JP5767477B2 - How to observe rubber materials - Google Patents
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本発明は、ゴム材料の観察方法に関し、詳しくはゴム材料中の充填剤の分散状態を観察する観察方法に関する。 The present invention relates to an observation method for a rubber material, and more particularly to an observation method for observing a dispersion state of a filler in a rubber material.
従来から、カーボンブラックやシリカなどの充填剤を配合したゴム材料が補強性などの点からタイヤなどに使用されている。ゴム材料中の充填剤の分散性はゴム強度などに大きく影響するため、充填剤の分散状態を正確に観察できる方法の確立が望まれている。 Conventionally, rubber materials containing fillers such as carbon black and silica have been used for tires and the like in terms of reinforcement. Since the dispersibility of the filler in the rubber material greatly affects the rubber strength and the like, establishment of a method capable of accurately observing the dispersion state of the filler is desired.
ゴム材料中の充填剤を観察する方法として、３次元透過型電子顕微鏡（３Ｄ−ＴＥＭ）を用いた方法が一般的に知られている。これは、観察するサンプルに対して電子線を照射し、透過した電子を結像して観察する顕微鏡（ＴＥＭ）とＣＴ法を組み合わせた方法である。しかしながら、３Ｄ−ＴＥＭでは、サンプルの厚さが２００ｎｍ以上であると、電子線が透過せず鮮明な像が得られないため、充填剤の分散性を観察する方法として満足できるものではない。 As a method for observing a filler in a rubber material, a method using a three-dimensional transmission electron microscope (3D-TEM) is generally known. This is a method in which a CT (TEM) is combined with a microscope (TEM) that irradiates a sample to be observed with an electron beam, forms an image of the transmitted electrons, and observes them. However, in 3D-TEM, if the thickness of the sample is 200 nm or more, an electron beam does not pass through and a clear image cannot be obtained.
また、特許文献１には、透過型電子顕微鏡を用いてゴム材料中のカーボンブラックの分散状態を観察することが記載されているが、未だ満足できる方法ではなく、３次元構造中での分散状態を観察することについても検討されていない。 Further, Patent Document 1 describes observing the dispersion state of carbon black in a rubber material using a transmission electron microscope, but this is not a satisfactory method, and the dispersion state in a three-dimensional structure is not yet satisfactory. It has not been studied to observe.
本発明は、前記課題を解決し、厚さ２００ｎｍ以上のゴム材料でも充填剤の分散状態を詳細に観察できるゴム材料の観察方法を提供することを目的とする。 An object of the present invention is to solve the above-mentioned problems and to provide a method for observing a rubber material that enables detailed observation of a dispersion state of a filler even with a rubber material having a thickness of 200 nm or more.
本発明は、充填剤を含有するゴム材料の観察方法であって、走査透過電子顕微鏡を用いて取得した該ゴム材料の各回転角度における画像からトモグラフィー法により３次元構造を再構築し、ゴム材料中の充填剤の分散状態を観察することを特徴とするゴム材料の観察方法に関する。 The present invention relates to a method for observing a rubber material containing a filler, wherein a three-dimensional structure is reconstructed by a tomography method from images at each rotation angle of the rubber material obtained using a scanning transmission electron microscope, and the rubber material The present invention relates to a method for observing a rubber material, which is characterized by observing the dispersion state of the filler therein.
上記観察方法において、上記ゴム材料の厚さは２００〜１５００ｎｍであることが好ましい。また、上記ゴム材料と検出器との距離は５〜２００ｃｍであることが好ましい。 In the observation method, the rubber material preferably has a thickness of 200 to 1500 nm. The distance between the rubber material and the detector is preferably 5 to 200 cm.
本発明によれば、充填剤を含有するゴム材料の観察方法であって、走査透過電子顕微鏡を用いて取得した該ゴム材料の各回転角度における画像からトモグラフィー法により３次元構造を再構築し、ゴム材料中の充填剤の分散状態を観察することを特徴とするゴム材料の観察方法であるので、厚さ２００ｎｍ以上のゴム材料でもサンプル内の充填剤の分散状態を正確に観察できる。 According to the present invention, a rubber material observation method containing a filler, reconstructing a three-dimensional structure by a tomography method from an image at each rotation angle of the rubber material obtained using a scanning transmission electron microscope, Since the rubber material observation method is characterized by observing the dispersion state of the filler in the rubber material, the dispersion state of the filler in the sample can be accurately observed even with a rubber material having a thickness of 200 nm or more.
本発明の充填剤を含有するゴム材料の観察方法は、走査透過電子顕微鏡（ＳＴＥＭ）を用いて取得した該ゴム材料の各回転角度における画像からトモグラフィー法により３次元構造を再構築し、ゴム材料中の充填剤の分散状態を観察する方法である。ＳＴＥＭを用いてＴＥＭよりも電子線を集束することにより、電子線が照射された箇所の焦点を合わせることが可能な距離をサンプルの厚さ方向に深くできる。そのため、厚み２００ｎｍ以上のゴム材料であっても電子線を走査し、サンプルの種々の測定角度において、それぞれ鮮明な電子線透過像を得ることができる。従って、得られた各電子線透過像をトモグラフィー法により再構築して３次元構造を示す立体画像を取得でき、ゴム材料中の充填剤の分散状態を正確に観察できる。 The method for observing a rubber material containing the filler according to the present invention comprises reconstructing a three-dimensional structure by a tomography method from images at each rotation angle of the rubber material obtained using a scanning transmission electron microscope (STEM). This is a method of observing the dispersion state of the filler inside. By focusing the electron beam using the STEM rather than the TEM, the distance at which the electron beam is irradiated can be made deeper in the thickness direction of the sample. Therefore, even a rubber material having a thickness of 200 nm or more can scan an electron beam and obtain clear electron beam transmission images at various measurement angles of the sample. Therefore, each obtained electron beam transmission image can be reconstructed by the tomography method to obtain a three-dimensional image showing a three-dimensional structure, and the dispersion state of the filler in the rubber material can be accurately observed.
本発明では、公知の特開２００８−６６０５７号公報に記載の走査透過電子顕微鏡を使用でき、例えば、図１で示した走査透過電子顕微鏡装置１００を使用できる。 In the present invention, a scanning transmission electron microscope described in JP-A-2008-66057 can be used, and for example, the scanning transmission electron microscope apparatus 100 shown in FIG. 1 can be used.
図１では、電子銃１、該電子銃１から放出された一次電子線２、該一次電子線２を試料５上に集束させるための集束レンズ３、試料５上をＸ方向、Ｙ方向に走査するためのＸ方向走査コイル４Ｘ、Ｙ方向走査コイル４Ｙを示している。試料５を固定する試料ホルダー６は、中央部に電子線光軸Ｏに沿って、試料５を透過した電子（透過電子７）が通過する孔（電子線通過孔８）が設けられている。 In FIG. 1, an electron gun 1, a primary electron beam 2 emitted from the electron gun 1, a focusing lens 3 for focusing the primary electron beam 2 on a sample 5, and scanning on the sample 5 in the X and Y directions. The X direction scanning coil 4X and the Y direction scanning coil 4Y are shown. The sample holder 6 for fixing the sample 5 is provided with a hole (electron beam passage hole 8) through which electrons (transmission electrons 7) transmitted through the sample 5 pass along the electron beam optical axis O in the center.
試料ステージ９には、試料ホルダー６が装着され、中央部に電子線光軸Ｏに沿って、電子線通過孔８に連続する電子線通過孔１０が設けられている。また、透過電子７の通過を制限する散乱角制限絞り１１が設けられ、該散乱角制限絞り１１を通過した透過電子１２が示されている。更に、透過電子１２を光に変換するシンチレーター１３及び該変換された光を電子信号に変換する光電子増倍管１４が設けられ、透過電子検出手段を構成する。なお、試料ステージ９、散乱角制限絞り１１、シンチレーター１３、光電子増倍管１４は走査透過電子顕微鏡装置本体の試料室（図示せず）内に配置され、試料ホルダー６は試料ステージ９に対し着脱可能である。 A sample holder 6 is mounted on the sample stage 9, and an electron beam passage hole 10 that is continuous with the electron beam passage hole 8 is provided along the electron beam optical axis O at the center. Further, a scattering angle limiting stop 11 that restricts the passage of the transmitted electrons 7 is provided, and the transmitted electrons 12 that have passed through the scattering angle limiting stop 11 are shown. Further, a scintillator 13 that converts the transmitted electrons 12 into light and a photomultiplier tube 14 that converts the converted light into an electronic signal are provided, and constitutes a transmitted electron detection means. The sample stage 9, the scattering angle limiting aperture 11, the scintillator 13, and the photomultiplier tube 14 are arranged in a sample chamber (not shown) of the scanning transmission electron microscope apparatus body, and the sample holder 6 is attached to and detached from the sample stage 9. Is possible.
上記構成の走査透過電子顕微鏡装置は以下のように動作する。
先ず、オペレーターは、試料５が固定されている試料ホルダー６を試料ステージ９上に装着する。電子銃１から放出された一次電子線２は、加速手段（図示せず）で加速され、集束レンズ３によって集束され、Ｘ方向、Ｙ方向走査コイル４Ｘ、４Ｙによって試料５上を走査する。このような電子線２による試料５上の走査により、試料５中で散乱し、又は散乱することなく試料５を透過した電子７が試料５の下面から出射する。
The scanning transmission electron microscope apparatus having the above configuration operates as follows.
First, the operator mounts the sample holder 6 on which the sample 5 is fixed on the sample stage 9. The primary electron beam 2 emitted from the electron gun 1 is accelerated by acceleration means (not shown), focused by the focusing lens 3, and scanned on the sample 5 by the X-direction and Y-direction scanning coils 4X and 4Y. By such scanning on the sample 5 by the electron beam 2, the electrons 7 scattered in the sample 5 or transmitted through the sample 5 without scattering are emitted from the lower surface of the sample 5.
透過電子７は、試料５の内部状態、厚さ、原子種によって、強度、散乱角度が異なる。また、透過電子７の散乱角度は、電子線２の加速電圧でも変化し、例えば、加速電圧が低くなると試料５で散乱される割合が多くなり、試料５の下面から出射する透過電子の電子線光軸Ｏからの出射角度（散乱角度）が大きくなる。 The transmitted electrons 7 differ in intensity and scattering angle depending on the internal state, thickness, and atomic species of the sample 5. The scattering angle of the transmitted electrons 7 also changes with the acceleration voltage of the electron beam 2. For example, when the acceleration voltage decreases, the ratio of scattering by the sample 5 increases, and the electron beam of transmitted electrons emitted from the lower surface of the sample 5. The emission angle (scattering angle) from the optical axis O increases.
試料５の下面から出射した透過電子７は、試料ホルダー６と試料ステージ９の孔８、１０を通過した後、散乱角制限絞り１１に達する。該絞り１１は、特定の散乱角を有する透過電子のみが通過できるように中心部に開けられた孔の口径が制限されている。このような透過電子の通過を制限させる散乱角制限絞りとしては、上記に示した構造のように中央部に孔を有し、該孔の口径で透過電子の通過を制限するものの外に、図２に示すように、中心部に遮蔽板１７を配置して透過電子７の通過を制限するもの（散乱角制限絞り１６）も挙げられる。一般的に、散乱角制限絞り１１を使用すると電子線透過像は明視野像を形成し、散乱角制限絞り１６を使用すると暗視野像を形成する。 The transmitted electrons 7 emitted from the lower surface of the sample 5 pass through the holes 8 and 10 of the sample holder 6 and the sample stage 9 and then reach the scattering angle limiting stop 11. The aperture 11 has a limited aperture diameter in the center so that only transmitted electrons having a specific scattering angle can pass therethrough. As a scattering angle limiting diaphragm for restricting the passage of transmitted electrons, a hole is provided at the center as in the structure shown above, and in addition to the structure that restricts the passage of transmitted electrons by the diameter of the hole, As shown in FIG. 2, there may be mentioned one in which a shielding plate 17 is arranged at the center to restrict the passage of transmitted electrons 7 (scattering angle limiting stop 16). In general, when the scattering angle limiting stop 11 is used, the electron beam transmission image forms a bright field image, and when the scattering angle limiting stop 16 is used, a dark field image is formed.
散乱角制限絞り１１を通過した透過電子１２は、シンチレーター１３に衝突して光に変換され、更に光電子増倍管１４によって電気信号に変換される。増幅手段（図示せず）で増幅され、Ａ/Ｄ変換器（図示せず）を介して表示手段（図示せず）に送られる。表示手段は、送られてきた信号を輝度変調し、試料５の内部構造を反映した電子線透過像を表示し、走査位置に応じた複数の像を取得できる。 The transmitted electrons 12 that have passed through the scattering angle limiting aperture 11 collide with the scintillator 13 and are converted into light, and further converted into an electric signal by the photomultiplier tube 14. Amplified by an amplifying means (not shown) and sent to a display means (not shown) via an A / D converter (not shown). The display means modulates the luminance of the transmitted signal, displays an electron beam transmission image reflecting the internal structure of the sample 5, and can acquire a plurality of images corresponding to the scanning position.
本発明は、上記構成を持つＳＴＥＭなどにより取得した画像をトモグラフィー法で３次元構造を再構築する方法であり、通常、走査透過電子顕微鏡装置には試料５を回転させる試料傾斜部が設けられている。 The present invention is a method for reconstructing a three-dimensional structure by a tomography method using an image acquired by a STEM or the like having the above-described configuration. Usually, a scanning transmission electron microscope apparatus is provided with a sample inclined portion for rotating a sample 5. Yes.
図３は試料傾斜部の説明図であり、試料５は水平線Ｈに対してθだけ傾斜している。傾斜した試料５に電子線ｅが照射され、試料５を透過した電子線は透過電子線ｅ′となる。パソコンなどから試料傾斜部に制御信号が出力され、試料を所定角度に傾斜できる。 FIG. 3 is an explanatory diagram of the sample inclined portion, and the sample 5 is inclined by θ with respect to the horizontal line H. FIG. The inclined sample 5 is irradiated with the electron beam e, and the electron beam transmitted through the sample 5 becomes a transmitted electron beam e ′. A control signal is output from the personal computer or the like to the sample tilting section, and the sample can be tilted at a predetermined angle.
例えば、オペレーターが測定開始角度まで試料を傾斜させ、ＳＴＥＭ像を取得する。ここで、最初の回転角度θはオペレーターが適宜設定でき、例えば＋７０度に設定される。ＳＴＥＭ像の取得後、オペレーターが設定した測定終了角度まで、試料の傾斜及び画像の取得のステップを繰り返し、回転シリーズ像（複数の画像）が得られる。なお、オペレーターは設定により、試料を任意の角度の単位で傾斜させることができる。得られた複数の画像をトモグラフィー法で３次元構造を再構築し、ゴム材料中の充填剤の分散状態を観察できる立体画像を取得できる。 For example, the operator tilts the sample to the measurement start angle and acquires a STEM image. Here, the first rotation angle θ can be appropriately set by the operator, and is set to +70 degrees, for example. After acquiring the STEM image, the sample tilt and image acquisition steps are repeated until the measurement end angle set by the operator, and a rotation series image (a plurality of images) is obtained. Note that the operator can tilt the sample by an arbitrary angle unit by setting. A three-dimensional structure can be obtained by reconstructing a three-dimensional structure of the obtained images by a tomography method and observing the dispersion state of the filler in the rubber material.
以上のとおり、充填剤を含有するゴム材料のサンプルについて、例えば、走査透過電子顕微鏡を用いて集束された電子線をサンプルに走査して複数の電子線透過像を取得する工程１と、該サンプルを所定角度単位で回転し、各角度ごとに同様の方法で複数の電子線透過像を取得するステップを繰り返す工程２と、トモグラフィー法を用いて、該工程１及び２で取得した電子線透過像を再構築する工程３とを含む方法により、サンプル中の充填剤の分散状態を観察できる。 As described above, for a sample of a rubber material containing a filler, for example, Step 1 of obtaining a plurality of electron beam transmission images by scanning the sample with a focused electron beam using a scanning transmission electron microscope, and the sample Step 2 of repeating a step of acquiring a plurality of electron beam transmission images by the same method for each angle, and the electron beam transmission images acquired in Steps 1 and 2 using the tomography method By the method including the step 3 of reconstructing, the dispersion state of the filler in the sample can be observed.
走査透過電子顕微鏡装置１００では、電子線２の加速電圧は、好ましくは１００〜３０００ｋＶである。該加速電圧が下限未満であると電子線がサンプルを透過しないため、観察できないおそれがある。上限を超えると、厚みが厚いサンプルでも電子線が透過するが、ダメージが大きく観察できないおそれがある。 In the scanning transmission electron microscope apparatus 100, the acceleration voltage of the electron beam 2 is preferably 100 to 3000 kV. If the acceleration voltage is less than the lower limit, the electron beam does not pass through the sample, and thus there is a possibility that it cannot be observed. If the upper limit is exceeded, even if the sample is thick, the electron beam is transmitted, but the damage is so large that it may not be observed.
試料５（ゴム材料）の傾斜角度単位（試料傾斜部の傾斜ステップ毎に傾ける角度）は、好ましくは０．５〜４度、より好ましくは１〜２度である。０．５度未満であると、撮影時間が長くなりサンプルがダメージを受け、鮮明な像を取得できないおそれがあり、４度を超えると、再構成後のスライス像が不鮮明になるおそれがある。 The tilt angle unit of the sample 5 (rubber material) (the tilt angle for each tilt step of the sample tilt portion) is preferably 0.5 to 4 degrees, more preferably 1 to 2 degrees. If the angle is less than 0.5 degrees, the photographing time becomes long and the sample may be damaged, and a clear image may not be obtained. If the angle exceeds 4 degrees, the slice image after reconstruction may become unclear.
また、試料５の回転角度θは特に限定されず、サンプルをロッドの形状に加工し理論上の理想としては−１８０度〜＋１８０度の全範囲で測定することが好ましいが、装置上の制限より好ましくは−９０度〜＋９０度、より好ましくは−７０度〜＋７０度の範囲で測定する。 Further, the rotation angle θ of the sample 5 is not particularly limited, and it is preferable that the sample is processed into a rod shape and measured as a theoretical ideal in the entire range of −180 degrees to +180 degrees. The measurement is preferably performed in the range of −90 degrees to +90 degrees, more preferably −70 degrees to +70 degrees.
走査透過電子顕微鏡装置１００において、試料５とシンチレーター１３との距離Ｌ１（カメラ長）は、好ましくは５〜２００ｃｍである。５ｃｍ未満であると、像が不鮮明になるおそれがある。２００ｃｍを超えると、像が不鮮明になるおそれがある。 In the scanning transmission electron microscope apparatus 100, the distance L1 (camera length) between the sample 5 and the scintillator 13 is preferably 5 to 200 cm. If it is less than 5 cm, the image may be unclear. If it exceeds 200 cm, the image may become unclear.
試料５の厚さＬ２は特に限定されず、２００ｎｍ未満、２００ｎｍ以上のいずれのサンプルでも充填剤の分散状態を良好に観察できる。厚さＬ２は、好ましくは２００〜１５００ｎｍ、より好ましくは５００〜１０００ｎｍである。１５００ｎｍまで観察可能になることで、２００ｎｍ以上のサンプルの充填剤の凝集構造の観察精度が高まり、充填剤の正確な分散状態を解析できる。 The thickness L2 of the sample 5 is not particularly limited, and the dispersion state of the filler can be satisfactorily observed in any sample of less than 200 nm and 200 nm or more. The thickness L2 is preferably 200 to 1500 nm, more preferably 500 to 1000 nm. By being able to observe up to 1500 nm, the observation accuracy of the aggregated structure of the filler of the sample of 200 nm or more is increased, and the accurate dispersion state of the filler can be analyzed.
本発明におけるゴム材料に含まれるゴム成分としては、天然ゴム（ＮＲ）、イソプレンゴム（ＩＲ）、ブチルゴム（ＩＩＲ）、ブタジエンゴム（ＢＲ）、スチレンブタジエンゴム（ＳＢＲ）、スチレンイソプレンブタジエンゴム（ＳＩＢＲ）、エチレンプロピレンジエンゴム（ＥＰＤＭ）、クロロプレンゴム（ＣＲ）、アクリロニトリルブタジエンゴム（ＮＢＲ）などが挙げられる。充填剤としては特に限定されず、例えば、カーボンブラック、シリカ、クレー、タルク、炭酸マグネシウム、水酸化マグネシウム等が挙げられる。また、上記ゴム材料には、硫黄、加硫促進剤などゴム工業において一般的に用いられている各種材料が適宜配合されてもよい。 The rubber component contained in the rubber material in the present invention includes natural rubber (NR), isoprene rubber (IR), butyl rubber (IIR), butadiene rubber (BR), styrene butadiene rubber (SBR), and styrene isoprene butadiene rubber (SIBR). Ethylene propylene diene rubber (EPDM), chloroprene rubber (CR), acrylonitrile butadiene rubber (NBR), and the like. The filler is not particularly limited, and examples thereof include carbon black, silica, clay, talc, magnesium carbonate, magnesium hydroxide and the like. Moreover, various materials generally used in the rubber industry such as sulfur and a vulcanization accelerator may be appropriately blended with the rubber material.
実施例に基づいて、本発明を具体的に説明するが、本発明はこれらのみに限定されるものではない。 The present invention will be specifically described based on examples, but the present invention is not limited to these examples.
＜実施例及び比較例＞
以下、実施例及び比較例で使用した各種薬品、装置について、まとめて説明する。
（薬品）
ＳＢＲ：住友化学（株）製のＳＢＲ１５０２
シリカ：ローディアジャパン（株）製の１１５Ｇｒ
シランカップリング剤：デグッサ社製のＳｉ６９
硫黄：鶴見化学（株）製の粉末硫黄
加硫促進剤Ａ：大内新興化学工業（株）製のノクセラーＮＳ
加硫促進剤Ｂ：大内新興化学工業（株）製のノクセラーＤ
（装置）
ミクロトーム：ＬＥＩＣＡ社製のウルトラミクロトームＥＭ ＶＣ６
電子顕微鏡：日本電子（株）製の透過型電子顕微鏡ＪＥＭ２１００Ｆ
<Examples and Comparative Examples>
Hereinafter, various chemicals and devices used in Examples and Comparative Examples will be described together.
(Medicine)
SBR: SBR1502 manufactured by Sumitomo Chemical Co., Ltd.
Silica: 115Gr made by Rhodia Japan
Silane coupling agent: Si69 manufactured by Degussa
Sulfur: Powder sulfur vulcanization accelerator made by Tsurumi Chemical Co., Ltd. A: Noxeller NS made by Ouchi Shinsei Chemical Co., Ltd.
Vulcanization accelerator B: Noxeller D manufactured by Ouchi Shinsei Chemical Co., Ltd.
(apparatus)
Microtome: Ultramicrotome EM VC6 manufactured by LEICA
Electron microscope: Transmission electron microscope JEM2100F manufactured by JEOL Ltd.
表１に示す配合処方にしたがい、バンバリーミキサーを用いて、硫黄及び加硫促進剤以外の材料を排出温度１６０℃の条件下で４分間混練りし、混練り物を得た。次に、得られた混練り物に硫黄及び加硫促進剤を添加し、オープンロールを用いて、１００℃の条件下で２分間練り込み、未加硫ゴム組成物を得た。更に、得られた未加硫ゴム組成物を１７５℃で３０分間加硫することにより、加硫ゴム組成物を得た。 In accordance with the formulation shown in Table 1, using a Banbury mixer, materials other than sulfur and the vulcanization accelerator were kneaded for 4 minutes at a discharge temperature of 160 ° C. to obtain a kneaded product. Next, sulfur and a vulcanization accelerator were added to the obtained kneaded product, and kneaded for 2 minutes at 100 ° C. using an open roll to obtain an unvulcanized rubber composition. Furthermore, the obtained unvulcanized rubber composition was vulcanized at 175 ° C. for 30 minutes to obtain a vulcanized rubber composition.
得られた加硫ゴム組成物をミクロトームを用いてサンプル（切片）を作製した。サンプルの厚さは以下の通りであった。
サンプル（１）：５００ｎｍ
サンプル（２）：１８９ｎｍ
A sample (section) of the obtained vulcanized rubber composition was prepared using a microtome. The sample thickness was as follows.
Sample (1): 500 nm
Sample (2): 189 nm
（実施例）
得られたサンプル（１）をメッシュに載せ、電子顕微鏡のサンプル室内にセットし、カメラ長１５０ｃｍ、電子線照射の加速電圧を２００ｋＶに設定した。ＳＴＥＭモードにて、様々な回転角度（−６０度〜＋６０度）で電子線を走査し、各ＳＴＥＭ像を取得した。なお、サンプルを１度ずつ回転させて所定の回転角度に調整して、各回転角度におけるＳＴＥＭ像を取得した。得られたすべてのＳＴＥＭ像をコンピュータトモグラフィー法により再構成することで、各断面スライス像を取得し、ゴム成分を黒色、フィラーを白色として各画像を得た。各画像を再構築し、サンプルの３次元像を取得した（図４）。
(Example)
The obtained sample (1) was placed on a mesh, set in a sample chamber of an electron microscope, a camera length of 150 cm, and an acceleration voltage of electron beam irradiation were set to 200 kV. In the STEM mode, the electron beam was scanned at various rotation angles (−60 degrees to +60 degrees), and each STEM image was acquired. The sample was rotated by 1 degree and adjusted to a predetermined rotation angle, and STEM images at each rotation angle were obtained. All the obtained STEM images were reconstructed by a computer tomography method to obtain each slice image, and each image was obtained with the rubber component black and the filler white. Each image was reconstructed to obtain a three-dimensional image of the sample (FIG. 4).
（比較例）
試料としてサンプル（２）を使用した点、モードを３Ｄ−ＴＥＭとした点以外は、実施例と同様の条件で３次元像を取得した（図５）。
(Comparative example)
A three-dimensional image was obtained under the same conditions as in the example except that the sample (2) was used as a sample and the mode was 3D-TEM (FIG. 5).
３Ｄ−ＴＥＭによる観察は厚さ２００ｎｍ以下のサンプルに限られたが、走査透過電子顕微鏡を用いたトモグラフィー（３Ｄ−ＳＴＥＭ）により、厚さ５００ｎｍのサンプルでもフィラーの分散状態を観察できることが明らかとなった。 Observation by 3D-TEM was limited to samples with a thickness of 200 nm or less, but it became clear by the tomography using a scanning transmission electron microscope (3D-STEM) that the filler dispersion state can be observed even with a sample with a thickness of 500 nm. It was.
１ 電子銃
２ 一次電子線
３ 集束レンズ
４Ｘ Ｘ方向走査コイル
４Ｙ Ｙ方向走査コイル
５ 試料
６ 試料ホルダー
７、１２、１５ 透過電子
８、１０ 電子線通過孔
９ 試料ステージ
１１、１６ 散乱角制限絞り
１３ シンチレーター
１４ 光電子増倍管
１７ 遮蔽板
１００ 走査透過電子顕微鏡装置
DESCRIPTION OF SYMBOLS 1 Electron gun 2 Primary electron beam 3 Focusing lens 4X X direction scanning coil 4Y Y direction scanning coil 5 Sample 6 Sample holder 7, 12, 15 Transmission electron 8, 10 Electron beam passage hole 9 Sample stage 11, 16 Scattering angle restriction | limiting aperture 13 Scintillator 14 photomultiplier tube 17 shielding plate 100 scanning transmission electron microscope apparatus
Claims (2)
走査透過電子顕微鏡を用いて加速電圧１００〜３０００ｋＶで電子線を集束し、電子線が照射された箇所の焦点を合わせることが可能な距離をサンプルの厚さ方向に深くすることにより取得した、厚さが５００〜１０００ｎｍであるゴム材料の各回転角度における画像からトモグラフィー法により３次元構造を再構築し、ゴム材料中の充填剤の分散状態を観察する
ことを特徴とするゴム材料の観察方法。 A method for observing a rubber material containing a filler,
Thickness obtained by converging an electron beam at an acceleration voltage of 100 to 3000 kV using a scanning transmission electron microscope and increasing the distance at which the electron beam can be focused in the thickness direction of the sample. A method for observing a rubber material, characterized in that a three-dimensional structure is reconstructed by a tomography method from images at each rotation angle of the rubber material having a thickness of 500 to 1000 nm, and the dispersion state of the filler in the rubber material is observed.
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