JP2009063565A - Image processing method, and method of measuring particle size distribution using the same - Google Patents
Image processing method, and method of measuring particle size distribution using the same Download PDFInfo
- Publication number
- JP2009063565A JP2009063565A JP2008206215A JP2008206215A JP2009063565A JP 2009063565 A JP2009063565 A JP 2009063565A JP 2008206215 A JP2008206215 A JP 2008206215A JP 2008206215 A JP2008206215 A JP 2008206215A JP 2009063565 A JP2009063565 A JP 2009063565A
- Authority
- JP
- Japan
- Prior art keywords
- particle size
- size distribution
- image
- particles
- measurement object
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000002245 particle Substances 0.000 title claims abstract description 185
- 238000000034 method Methods 0.000 title claims abstract description 65
- 238000009826 distribution Methods 0.000 title claims abstract description 55
- 238000003672 processing method Methods 0.000 title claims description 21
- 238000005259 measurement Methods 0.000 claims abstract description 76
- 238000012545 processing Methods 0.000 claims abstract description 39
- 238000003384 imaging method Methods 0.000 claims abstract description 16
- 239000002923 metal particle Substances 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 89
- 239000003054 catalyst Substances 0.000 claims description 79
- 229910052697 platinum Inorganic materials 0.000 claims description 44
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 20
- 239000000126 substance Substances 0.000 claims description 16
- 229910052799 carbon Inorganic materials 0.000 claims description 13
- 230000005540 biological transmission Effects 0.000 claims description 12
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 10
- 229910000510 noble metal Inorganic materials 0.000 claims description 9
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 7
- 239000000446 fuel Substances 0.000 claims description 7
- 229910052707 ruthenium Inorganic materials 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 239000005518 polymer electrolyte Substances 0.000 claims description 6
- 239000012876 carrier material Substances 0.000 claims description 5
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052737 gold Inorganic materials 0.000 claims description 5
- 239000010931 gold Substances 0.000 claims description 5
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- 229910052703 rhodium Inorganic materials 0.000 claims description 5
- 239000010948 rhodium Substances 0.000 claims description 5
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 230000003287 optical effect Effects 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 3
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 3
- 229910002065 alloy metal Inorganic materials 0.000 claims description 2
- 238000000691 measurement method Methods 0.000 abstract description 3
- 230000005484 gravity Effects 0.000 description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000013078 crystal Substances 0.000 description 9
- CFQCIHVMOFOCGH-UHFFFAOYSA-N platinum ruthenium Chemical compound [Ru].[Pt] CFQCIHVMOFOCGH-UHFFFAOYSA-N 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 239000010419 fine particle Substances 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 238000002411 thermogravimetry Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 206010027146 Melanoderma Diseases 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000011246 composite particle Substances 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002116 nanohorn Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000011548 physical evaluation Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Landscapes
- Inert Electrodes (AREA)
- Catalysts (AREA)
Abstract
Description
本発明は、粒度分布測定のための画像処理方法に関するものである。 The present invention relates to an image processing method for measuring a particle size distribution.
例えば、固体高分子形燃料電池において、その触媒粒子の粒度分布を簡易に測定することは、その炭素担持貴金属触媒の性能を予測し、その電池性能をシミュレーションすることにおいて、大変重要である。従来、このような測定を行なうにあたっては、透過型電子顕微鏡などから得られた画像から、触媒粒子を手作業によって抽出し、各粒子の粒子径から粒度分布を測定するなどの手法がとられていた。 For example, in a polymer electrolyte fuel cell, simply measuring the particle size distribution of the catalyst particles is very important in predicting the performance of the carbon-supported noble metal catalyst and simulating the cell performance. Conventionally, in order to perform such a measurement, a method has been employed in which catalyst particles are manually extracted from an image obtained from a transmission electron microscope or the like, and a particle size distribution is measured from the particle diameter of each particle. It was.
しかしながら、上記の方法では触媒粒子を手作業で抽出するため、測定にかかる時間も長く、測定者によって結果が異なる場合もあり、測定粒子の数が２００個程度までが測定の限界であった。 However, in the above method, since the catalyst particles are manually extracted, the time required for the measurement is long, and the result may vary depending on the measurer. The limit of the measurement is about 200 particles.
また、画像処理ソフトを使用して粒度分布測定を行う場合、手作業によって粒子の輪郭を書き込むなどして粒子を抽出し、粒度分布を測定する方法があるが、やはり時間がかかる。さらに、画像処理ソフトが有する２値化などの処理を行い、触媒粒子だけを抽出する方法もあるが、例えば固体高分子形燃料電池では、触媒粒子の担体として用いられている炭素は多結晶であり、グラファイト結晶面に見られる格子縞や、表面状態の違い、表面の凹凸などにより輝度差が生じ、測定対象物でない部分も抽出してしまうという問題がある。 In addition, when performing particle size distribution measurement using image processing software, there is a method of measuring the particle size distribution by extracting the particles by manually writing the outline of the particles, but it still takes time. Furthermore, there is a method of extracting only the catalyst particles by performing processing such as binarization that the image processing software has. For example, in a polymer electrolyte fuel cell, the carbon used as the catalyst particle carrier is polycrystalline. In addition, there is a problem that brightness differences occur due to lattice fringes seen on the graphite crystal plane, surface state differences, surface irregularities, etc., and portions that are not measurement objects are also extracted.
また、特許文献１には、コークス製造過程における炭素の粒度分布を測る方法が開示されている。特許文献１の方法では、測定対象物を撮像装置により撮像し、撮像された原画像にぼかし処理を行う。そして、ぼかし処理をおこなったぼかし画像に２値化処理をすることにより、所定粒径以上の測定対象物の粒径分布を測定する。さらに、撮像された原画像とぼかし画像の差分により形成された差分画像を２値化処理し、前記所定粒径未満の測定対象物の粒径分布を測定する。最後に、これら２種類の粒径測定分布の測定結果に基づいて、全体の粒径分布を測定する。 Patent Document 1 discloses a method for measuring the particle size distribution of carbon in the coke production process. In the method of Patent Document 1, a measurement object is imaged by an imaging device, and blurring processing is performed on the captured original image. And the particle size distribution of the measuring object more than a predetermined particle size is measured by binarizing the blurred image that has been subjected to the blur processing. Further, the difference image formed by the difference between the captured original image and the blurred image is binarized, and the particle size distribution of the measurement object having the particle size smaller than the predetermined particle size is measured. Finally, the entire particle size distribution is measured based on the measurement results of these two types of particle size measurement distributions.
上記特許文献１の方法では、原画とぼかし画像の２枚の画像を必要とし、２値化処理を２度行い、差分処理も必要など、作業工程が多い。また、粒子径によってはぼかし画像により粒子像が消失してしまう場合があり、拡大画像でも数ミリメートルにしかならないナノオーダーの粒子径を有する粒子の粒度分布測定では正確な測定を行うことは困難である。
炭素のような多結晶体上にある、ナノオーダーの金属粒子の粒度分布を正確に測定しようとすれば、まず的確な画像を撮影し、正確に金属粒子を抽出しなければならない。これを従来の方法で行なう場合、相当な労力と時間を必要とする問題がある。さらには、粒子と輝度ムラの区別をつけるのに、ある程度の知識と経験とを要するといった問題もある。 In order to accurately measure the particle size distribution of nano-order metal particles on a polycrystal such as carbon, an accurate image must first be taken and the metal particles must be accurately extracted. When this is done by conventional methods, there is a problem that requires considerable labor and time. Furthermore, there is a problem that it requires a certain amount of knowledge and experience to distinguish between particles and luminance unevenness.
本発明は、上記の問題点に鑑みてなされたものであり、その目的は、画像処理を用いて、多結晶体上にある金属粒子の粒度を簡易かつ正確に求めることができる粒度測定方法を実現することにある。 The present invention has been made in view of the above problems, and its purpose is to provide a particle size measuring method capable of easily and accurately determining the particle size of metal particles on a polycrystalline body using image processing. It is to be realized.
本発明に係る画像処理方法は、上記課題を解決するために、担持体物質上に測定対象物の粒子が分散された被測定物質における、該測定対象物の粒度分布を測定するための画像処理方法において、上記被測定物質を撮像装置で撮影して得られる画像に、フーリエ変換を施し、複数の異なる周波数成分からなる画像信号に置き換える第１の工程と、上記第１の工程によって得られた画像信号から、測定対象物の粒子によって生じる特定周波数の画像信号を選択することによって、上記測定対象物の粒子を抽出する第２の工程と、を備えることを特徴としている。 In order to solve the above problems, an image processing method according to the present invention performs image processing for measuring the particle size distribution of a measurement object in a measurement object in which particles of the measurement object are dispersed on a carrier material. In the method, a first step of performing Fourier transform on an image obtained by photographing the substance to be measured with an imaging device and replacing the image signal with a plurality of different frequency components, and obtained by the first step And a second step of extracting the particles of the measurement object by selecting an image signal of a specific frequency generated by the particles of the measurement object from the image signal.
上記の構成によれば、上記第２の工程において選択される特定周波数は、測定対象物となる粒子によって生じる周波数成分となるように設定する。そして、測定対象物でない部分によって生じる周波数成分は、上記第２の工程によってカットされるようにする。 According to said structure, the specific frequency selected in the said 2nd process is set so that it may become a frequency component produced by the particle | grains used as a measuring object. And the frequency component produced by the part which is not a measuring object is cut by the said 2nd process.
このように、測定対象物となる粒子によって生じる特定の周波数成分のみを選択することにより、撮像画像の中から測定対象物の粒子の抽出が容易に行なえる。すなわち、測定対象物である粒子以外にも、部分的に結晶構造をとる別の粒子が存在するような場合に、測定対象物による周波数成分と、それ以外の粒子による周波数成分との相違に着目し、単純な画像処理で目的の粒子のみを正確に抽出することができる。 In this way, by selecting only a specific frequency component generated by the particles that are the measurement object, the particles of the measurement object can be easily extracted from the captured image. In other words, when there are other particles that have a partial crystal structure in addition to the particles that are the measurement object, pay attention to the difference between the frequency components of the measurement object and the frequency components of the other particles. In addition, only target particles can be accurately extracted by simple image processing.
上記画像処理方法は、上記第２の工程では、バンドパスフィルタ処理によって特定周波数の画像信号を選択する構成とすることが好ましい。 The image processing method is preferably configured to select an image signal having a specific frequency by band-pass filter processing in the second step.
上記画像処理方法はまた、測定対象物の担持状態を計測し、触媒粒子均一度を評価すること構成とすることが好ましい。上記担持状態とは、抽出された測定対象物の各重心間の平均距離を示したものであり、上記触媒粒子均一度とは、重心間の距離の統計的標準偏差を示す。 The image processing method is preferably configured to measure the carrying state of the measurement object and to evaluate the uniformity of the catalyst particles. The supported state indicates an average distance between the centroids of the extracted measurement object, and the catalyst particle uniformity indicates a statistical standard deviation of the distance between the centroids.
また、本発明に係る粒度分布測定方法は、上記画像処理方法を用いて測定対象物の粒度分布を測定することを特徴としている。 The particle size distribution measuring method according to the present invention is characterized in that the particle size distribution of the measurement object is measured using the image processing method.
上記粒度分布測定方法においては、上記担持体物質は、少なくとも被測定物質よりも非晶質成分が多い物質である構成とすることができる。 In the particle size distribution measuring method, the carrier material can be configured to be a material having more amorphous components than the substance to be measured.
上記粒度分布測定方法においては、上記担持体物質は、炭素、酸化ケイ素、酸化アルミニウム、酸化チタン、酸化モリブデン、酸化ジルコニウムのうち、少なくとも１種からなる物質である構成とすることができる。 In the particle size distribution measuring method, the support material may be a material composed of at least one of carbon, silicon oxide, aluminum oxide, titanium oxide, molybdenum oxide, and zirconium oxide.
また、上記粒度分布測定方法においては、上記測定対象物は、鉄、コバルト、モリブデン、ニッケル、チタン、バナジウム、クロム、白金、パラジウム、ロジウム、金、銀、またはルテニウムのうち、少なくとも一種からなる金属粒子、複合金属粒子または合金金属粒子である構成とすることができる。 In the particle size distribution measuring method, the measurement object is a metal composed of at least one of iron, cobalt, molybdenum, nickel, titanium, vanadium, chromium, platinum, palladium, rhodium, gold, silver, or ruthenium. The structure may be particles, composite metal particles, or alloy metal particles.
また、上記粒度分布測定方法においては、上記測定対象物の粒度分布における粒度が、０．１ナノメートルから２０ナノメートルの間にある、または撮像による拡大画像において、０．１ミリメートルから２０ミリメートルの間にある構成とすることができる。 In the particle size distribution measuring method, the particle size in the particle size distribution of the measurement object is between 0.1 nanometer and 20 nanometers, or 0.1 to 20 millimeters in an enlarged image obtained by imaging. An intervening configuration can be adopted.
また、上記粒度分布測定方法においては、上記撮像装置が、透過型電子顕微鏡、走査型電子顕微鏡、光学顕微鏡、またはレーザー式電子顕微鏡である構成とすることができる。 Moreover, in the said particle size distribution measuring method, the said imaging device can be set as the structure which is a transmission electron microscope, a scanning electron microscope, an optical microscope, or a laser type electron microscope.
また、上記粒度分布測定方法においては、上記撮像装置で撮影して得られる画像が、ネガフィルム、ポジ写真、あるいはデジタル画像である構成とすることができる。 Moreover, in the said particle size distribution measuring method, the image obtained by image | photographing with the said imaging device can be set as the structure which is a negative film, a positive photograph, or a digital image.
また、上記粒度分布測定方法においては、上記被測定物質が、固体高分子形燃料電池に使用される炭素担持貴金属触媒である構成とすることができる。 Moreover, in the said particle size distribution measuring method, the said to-be-measured substance can be set as the structure which is a carbon carrying noble metal catalyst used for a polymer electrolyte fuel cell.
また、上記粒度分布測定方法においては、上記炭素担持貴金属触媒が、白金、ロジウム、パラジウム、ルテニウム、および金のうち、少なくとも１種からなる炭素担持複合触媒である構成とすることができる。 In the particle size distribution measuring method, the carbon-supported noble metal catalyst may be a carbon-supported composite catalyst composed of at least one of platinum, rhodium, palladium, ruthenium, and gold.
本発明に係る画像処理方法およびそれを利用した粒度分布測定方法は、以上のように、担持体物質上に測定対象物の粒子が分散された被測定物質における、該測定対象物の粒度分布を測定するための画像処理方法において、上記被測定物質を撮像装置で撮影して得られる画像に、フーリエ変換を施し、複数の異なる周波数成分からなる画像信号に置き換える第１の工程と、上記第１の工程によって得られた画像信号から、測定対象物の粒子によって生じる特定周波数の画像信号を選択することによって、上記測定対象物の粒子を抽出する第２の工程と、を備える構成である。 As described above, the image processing method and the particle size distribution measurement method using the image processing method according to the present invention are the particle size distributions of the measurement object in the measurement object in which the particles of the measurement object are dispersed on the carrier material. In the image processing method for measurement, a first step of performing Fourier transform on an image obtained by photographing the substance to be measured with an imaging device and replacing the image signal with a plurality of different frequency components, and the first step And a second step of extracting particles of the measurement object by selecting an image signal of a specific frequency generated by the particles of the measurement object from the image signal obtained by the process.
それゆえ、上記第２の工程において選択される特定周波数は、測定対象物となる粒子によって生じる周波数成分となり、測定対象物でない部分によって生じる周波数成分は、上記第２の工程によってカットされる。 Therefore, the specific frequency selected in the second step is a frequency component generated by the particles to be measured, and the frequency component generated by a portion that is not the measurement target is cut by the second step.
このように、測定対象物となる粒子によって生じる特定の周波数成分のみを選択することにより、撮像画像の中から測定対象物の粒子の抽出が容易に行なえる。すなわち、測定対象物である粒子以外にも、部分的に結晶構造をとる別の粒子が存在するような場合に、測定対象物による周波数成分と、それ以外の粒子による周波数成分との相違に着目し、単純な画像処理で目的の粒子のみを正確に抽出することができるといった効果を奏する。 In this way, by selecting only a specific frequency component generated by the particles that are the measurement object, the particles of the measurement object can be easily extracted from the captured image. In other words, when there are other particles that have a partial crystal structure in addition to the particles that are the measurement object, pay attention to the difference between the frequency components of the measurement object and the frequency components of the other particles. In addition, there is an effect that only target particles can be accurately extracted by simple image processing.
本発明により、計測が自動化可能なため、評価試験コストが削減でき、また、一度の計測で、結晶粒子径だけでなく、触媒粒子の均一度も評価することができ、電気化学測定、ＭＥＡ作製および電池作製をせずに触媒の活性評価が可能となる。また、規則的な結晶粒子のみを抽出することができるため、目視よりも結晶子径に近い値を算出することができる。 According to the present invention, since the measurement can be automated, the cost of the evaluation test can be reduced, and not only the crystal particle diameter but also the uniformity of the catalyst particles can be evaluated by one measurement. Electrochemical measurement, MEA production Further, the activity of the catalyst can be evaluated without producing a battery. Moreover, since only regular crystal particles can be extracted, a value closer to the crystallite diameter can be calculated than visually.
本発明の一実施形態について図１ないし図３に基づいて説明すると以下の通りである。尚、以下の実施の形態の説明では、固体高分子形燃料電池等で用いられる炭素担持貴金属触媒の金属触媒粒子の粒度分布測定を行なう場合について例示する。但し、以下の実施の形態は一般的な例を示すものであり、本発明はこれに限定されるものではない。 An embodiment of the present invention will be described below with reference to FIGS. In the following description of the embodiments, a case where the particle size distribution measurement of the metal catalyst particles of the carbon-supported noble metal catalyst used in a polymer electrolyte fuel cell or the like is performed is illustrated. However, the following embodiment shows a general example, and the present invention is not limited to this.
本実施の形態にかかる炭素担持貴金属触媒は、担持体として、例えば、ケッチェンブラックＥＣ（ケッチェンブラック・インターナショナル社製）、およびバルカンＸＣ７２（キャボット社製）が好適に使用できる。また、上記担持体は、粒子状でなくてもよく、カーボンナノチューブ、カーボンナノファイバー、カーボンナノホーンでもよい。また、炭素材料以外にも、酸化チタン、酸化ケイ素、酸化モリブデン、酸化アルミニウム、酸化ジルコニウムのような触媒の担体に使用されるセラミック粒子の場合にも、本発明は有効に適用できる。上記担持体物質は、少なくとも被測定物質よりも非晶質成分が多い物質であることが好ましい。 For the carbon-supported noble metal catalyst according to the present embodiment, for example, Ketjen Black EC (manufactured by Ketjen Black International) and Vulcan XC72 (manufactured by Cabot) can be suitably used as the support. The carrier may not be in the form of particles, and may be a carbon nanotube, a carbon nanofiber, or a carbon nanohorn. In addition to the carbon material, the present invention can be effectively applied to ceramic particles used for a catalyst carrier such as titanium oxide, silicon oxide, molybdenum oxide, aluminum oxide, and zirconium oxide. The carrier material is preferably a material having more amorphous components than the substance to be measured.
また、金属触媒粒子としては、白金、または白金ルテニウム触媒が、本発明において好適に使用される。しかしながら、光を透過せず、電子顕微鏡で観察できる大きさの金属粒子であれば使用可能である。金属触媒粒子の材質としては、触媒としてよく使用される、鉄、コバルト、モリブデン、ニッケル、チタン、バナジウム、クロム、白金、パラジウム、ロジウム、金、銀、ルテニウムなどが使用可能であり、これらの金属材料のうち少なくとも一種からなる金属粒子、複合粒子、または合金粒子において、本発明は有効に適用できる。 As the metal catalyst particles, platinum or a platinum ruthenium catalyst is preferably used in the present invention. However, any metal particles that do not transmit light and can be observed with an electron microscope can be used. As the material of the metal catalyst particles, iron, cobalt, molybdenum, nickel, titanium, vanadium, chromium, platinum, palladium, rhodium, gold, silver, ruthenium, etc., which are often used as catalysts, can be used. The present invention can be effectively applied to metal particles, composite particles, or alloy particles made of at least one material.
続いて、本実施の形態にかかる金属触媒粒子の粒度分布測定方法について図１を参照して説明する。ここでは、ある条件において、アルコール還元法で作成した炭素担持白金触媒を用いる。 Next, a method for measuring the particle size distribution of metal catalyst particles according to the present embodiment will be described with reference to FIG. Here, a carbon-supported platinum catalyst prepared by an alcohol reduction method is used under certain conditions.
先ずは、測定対象物で炭素担持白金触媒の拡大像を撮像する（Ｓ１）。ここで、例として、炭素担持白金触媒を、透過型電子顕微鏡（日立製作所製Ｈ９０００）で観察し、７５万倍の拡大像を得た場合の撮像画像を図２に示す。また、撮像装置としては、透過型電子顕微鏡以外に、走査型電子顕微鏡、光学顕微鏡、またはレーザー式電子顕微鏡などが使用可能である。また、上記撮像装置で撮影して得られる画像は、ネガフィルム、ポジ写真、あるいはデジタル画像の何れであってもよい。 First, an enlarged image of the carbon-supported platinum catalyst is taken with the measurement object (S1). Here, as an example, a carbon-supported platinum catalyst is observed with a transmission electron microscope (H9000, manufactured by Hitachi, Ltd.), and an image captured when an enlarged image of 750,000 times is obtained is shown in FIG. In addition to the transmission electron microscope, a scanning electron microscope, an optical microscope, a laser electron microscope, or the like can be used as the imaging device. The image obtained by photographing with the imaging device may be a negative film, a positive photograph, or a digital image.
こうして得られた撮像画像をスキャナで取り込み、これを電子データ化する（Ｓ２）。但し、撮像装置で撮影して得られる画像がデジタル画像である場合は、それをそのまま電子データ画像として用いることができる。得られた電子データ画像は、画像処理装置を用いて解析を行う。画像処理装置として、ここではイメージプロプラス（メディアサイバーテティクス社製）を用いたが、同等の能力を有するものであれば、他のソフトを用いることもできる。例えば、他に使用可能な画像処理装置としては、シオン（シオンコーポレーション社製）、ＮＩＨ Ｉｍａｇｅ（アメリカ国立衛生研究所開発）などが挙げられる。 The captured image thus obtained is captured by a scanner and converted into electronic data (S2). However, when an image obtained by photographing with an imaging device is a digital image, it can be used as it is as an electronic data image. The obtained electronic data image is analyzed using an image processing apparatus. Here, Image Pro Plus (manufactured by Media Cybertechnics) is used as the image processing apparatus, but other software can be used as long as it has the same ability. For example, other usable image processing apparatuses include Zion (manufactured by Zion Corporation), NIH Image (developed by National Institutes of Health), and the like.
電子データ化された画像は、高解像度を有することが望ましく、４００ｄｐｉ以上、より好ましくは８００ｄｐｉ程度の解像度を有することが望ましい。また、解像度は高くなりすぎるとデータ容量が大きくなり、画像処理装置において処理できない（もしくは処理時間がかかりすぎる）場合がある。このため、電子データ化される画像の解像度は、使用される画像処理装置の処理能力を考慮して高解像度とすることが好ましい。現状の画像処理装置の処理能力では、１３００ｄｐｉ以下とすることが好ましい。 The image converted into electronic data preferably has a high resolution, and preferably has a resolution of 400 dpi or more, more preferably about 800 dpi. Further, if the resolution becomes too high, the data capacity increases, and the image processing apparatus may not be able to process (or takes too much processing time). For this reason, it is preferable that the resolution of the image converted into electronic data is set to a high resolution in consideration of the processing capability of the image processing apparatus used. The processing capability of the current image processing apparatus is preferably 1300 dpi or less.
画像処理装置に取り込まれた画像は、８ビットグレースケールに変換された後、バンドパスフィルタ処理が施される（Ｓ３）。この画像処理におけるバンドパスフィルタ処理は、具体的には以下のように行なわれる。すなわち、８ビットグレースケールに変換された画像に対してフーリエ変換を施し、これを複数の異なる周波数成分からなる画像信号に置き換える。そして、置き換えられた画像信号を、バンドパスフィルタに入力し、特定の周波数成分のみを通過させる。 The image captured by the image processing apparatus is converted into 8-bit gray scale, and then subjected to band pass filter processing (S3). Specifically, the band pass filter processing in this image processing is performed as follows. That is, Fourier transform is performed on an image converted to 8-bit gray scale, and this is replaced with an image signal composed of a plurality of different frequency components. Then, the replaced image signal is input to a band pass filter, and only a specific frequency component is passed.
このとき、バンドパスフィルタを通過する周波数成分は、測定対象物となる粒子によって生じる周波数成分となるように、上記バンドパスフィルタのカットオフ周波数を設定する。そして、触媒粒子の担体として用いられている炭素の結晶部分など、測定対象物でない部分によって生じる周波数成分は、上記フィルタ処理によってカットされるようにする。この時、担持体物質が少なくとも被測定物質よりも非晶質成分が多い物質であれば、担持体物質によって生じる周波数成分が測定対象物となる粒子によって生じる周波数成分と大きく異なり、測定対象物となる粒子によって生じる特定の周波数成分を通過させ易くなる。 At this time, the cut-off frequency of the band-pass filter is set so that the frequency component passing through the band-pass filter is a frequency component generated by the particles to be measured. A frequency component generated by a portion that is not an object to be measured, such as a carbon crystal portion used as a carrier for catalyst particles, is cut by the filtering process. At this time, if the carrier substance is a substance having more amorphous components than the substance to be measured, the frequency component generated by the carrier substance is significantly different from the frequency component generated by the particles to be measured. It becomes easy to pass a specific frequency component generated by the particles.
本発明においては、上述のようなバンドパスフィルタ処理によって、測定対象物となる粒子によって生じる特定の周波数成分のみを通過させることにより、撮像画像の中から測定対象物の粒子の抽出が容易に行なえる。すなわち、測定対象物である粒子以外にも、部分的に結晶構造をとる別の粒子が存在するような場合に、測定対象物による周波数成分と、それ以外の粒子による周波数成分との相違に着目し、単純な画像処理で目的の粒子のみを正確に抽出することができる。 In the present invention, by passing only a specific frequency component generated by the particles to be measured by the band-pass filter processing as described above, the particles of the measurement object can be easily extracted from the captured image. The In other words, when there are other particles that have a partial crystal structure in addition to the particles that are the measurement object, pay attention to the difference between the frequency components of the measurement object and the frequency components of the other particles. In addition, only target particles can be accurately extracted by simple image processing.
本実施の形態において、上記フィルタ処理を行う場合のバンドパスフィルタにおける好ましいフィルタサイズの値は、ハイサイズ８０〜１００、ローサイズ５〜１５程度である。ハイサイズが８０より小さい、あるいはローサイズが１５より大きいと、フィルタにより通過する周波数成分が少なくなり、測定対象物を実際より小さく抽出するという不具合が生じる。また、ハイサイズが１００より大きい、あるいはローサイズが５より小さいと、測定対象物以外の像を抽出してしまい、実際より大きい像になったり、担持体の黒色部分を粒子として抽出してしまったりするという不具合が生じる。ハイサイズとは、選択する特定周波数範囲であるフィルタサイズのうち高周波数値を意味し、ローサイズとは低周波数値を意味する。 In the present embodiment, preferable filter size values in the band-pass filter when performing the above filter processing are high size 80-100 and low size 5-15. When the high size is smaller than 80 or the low size is larger than 15, the frequency component passing through the filter is reduced, and there is a problem that the measurement object is extracted smaller than the actual size. If the high size is larger than 100 or the low size is smaller than 5, an image other than the object to be measured is extracted, resulting in an image larger than the actual size, or the black portion of the carrier is extracted as particles. There is a problem that you get stuck. High size means a high-frequency value among filter sizes that are a specific frequency range to be selected, and low size means a low frequency value.
上記バンドパスフィルタ処理が施された後の画像信号に対しては、濃度ムラの有無が判定され（Ｓ４）、濃度ムラがあると判定された場合には上記画像信号に対して平坦化処理が行われる（Ｓ５）。尚、本発明においては、Ｓ４における濃度ムラの判定ステップを省略し、バンドパスフィルタ処理が施された後の画像信号に対して、必ず平坦化処理を行うものであっても良い。濃度ムラは、物体が存在しないバックグラウンド領域で画像の色の変化が見られる、触媒粒子とは無関係な黒色部分、あるいは白色部分が生じている、という点から判定できる。また、想定する触媒粒子の形状と粒子径範囲が設定できる場合は、それから外れたものが抽出された場合、濃度ムラなどが原因であると判定することもできる。 Whether or not there is density unevenness is determined for the image signal that has been subjected to the bandpass filter processing (S4). If it is determined that there is density unevenness, a flattening process is performed on the image signal. Performed (S5). In the present invention, the step of determining density unevenness in S4 may be omitted, and a flattening process may be necessarily performed on the image signal after the band pass filter process is performed. Density unevenness can be determined from the point that a color change of an image is seen in a background area where no object exists, and a black part or a white part unrelated to catalyst particles is generated. In addition, when the assumed shape and particle diameter range of the catalyst particles can be set, it is possible to determine that the cause is density unevenness or the like when an outlier is extracted.
この平坦化処理は、担持体およびバックグラウンドにある濃度ムラを解消するものであり、平坦化フィルタを用いてバックグラウンドの濃度を平均化する。この平坦化フィルタにおけるフィルタ値は、前記バンドパスフィルタ処理時における、ハイサイズとローサイズとの間の値が好ましく、より好ましくはハイサイズの５０％〜９０％程度の値である。９０％より大きいと、測定対象物との区別がつかなくなり、５０％より小さいと、測定対象物が淡色化されてしまい、抽出しにくいという不具合が生じる。 This flattening process eliminates uneven density in the carrier and background, and averages the background density using a flattening filter. The filter value in the flattening filter is preferably a value between the high size and the low size at the time of the bandpass filter processing, and more preferably a value of about 50% to 90% of the high size. If it is larger than 90%, it cannot be distinguished from the object to be measured, and if it is smaller than 50%, the object to be measured is lightened and it is difficult to extract.
上記Ｓ５で平坦化処理が施された画像信号（もしくは、上記Ｓ４で濃度ムラが無いと判定された画像信号）に対し、最後にコントラスト調整（例えば、２値化処理）を行なう（Ｓ６）。これにより、測定対象物を抽出することができる。例として、図２に示す撮像画像から、上記画像処理によって測定対象物である白金触媒粒子を抽出した場合の画像を図３に示す。図３の画像では、図２の撮像画像に比べ、担持体である炭素１の結晶等が解消され、測定対象物である白金触媒粒子２が鮮明に抽出されていることが分かる。 Finally, contrast adjustment (for example, binarization processing) is performed on the image signal subjected to the flattening process in S5 (or the image signal determined to have no density unevenness in S4) (S6). Thereby, a measurement object can be extracted. As an example, FIG. 3 shows an image when platinum catalyst particles as a measurement object are extracted from the captured image shown in FIG. 2 by the image processing. In the image of FIG. 3, it can be seen that, compared with the captured image of FIG. 2, the crystal of carbon 1 as the carrier is eliminated, and the platinum catalyst particles 2 as the measurement object are clearly extracted.
尚、こうした画像処理によって得られた粒度から、平均粒子径、各粒子の重心間距離の平均、および各重心間距離から算出した、統計的標準偏差を求めることができる。これらの数値はエックス線回折装置のような物理的評価による平均粒子径とほぼ近い値となり、触媒性能、担持量とも相関することが確認された。また、本発明の画像処理方法は、ナノ粒子の粒度を正確に求めることができるばかりでなく、固体高分子型燃料電池用触媒においては、その粒度と統計的標準偏差から、電池性能を評価する要素となり得ることがわかった。 The statistical standard deviation calculated from the average particle diameter, the average of the distance between the centroids of each particle, and the distance between the centroids can be obtained from the particle size obtained by such image processing. These numerical values are close to the average particle diameter by physical evaluation as with an X-ray diffractometer, and it was confirmed that they correlate with catalyst performance and loading. In addition, the image processing method of the present invention can accurately determine the particle size of the nanoparticles, and in the case of a polymer electrolyte fuel cell catalyst, the cell performance is evaluated from the particle size and statistical standard deviation. It turns out that it can be an element.
本発明の粒度分布測定方法は、測定対象物の粒度分布における粒度が、０．１ナノメートルから２０ナノメートルの間にある場合、または撮像による拡大画像において、０．１ミリメートルから２０ミリメートルの間にある場合に好適に利用できる。これは、粒度が２０ナノメートルより大きい場合、あるいは拡大画像において２０ミリメートルより大きい場合は、簡易な画像処理で粒度を測定することができるが、これより小さい場合は、従来の方法では測定が難しく、本発明によって測定が可能になるためである。 In the particle size distribution measurement method of the present invention, when the particle size in the particle size distribution of the measurement object is between 0.1 nanometer and 20 nanometers, or in an enlarged image by imaging, between 0.1 millimeters and 20 millimeters Can be suitably used. If the particle size is larger than 20 nanometers or larger than 20 millimeters in the enlarged image, the particle size can be measured by simple image processing, but if it is smaller than this, measurement by the conventional method is difficult. This is because the present invention enables measurement.
〔実施例１〕
ある条件におけるアルコール還元法を用いて、ケッチェンブラックＥＣに白金微粒子を担持した炭素担持白金触媒を作製した。この炭素担持白金触媒に対し、リガク社製エックス線回折装置によって白金のエックス線パターンを測定し、シェラー式により計算された平均粒子径は２．０ナノメートル、リガク社製熱重量分析により測定された担持量は３０重量％であった。
[Example 1]
Using an alcohol reduction method under certain conditions, a carbon-supported platinum catalyst having platinum fine particles supported on ketjen black EC was prepared. For this carbon-supported platinum catalyst, the X-ray pattern of platinum was measured by an X-ray diffractometer manufactured by Rigaku, and the average particle size calculated by the Scherrer equation was 2.0 nanometers, the support measured by thermogravimetric analysis manufactured by Rigaku The amount was 30% by weight.
次に、上記炭素担持白金触媒における粒度分布を本発明の方法で測定すべく、該炭素担持白金触媒を透過型電子顕微鏡で観察し、該担持触媒の７５万倍のモノクロ写真が撮影された。これを、８００ｄｐｉでエプソン社製スキャナに取り込み、電子データに変換した。該画像を、イメージプロプラスにとりこみ、測定エリアを選択した。バンドパスフィルタ処理を行い、ローサイズパラメーターを５、ハイサイズパラメーターを９０とした。平坦化処理はパラメーターを７５とし、さらにコントラスト調整（２値化）を行って、白金粒子を抽出した。 Next, in order to measure the particle size distribution in the carbon-supported platinum catalyst by the method of the present invention, the carbon-supported platinum catalyst was observed with a transmission electron microscope, and a monochrome photograph of 750,000 times the supported catalyst was taken. This was imported into an Epson scanner at 800 dpi and converted into electronic data. The image was loaded into Image Pro Plus and a measurement area was selected. Band pass filtering was performed, with the low size parameter set to 5 and the high size parameter set to 90. In the flattening process, the parameter was set to 75, and contrast adjustment (binarization) was further performed to extract platinum particles.
本発明の画像処理方法によって抽出した粒子３００個について、その粒度を測定し、平均粒子径１．９ナノメートルを算出した。さらに、測定対象物の担持状態として平均重心間距離５．５ナノメートル、触媒粒子均一度として、重心間距離の統計的標準偏差２．１ナノメートルを算出した。この結果は、上述したシェラー式により計算された平均粒子径とほぼ等しく、本発明の方法によって精度の高い計測結果が得られたことが確認された。 The particle size of 300 particles extracted by the image processing method of the present invention was measured, and an average particle size of 1.9 nanometers was calculated. Further, the average distance between the centers of gravity of 5.5 nanometers was calculated as the measurement object carrying state, and the statistical standard deviation of the distance between the centers of gravity of 2.1 nanometers was calculated as the catalyst particle uniformity. This result was almost equal to the average particle diameter calculated by the Scherrer equation described above, and it was confirmed that a highly accurate measurement result was obtained by the method of the present invention.
また、上記炭素担持白金触媒をカソード極、後述する実施例３で作製した炭素担持白金ルテニウム触媒をアノード極として、膜電極接合体（ＭＥＡ）を作製し、エレクトロケム社製標準セルにセットし、アノードに３ｍｏｌ／ｌメタノール水溶液を３００μＬ／ｍｉｎ、カソードに空気を５００ｍＬ／ｍｉｎで供給し、セル温度４０℃にて、電子負荷装置により、電力密度を測定したところ、３０ｍＷ／ｃｍ２を得た。 Further, a membrane electrode assembly (MEA) was prepared using the carbon-supported platinum catalyst as a cathode electrode, and the carbon-supported platinum ruthenium catalyst prepared in Example 3 described later as an anode electrode, and set in a standard cell manufactured by Electrochem, When a 3 mol / l aqueous methanol solution was supplied to the anode at 300 μL / min and air was supplied to the cathode at 500 mL / min, and the power density was measured with an electronic load device at a cell temperature of 40 ° C., 30 mW / cm 2 was obtained.
〔実施例２〕
ある条件におけるアルコール還元法を用いて、ケッチェンブラックＥＣに白金微粒子を担持した炭素担持白金触媒を作製した。この炭素担持白金触媒に対し、エックス線回折装置によって白金のエックス線パターンを測定し、シェラー式により計算された平均粒子径は２．２ナノメートル、熱重量分析により測定された担持量は４２重量％であった。
[Example 2]
Using an alcohol reduction method under certain conditions, a carbon-supported platinum catalyst having platinum fine particles supported on ketjen black EC was prepared. For this carbon-supported platinum catalyst, the X-ray pattern of platinum was measured by an X-ray diffractometer, the average particle diameter calculated by the Scherrer equation was 2.2 nanometers, and the supported amount measured by thermogravimetric analysis was 42% by weight. there were.
次に、上記炭素担持白金触媒における粒度分布を本発明の方法で測定すべく、該炭素担持白金触媒を透過型電子顕微鏡で観察し、該担持触媒の７５万倍のモノクロ写真が撮影された。これを、８００ｄｐｉでスキャナに取り込み、電子データに変換した。該画像を、イメージプロプラスにとりこみ、８ビットグレースケールに変換後、測定エリアを選択した。バンドパスフィルタ処理を行い、ローサイズパラメーターを５、ハイサイズパラメーターを９０とした。平坦化処理は、パラメーターを７５とし、さらにコントラスト調整（２値化）を行って、白金粒子を抽出した。 Next, in order to measure the particle size distribution in the carbon-supported platinum catalyst by the method of the present invention, the carbon-supported platinum catalyst was observed with a transmission electron microscope, and a monochrome photograph of 750,000 times the supported catalyst was taken. This was captured by a scanner at 800 dpi and converted into electronic data. The image was taken into Image Pro Plus and converted to 8-bit gray scale, and then the measurement area was selected. Band pass filtering was performed, with the low size parameter set to 5 and the high size parameter set to 90. In the flattening process, the parameter was set to 75, and contrast adjustment (binarization) was further performed to extract platinum particles.
本発明の画像処理方法によって抽出した抽出した粒子３００個について、粒度を測定し、平均粒子径２．２ナノメートルを算出した。さらに、測定対象物の担持状態として、平均重心間距離４．３ナノメートル、触媒粒子均一度として、重心間距離の統計的標準偏差２．０ナノメートルを算出した。この結果は、上述したシェラー式により計算された平均粒子径とほぼ等しく、本発明の方法によって精度の高い計測結果が得られたことが確認された。 The particle size of 300 extracted particles extracted by the image processing method of the present invention was measured, and an average particle size of 2.2 nanometers was calculated. Further, a mean standard distance between the center of gravity of 4.3 nanometer was calculated as the measurement object support state, and a statistical standard deviation of the center of gravity distance of 2.0 nanometer was calculated as the catalyst particle uniformity. This result was almost equal to the average particle diameter calculated by the Scherrer equation described above, and it was confirmed that a highly accurate measurement result was obtained by the method of the present invention.
また、上記炭素担持白金触媒をカソード極、後述する実施例３で作製した炭素担持白金ルテニウム触媒をアノード極として、膜電極接合体（ＭＥＡ）を作製し、エレクトロケム社製標準セルにセットし、アノードに３ｍｏｌ／ｌメタノール水溶液を３００μＬ／ｍｉｎ、カソードに空気を５００ｍＬ／ｍｉｎで供給し、セル温度４０℃にて、電子負荷装置により、電力密度を測定したところ、３５ｍＷ／ｃｍ２を得た。 Further, a membrane electrode assembly (MEA) was prepared using the carbon-supported platinum catalyst as a cathode electrode, and the carbon-supported platinum ruthenium catalyst prepared in Example 3 described later as an anode electrode, and set in a standard cell manufactured by Electrochem, When a 3 mol / l aqueous methanol solution was supplied to the anode at 300 μL / min and air was supplied to the cathode at 500 mL / min, and the power density was measured with an electronic load device at a cell temperature of 40 ° C., 35 mW / cm 2 was obtained.
〔実施例３〕
ある条件における含浸法を用いて、東京化成工業社製アナターゼ型酸化チタンに、白金微粒子を担持した触媒を作製した。この触媒に対し、エックス線回折装置によって白金のエックス線パターンを測定し、シェラー式により計算された平均粒子径は、６．７ナノメートルであった。担持量は実測していないが、仕込み量は５重量％とした。
Example 3
Using an impregnation method under certain conditions, a catalyst having platinum fine particles supported on anatase-type titanium oxide manufactured by Tokyo Chemical Industry Co., Ltd. was prepared. For this catalyst, the X-ray pattern of platinum was measured by an X-ray diffractometer, and the average particle size calculated by the Scherrer equation was 6.7 nanometers. Although the loading amount was not actually measured, the charging amount was 5% by weight.
次に、上記炭素担持白金触媒における粒度分布を本発明の方法で測定すべく、該触媒を日本電子社製走査型電子顕微鏡で観察し、６００ｄｐｉの電子データを得た。実施例１と同様にバンドパスフィルタ処理、コントラスト調整（２値化）を行った。ただし、バンドパスフィルタ処理のローサイズパラメーターは１０、ハイサイズパラメーターは８５とした。濃度ムラが小さかったため、平坦化処理は行わなかった。 Next, in order to measure the particle size distribution in the carbon-supported platinum catalyst by the method of the present invention, the catalyst was observed with a scanning electron microscope manufactured by JEOL Ltd., and 600 dpi electronic data was obtained. In the same manner as in Example 1, bandpass filter processing and contrast adjustment (binarization) were performed. However, the low size parameter of the bandpass filter processing was 10 and the high size parameter was 85. Since the density unevenness was small, the flattening process was not performed.
本発明の画像処理方法によって抽出した抽出した粒子３００個について、粒度を測定し、平均粒子径６．６ナノメートルを算出した。さらに、測定対象物の担持状態として、平均重心間距離２６．５ナノメートル、触媒粒子均一度として、重心間距離の統計的標準偏差２．５ナノメートルを得た。この結果は、上述したシェラー式により計算された平均粒子径とほぼ等しく、本発明の方法によって精度の高い計測結果が得られたことが確認された。 The particle size of 300 extracted particles extracted by the image processing method of the present invention was measured, and an average particle size of 6.6 nanometers was calculated. Furthermore, a mean distance between the centers of gravity of 26.5 nanometers was obtained as the loading state of the measurement object, and a statistical standard deviation of the distance between the centers of gravity of 2.5 nanometers was obtained as the catalyst particle uniformity. This result was almost equal to the average particle diameter calculated by the Scherrer equation described above, and it was confirmed that a highly accurate measurement result was obtained by the method of the present invention.
〔実施例４〕
ある条件におけるアルコール同時還元法を用いて、ケッチェンブラックＥＣに、白金およびルテニウムを担持し、炭素担持白金ルテニウム触媒を作製した。この炭素担持白金ルテニウム触媒に対し、エックス線回折装置を用いて白金ルテニウムのエックス線回折パターンを測定し、シェラー式によって計算された平均粒子径は３．７ナノメートルであった。熱重量分析装置によって測定された担持量は、３０重量％であった。リガク社製蛍光エックス線分析装置によって測定された白金とルテニウムの組成比はモル比１：１であった。
Example 4
Using a simultaneous alcohol reduction method under certain conditions, platinum and ruthenium were supported on Ketjen Black EC to prepare a carbon-supported platinum ruthenium catalyst. For this carbon-supported platinum ruthenium catalyst, an X-ray diffraction pattern of platinum ruthenium was measured using an X-ray diffractometer, and the average particle size calculated by the Scherrer equation was 3.7 nanometers. The supported amount measured by a thermogravimetric analyzer was 30% by weight. The composition ratio of platinum and ruthenium measured by a Rigaku fluorescent X-ray analyzer was a molar ratio of 1: 1.
次に、上記炭素担持白金ルテニウム触媒における粒度分布を本発明の方法で測定すべく、該炭素担持白金ルテニウム触媒を、透過型電子顕微鏡で観察し、該担持触媒の７５万倍のモノクロ写真が撮影された。これを、８００ｄｐｉでスキャナに取り込み、電子データに変換した。該画像を、イメージプロプラスにとりこみ、測定エリアを選択した。バンドパスフィルタ処理を行い、実施例１と同様に、ローサイズパラメーターを５、ハイサイズパラメーターを９０とした。平坦化処理は、パラメーターを７５とし、さらにコントラスト調整（２値化）を行って、白金粒子を抽出した。 Next, in order to measure the particle size distribution in the carbon-supported platinum ruthenium catalyst by the method of the present invention, the carbon-supported platinum ruthenium catalyst was observed with a transmission electron microscope, and a monochrome photograph of 750,000 times the supported catalyst was taken. It was done. This was captured by a scanner at 800 dpi and converted into electronic data. The image was loaded into Image Pro Plus and a measurement area was selected. Band-pass filter processing was performed, and the low size parameter was set to 5 and the high size parameter was set to 90, as in Example 1. In the flattening process, the parameter was set to 75, and contrast adjustment (binarization) was further performed to extract platinum particles.
本発明の画像処理方法によって抽出した粒子３００個について、粒度を測定し、平均粒子径３．５ナノメートルを算出した。さらに、測定対象物の担持状態として、平均重心間距離６．６ナノメートル、触媒粒子均一度として、重心間距離の統計的標準偏差２．１ナノメートルを算出した。この結果は、上述したシェラー式により計算された平均粒子径とほぼ等しく、本発明の方法によって精度の高い計測結果が得られたことが確認された。 The particle size of 300 particles extracted by the image processing method of the present invention was measured, and an average particle size of 3.5 nanometers was calculated. Furthermore, a statistical standard deviation of 2.1 nanometers between the center of gravity was calculated as an average distance between the center of gravity of 6.6 nanometers as the carrying state of the measurement object, and a catalyst particle uniformity. This result was almost equal to the average particle diameter calculated by the Scherrer equation described above, and it was confirmed that a highly accurate measurement result was obtained by the method of the present invention.
性能試験は、実施例１に準ずる。 The performance test is in accordance with Example 1.
〔実施例５〕
ある条件におけるアルコール還元法のうち、還元温度保持時間（（ａ）１５分、（ｂ）３０分、（ｃ）６０分）を変化させた条件を用いて、ケッチェンブラックＥＣに白金微粒子を担持した炭素担持白金触媒を、３種作製した。この炭素担持白金触媒に対し、リガク社製エックス線回折装置によって白金のエックス線パターンを測定し、シェラー式により計算された平均粒子径は（ａ）１．９、（ｂ）１．９、（ｃ）２．２ナノメートル、リガク社製熱重量分析により測定された担持量は（ａ）２２、（ｂ）２５、（ｃ）３３重量％であった。
Example 5
Of the alcohol reduction method under certain conditions, platinum fine particles are supported on ketjen black EC using conditions where the reduction temperature holding time ((a) 15 minutes, (b) 30 minutes, (c) 60 minutes) is changed. Three types of carbon-supported platinum catalysts were prepared. For this carbon-supported platinum catalyst, the X-ray pattern of platinum was measured with an X-ray diffractometer manufactured by Rigaku Corporation, and the average particle sizes calculated by the Scherrer equation were (a) 1.9, (b) 1.9, (c). The loadings measured by thermogravimetric analysis at 2.2 nm and Rigaku Corporation were (a) 22, (b) 25, and (c) 33% by weight.
次に、上記炭素担持白金触媒における粒度分布を本発明の方法で測定すべく、該炭素担持白金触媒を透過型電子顕微鏡で観察し、該担持触媒の７５万倍のモノクロ写真が撮影された。これを、８００ｄｐｉでエプソン社製スキャナに取り込み、電子データに変換した。該画像を、イメージプロプラスにとりこみ、測定エリアを選択した。バンドパスフィルタ処理を行い、ローサイズパラメーターを５、ハイサイズパラメーターを９０とした。平坦化処理はパラメーターを７５とし、さらにコントラスト調整（２値化）を行って、白金粒子を抽出した。 Next, in order to measure the particle size distribution in the carbon-supported platinum catalyst by the method of the present invention, the carbon-supported platinum catalyst was observed with a transmission electron microscope, and a monochrome photograph of 750,000 times the supported catalyst was taken. This was imported into an Epson scanner at 800 dpi and converted into electronic data. The image was loaded into Image Pro Plus and a measurement area was selected. Band pass filtering was performed, with the low size parameter set to 5 and the high size parameter set to 90. In the flattening process, the parameter was set to 75, and contrast adjustment (binarization) was further performed to extract platinum particles.
本発明の画像処理方法によって抽出した粒子３００個について、その粒度を測定し、平均粒子径（ａ）１．９、（ｂ）１．９、（ｃ）２．０ナノメートルを算出した。さらに、測定対象物の担持状態として、平均重心間距離（ａ）５．２、（ｂ）５．３、（ｃ）５．６ナノメートル、触媒粒子均一度として、重心間距離の統計的標準偏差（ａ）０．６、（ｂ）０．６、（ｃ）０．７ナノメートルを算出した。この結果は、上述したシェラー式により計算された平均粒子径とほぼ等しく、本発明の方法によって精度の高い計測結果が得られたことが確認された。 The particle size of 300 particles extracted by the image processing method of the present invention was measured, and the average particle size (a) 1.9, (b) 1.9, and (c) 2.0 nanometers were calculated. In addition, the average object distance between the centers of gravity (a) 5.2, (b) 5.3, (c) 5.6 nanometers as the carrying state of the measurement object, and the catalyst particle uniformity as a statistical standard for the distance between the centers of gravity Deviations (a) 0.6, (b) 0.6, and (c) 0.7 nanometers were calculated. This result was almost equal to the average particle diameter calculated by the Scherrer equation described above, and it was confirmed that a highly accurate measurement result was obtained by the method of the present invention.
また、上記炭素担持白金触媒をカソード極、前述した実施例３で作製した炭素担持白金ルテニウム触媒をアノード極として、膜電極接合体（ＭＥＡ）を作製し、エレクトロケム社製標準セルにセットし、アノードに３ｍｏｌ／ｌメタノール水溶液を３００μＬ／ｍｉｎ、カソードに空気を５００ｍＬ／ｍｉｎで供給し、セル温度４０℃にて、電子負荷装置により、電力密度を測定したところ、（ａ）２９、（ｂ）２７、（ｃ）２５ｍＷ／ｃｍ２を得た。 Further, using the carbon-supported platinum catalyst as a cathode electrode and the carbon-supported platinum ruthenium catalyst prepared in Example 3 as described above as an anode electrode, a membrane electrode assembly (MEA) was prepared, and set in a standard cell manufactured by Electrochem, When a 3 mol / l methanol aqueous solution was supplied to the anode at 300 μL / min and air was supplied to the cathode at 500 mL / min, and the power density was measured with an electronic load device at a cell temperature of 40 ° C., (a) 29, (b) 27, (c) 25 mW / cm 2 was obtained.
本発明の重心間距離の標準偏差を算出する粒度分布測定法によって、触媒の活性と相関のあるデータを得ることができた。 Data correlating with the activity of the catalyst could be obtained by the particle size distribution measuring method for calculating the standard deviation of the distance between the centers of gravity of the present invention.
〔比較例１〕
実施例１で得た透過型電子顕微鏡画像を、イメージプロプラスにとりこみ、バンドパスフィルタ処理を行わずに平坦化とコントラスト調整（２値化）を行ったが、炭素の格子縞も抽出してしまい、白金粒子は正しく抽出できなかった。
[Comparative Example 1]
The transmission electron microscope image obtained in Example 1 was incorporated into Image Pro Plus and flattening and contrast adjustment (binarization) were performed without performing bandpass filtering, but carbon lattice fringes were also extracted. The platinum particles could not be extracted correctly.
〔比較例２〕
実施例１で得た透過型電子顕微鏡画像を、２００個抽出し、ノギスによる粒子径の計測を行った。平均粒子径は１．７ｎｍとなり、Ｘ線回折による計測より小さい値となった。これは、目視による計測では炭素の凹凸による黒点をＰｔ粒子とみなしてしまい、抽出してしまうためである。
[Comparative Example 2]
200 transmission electron microscope images obtained in Example 1 were extracted, and the particle diameter was measured with calipers. The average particle size was 1.7 nm, which was smaller than that measured by X-ray diffraction. This is because the black spot due to the unevenness of carbon is regarded as Pt particles in visual measurement and extracted.
測定対象物である粒子以外にも、部分的に結晶構造をとる別の粒子が存在するような場合に、単純な画像処理で目的の粒子のみを正確に抽出することができ、固体高分子形燃料電池等で用いられる炭素担持貴金属触媒の金属触媒粒子の粒度分布測定などの用途に好適に使用できる。 If there are other particles that have a partial crystal structure in addition to the particles to be measured, only the target particles can be accurately extracted with simple image processing. It can be suitably used for applications such as particle size distribution measurement of metal catalyst particles of a carbon-supported noble metal catalyst used in a fuel cell or the like.
また、ＭＥＡや電池を作製せずに、その触媒粒子の形状、および担持状態から触媒活性を割り出すことができるため、上記炭素担持貴金属触媒の評価に好適に使用できる。 Further, since the catalytic activity can be determined from the shape and supported state of the catalyst particles without producing an MEA or battery, it can be suitably used for the evaluation of the carbon-supported noble metal catalyst.
１ 炭素（担持体物質）
２ 白金触媒粒子（測定対象物）
1 Carbon (support material)
2 Platinum catalyst particles (measurement object)
Claims (12)
上記被測定物質を撮像装置で撮影して得られる画像に、フーリエ変換を施し、複数の異なる周波数成分からなる画像信号に置き換える第１の工程と、
上記第１の工程によって得られた画像信号から、測定対象物の粒子によって生じる特定周波数の画像信号を選択することによって、上記測定対象物の粒子を抽出する第２の工程と、を備えることを特徴とする画像処理方法。 In an image processing method for measuring a particle size distribution of a measurement object in a measurement object in which particles of the measurement object are dispersed on a support material,
A first step of performing Fourier transform on an image obtained by imaging the substance to be measured with an imaging device and replacing the image signal with a plurality of different frequency components;
A second step of extracting particles of the measurement object by selecting an image signal of a specific frequency generated by the particles of the measurement object from the image signal obtained by the first step. A featured image processing method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008206215A JP5058913B2 (en) | 2007-08-09 | 2008-08-08 | Image processing method and particle size distribution measuring method using the same |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007208652 | 2007-08-09 | ||
| JP2007208652 | 2007-08-09 | ||
| JP2008206215A JP5058913B2 (en) | 2007-08-09 | 2008-08-08 | Image processing method and particle size distribution measuring method using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2009063565A true JP2009063565A (en) | 2009-03-26 |
| JP5058913B2 JP5058913B2 (en) | 2012-10-24 |
Family
ID=40558246
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2008206215A Expired - Fee Related JP5058913B2 (en) | 2007-08-09 | 2008-08-08 | Image processing method and particle size distribution measuring method using the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5058913B2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010236989A (en) * | 2009-03-31 | 2010-10-21 | Toyota Motor Corp | Method of creating particle size distribution model, method of predicting degradation of fuel cell catalyst using the method of creating particle size distribution model, and method of controlling fuel cell using the method of predicting degradation of fuel cell catalyst |
| WO2016121812A1 (en) * | 2015-01-28 | 2016-08-04 | 京セラ株式会社 | Suction nozzle |
| KR101767564B1 (en) * | 2015-11-12 | 2017-08-11 | 성균관대학교산학협력단 | A method of analysing images of rod-like particles |
| KR101923034B1 (en) | 2016-12-22 | 2018-11-29 | 성균관대학교산학협력단 | Particle arrangement acquiring method and particle arrangement acquiring device |
| KR20200112308A (en) * | 2019-03-21 | 2020-10-05 | 이화여자대학교 산학협력단 | Method for Cancer Cell Detection using Microvibration |
| US11619575B2 (en) | 2019-03-21 | 2023-04-04 | EWHA University—Industry Collaboration Foundation | Method of detecting cancer cells using micro-vibration |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102301536B1 (en) | 2015-03-10 | 2021-09-14 | 삼성전자주식회사 | Grain Analyzing Method and System using HRTEM Image |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02264845A (en) * | 1989-04-05 | 1990-10-29 | Nkk Corp | Method for measuring mean particle size of particulate material and method for automatic control of particle size |
| JP2003083868A (en) * | 2001-09-11 | 2003-03-19 | Nkk Corp | Measuring method of particle size distribution |
| JP2003197205A (en) * | 2001-12-26 | 2003-07-11 | Asahi Glass Co Ltd | Manufacturing method of solid high polymer fuel cell, and manufacturing method of gas diffusion electrode for it |
| JP2006126061A (en) * | 2004-10-29 | 2006-05-18 | Jfe Steel Kk | Method and device for measuring particle size distribution of powder and grain |
-
2008
- 2008-08-08 JP JP2008206215A patent/JP5058913B2/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02264845A (en) * | 1989-04-05 | 1990-10-29 | Nkk Corp | Method for measuring mean particle size of particulate material and method for automatic control of particle size |
| JP2003083868A (en) * | 2001-09-11 | 2003-03-19 | Nkk Corp | Measuring method of particle size distribution |
| JP2003197205A (en) * | 2001-12-26 | 2003-07-11 | Asahi Glass Co Ltd | Manufacturing method of solid high polymer fuel cell, and manufacturing method of gas diffusion electrode for it |
| JP2006126061A (en) * | 2004-10-29 | 2006-05-18 | Jfe Steel Kk | Method and device for measuring particle size distribution of powder and grain |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010236989A (en) * | 2009-03-31 | 2010-10-21 | Toyota Motor Corp | Method of creating particle size distribution model, method of predicting degradation of fuel cell catalyst using the method of creating particle size distribution model, and method of controlling fuel cell using the method of predicting degradation of fuel cell catalyst |
| US8660827B2 (en) | 2009-03-31 | 2014-02-25 | Toyota Jidosha Kabushiki Kaisha | Method of creating particle size distribution model, method of predicting degradation of fuel cell catalyst using the method of creating particle size distribution model, and method of controlling fuel cell using the method of predicting degradation of fuel cell catalyst |
| US8843355B2 (en) | 2009-03-31 | 2014-09-23 | Toyota Jidosha Kabushiki Kaisha | Method of controlling fuel cell using the method of predicting degradation of fuel cell catalyst |
| US9002689B2 (en) | 2009-03-31 | 2015-04-07 | Toyota Jidosha Kabushiki Kaisha | Method of predicting degradation of fuel cell catalyst using the method of creating particle size distribution model |
| JPWO2016121812A1 (en) * | 2015-01-28 | 2017-12-07 | 京セラ株式会社 | Suction nozzle |
| WO2016121812A1 (en) * | 2015-01-28 | 2016-08-04 | 京セラ株式会社 | Suction nozzle |
| US10099386B2 (en) | 2015-01-28 | 2018-10-16 | Kyocera Corporation | Suction nozzle |
| KR101767564B1 (en) * | 2015-11-12 | 2017-08-11 | 성균관대학교산학협력단 | A method of analysing images of rod-like particles |
| US10269106B2 (en) | 2015-11-12 | 2019-04-23 | Research & Business Foundation Sungkyunkwan University | Method of analysing images of rod-like particles |
| KR101923034B1 (en) | 2016-12-22 | 2018-11-29 | 성균관대학교산학협력단 | Particle arrangement acquiring method and particle arrangement acquiring device |
| KR20200112308A (en) * | 2019-03-21 | 2020-10-05 | 이화여자대학교 산학협력단 | Method for Cancer Cell Detection using Microvibration |
| KR102218746B1 (en) | 2019-03-21 | 2021-02-19 | 이화여자대학교 산학협력단 | Method for Cancer Cell Detection using Microvibration |
| US11619575B2 (en) | 2019-03-21 | 2023-04-04 | EWHA University—Industry Collaboration Foundation | Method of detecting cancer cells using micro-vibration |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5058913B2 (en) | 2012-10-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5058913B2 (en) | Image processing method and particle size distribution measuring method using the same | |
| Sneed et al. | 3D analysis of fuel cell electrocatalyst degradation on alternate carbon supports | |
| Huang et al. | Experimental Sabatier plot for predictive design of active and stable Pt-alloy oxygen reduction reaction catalysts | |
| Padgett et al. | Mitigation of PEM fuel cell catalyst degradation with porous carbon supports | |
| Dubau et al. | Probing the structure, the composition and the ORR activity of Pt3Co/C nanocrystallites during a 3422 h PEMFC ageing test | |
| Meier et al. | Design criteria for stable Pt/C fuel cell catalysts | |
| Chang et al. | Synthesis of highly dispersed Pt nanoclusters anchored graphene composites and their application for non-enzymatic glucose sensing | |
| JP2017183242A (en) | PdRu ALLOY ELECTRODE MATERIAL AND PRODUCTION METHOD THEREOF | |
| Meier et al. | Degradation mechanisms of Pt/C fuel cell catalysts under simulated start–stop conditions | |
| Han et al. | Balancing the galvanic replacement and reduction kinetics for the general formation of bimetallic CuM (M= Ru, Rh, Pd, Os, Ir, and Pt) hollow nanostructures | |
| Hung et al. | Corrosion of carbon support for PEM fuel cells by electrochemical quartz crystal microbalance | |
| Nikkuni et al. | Identical-location transmission electron microscopy study of Pt/C and Pt–Co/C nanostructured electrocatalyst aging: effects of morphological and compositional changes on the oxygen reduction reaction activity | |
| Zhang et al. | A review of electrocatalyst characterization by transmission electron microscopy | |
| Ahluwalia et al. | Durability of de-alloyed platinum-nickel cathode catalyst in low platinum loading membrane-electrode assemblies subjected to accelerated stress tests | |
| Yi et al. | High Performance Pd, PdNi, PdSn and PdSnNi Nanocatalysts Supported on Carbon Nanotubes for Electrooxidation of C2 C4 Alcohols | |
| Peng et al. | New approach for rapidly determining Pt accessibility of Pt/C fuel cell catalysts | |
| Martens et al. | Decoupling catalyst aggregation, ripening, and coalescence processes inside operating fuel cells | |
| Gontard et al. | Three‐dimensional shapes and spatial distributions of Pt and PtCr catalyst nanoparticles on carbon black | |
| JP2014081362A (en) | Evaluation method of electrode and evaluation device | |
| Tomboc et al. | Defect-induced electronic modification and surface reconstruction of catalysts during water oxidation process | |
| WO2020215600A1 (en) | Trace phosphate and ph-combined detector and method therefor | |
| JP2015077580A (en) | Carbon-carried catalyst | |
| Schröder et al. | Tracking the catalyst layer depth-dependent electrochemical degradation of a bimodal Pt/C fuel cell catalyst: a combined Operando small-and wide-angle x-ray scattering study | |
| Tetteh et al. | Calibrating SECCM measurements by means of a nanoelectrode ruler. The intrinsic oxygen reduction activity of PtNi catalyst nanoparticles | |
| Cai et al. | The electrochemical oxidation of sulphite on gold electrodes |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20100826 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20120126 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20120214 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20120703 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20120801 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20150810 Year of fee payment: 3 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| LAPS | Cancellation because of no payment of annual fees |