proportion to the number density of the electrolytic extraction particles 5 contained therein, it is easy to create a relational expression between the scattering intensity and the number density in advance.
- the number density in the solution can be known.
- the lower limit value of the application size of the FFF device 3 is, for example, 1 nm.
- the separation performance of the regenerated cellulose membrane that separates the electrolytically extracted particles 5 and the solution is close, and the possibility of passing through the regenerated cellulose membrane increases, so that application becomes difficult.
- the composition of the fine particles in the electrolytically extracted particles 5, that is, the fine particles in the metal material 4 can be further analyzed with respect to the solution separated for each size.
- any method such as various mass spectrometry methods, spectroscopic analysis methods, and chemical analysis methods can be applied.
- composition analysis By performing composition analysis on the solution after the particle size measurement, it is possible to clarify which component in the metal material 4 the fine particles having the measured particle size are derived from.
- the size and number density were measured by the fine particle analysis method according to the present embodiment using an FFF apparatus.
- a high-Si steel sample (Si: 3% by mass, Mn: 0.1% by mass, S: 0.03% by mass, Al: 0.03% by mass, N: 0.01% by mass) is 20 mm ⁇ 40 mm ⁇ 0.
- the metal layer was processed by removing the oxide film such as the surface scale by chemical polishing.
- the high Si-based steel samples were sampled from steel materials manufactured under the conditions that the heating temperature in the manufacturing process was a normal temperature (1000 ° C.) and a high temperature (1100 ° C.) higher by about 100 ° C. than normal. Metal sample pieces having different manufacturing conditions were prepared.
- This metal sample piece was electrolyzed by the SPEED method using the particle extraction apparatus in steel shown in FIG.
- the electrolytic solution a 3% by mass methyl salicylate + 1% by mass salicylic acid + 1% by mass TMAC + 0.05% by mass SDS dispersing agent system capable of stably electrolyzing a sulfide system was used.
- the metal sample piece was lightly washed with methanol and left in a beaker containing another clean methanol.
- the electrolytic solution was filtered through a filter, and the obtained filter was placed in the beaker and irradiated with ultrasonic waves for about 1 minute to disperse the fine particles deposited on the surface of the metal sample piece in the methanol solution.
- FIG. 6 shows the result of comparing the time required to measure the size and number density distribution function of the fine particles.
- the conventional method of measuring the number density distribution from the photo determination by microscopic observation requires about 30 days, and the person in charge of the work needs a high level of TEM observation operation ability.
- the time when performed in the above embodiment was about 1 day including the melting work.
- FIG. 7 shows an example of the result of component analysis using a normal ICP (inductively coupled plasma) mass spectrometer for the solution discharged after size and number density measurement after separation for each size by an FFF device. Indicates. The horizontal axis indicates the size of the fine particles. As shown in FIG. 7, it was possible to clearly grasp that the component change of Al, Cu, and Mn occurred at every pitch of about 10 nm. Further, the drain solution for each size obtained here is information on the crystal structure of fine particles extracted for each size, if the solution is dried and then analyzed by a normal X-ray crystal structure analyzer (XRD). Can be obtained.
- XRD normal X-ray crystal structure analyzer
- the number density distribution of fine particles contained in a steel material can be obtained accurately and quickly. Therefore, it is possible to quickly feed back the preferred density and size of fine particles in the production of high quality steel and factory operating conditions. Even when a large-scale production process of new products is implemented or when a normal analysis method requires a great deal of labor and cost, the application of the present invention enables quick and inexpensive material evaluation. Therefore, the present invention has great industrial utility value.
- the present invention has an extremely high industrial value as a measurement technique suitable for, for example, a quality control test for a metal material and an inspection for optimizing the operating conditions of a factory.
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Abstract
Description
Flow Fractionation)法を利用した金属材料中微粒子(析出物及び非金属介在物)の粒度測定方法に関する。
該分離抽出された微粒子を溶媒に分散させて分散液を作製し、フィールドフローフラクショネーション装置を用いて、該分散液を所定のサイズ毎に複数の微粒子分散溶液に分離する工程と、
該所定のサイズ毎に分離された各微粒子分散溶液にレーザ光を照射し、その反射強度の角度依存性から微粒子のサイズの絶対値を計測すると共に、反射強度の強さから個数密度を計測する工程と、
を有することを特徴とする金属材料中微粒子の粒度分布測定方法。
(2) 前記微粒子のサイズが20μm以下であることを特徴とする(1)に記載の金属材料中微粒子の粒度分布測定方法。
(3) 前記溶媒が有機溶媒であることを特徴とする(1)又は(2)に記載の金属材料中微粒子の粒度分布測定方法。
(4) 前記溶媒として界面活性剤を含むものを用いることを特徴とする(1)~(3)のいずれかに記載の金属材料中微粒子の粒度分布測定方法。
(5) 前記微粒子の分離抽出を、非水溶媒系電解法により行うことを特徴とする(1)~(4)のいずれかに記載の金属材料中微粒子の粒度分布測定方法。
(6) 前記非水溶媒系電解法が非水溶媒系定電位電解法であることを特徴とする(5)に記載の金属材料中微粒子の粒度分布測定方法。
(7) 前記非水溶媒系電解法による微粒子の分離抽出を、界面活性剤を含む非水溶媒系電解液を用いて行うことを特徴とする(5)又は(6)に記載の金属材料中微粒子の粒度分布測定方法。
(8) 前記個数密度を計測する工程の後に、更に、前記微粒子の組成分析を行う工程を有することを特徴とする(1)~(7)のいずれかに記載の金属材料中微粒子の粒度分布測定方法。
(9) 前記個数密度を計測する工程の後に、更に、前記微粒子の結晶構造解析を行う工程を有することを特徴とする(1)~(8)に記載の金属材料中微粒子の粒度分布測定方法。
K:光学定数
C:濃度
Ra:溶媒のレイリー比
M:分子量
A2:第二ビリアル係数
P(θ):角度に依存する関数
Claims (9)
- 微粒子抽出手段を用いて、測定対象の金属材料中の微粒子を溶液中で分離抽出する工程と、
該分離抽出された微粒子を溶媒に分散させて分散液を作製し、フィールドフローフラクショネーション装置を用いて、該分散液を所定のサイズ毎に複数の微粒子分散溶液に分離する工程と、
該所定のサイズ毎に分離された各微粒子分散溶液にレーザ光を照射し、その反射強度の角度依存性から微粒子のサイズの絶対値を計測すると共に、反射強度の強さから個数密度を計測する工程と、
を有することを特徴とする金属材料中微粒子の粒度分布測定方法。 - 前記微粒子のサイズが20μm以下であることを特徴とする請求項1に記載の金属材料中微粒子の粒度分布測定方法。
- 前記溶媒が有機溶媒であることを特徴とする請求項1に記載の金属材料中微粒子の粒度分布測定方法。
- 前記溶媒として界面活性剤を含むものを用いることを特徴とする請求項1に記載の金属材料中微粒子の粒度分布測定方法。
- 前記微粒子の分離抽出を、非水溶媒系電解法により行うことを特徴とする請求項1に記載の金属材料中微粒子の粒度分布測定方法。
- 前記非水溶媒系電解法が非水溶媒系定電位電解法であることを特徴とする請求項5に記載の金属材料中微粒子の粒度分布測定方法。
- 前記非水溶媒系電解法による微粒子の分離抽出を、界面活性剤を含む非水溶媒系電解液を用いて行うことを特徴とする請求項5に記載の金属材料中微粒子の粒度分布測定方法。
- 前記個数密度を計測する工程の後に、更に、前記微粒子の組成分析を行う工程を有することを特徴とする請求項1に記載の金属材料中微粒子の粒度分布測定方法。
- 前記個数密度を計測する工程の後に、更に、前記微粒子の結晶構造解析を行う工程を有することを特徴とする請求項1に記載の金属材料中微粒子の粒度分布測定方法。
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KR20100137539A (ko) | 2010-12-30 |
KR101165162B1 (ko) | 2012-07-11 |
EP2270469B1 (en) | 2020-06-03 |
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CN102016543B (zh) | 2013-04-10 |
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US8384897B2 (en) | 2013-02-26 |
US20110019187A1 (en) | 2011-01-27 |
CN102016543A (zh) | 2011-04-13 |
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