JPH0225447B2 - - Google Patents
Info
- Publication number
- JPH0225447B2 JPH0225447B2 JP57181392A JP18139282A JPH0225447B2 JP H0225447 B2 JPH0225447 B2 JP H0225447B2 JP 57181392 A JP57181392 A JP 57181392A JP 18139282 A JP18139282 A JP 18139282A JP H0225447 B2 JPH0225447 B2 JP H0225447B2
- Authority
- JP
- Japan
- Prior art keywords
- contrast
- phase
- tetroxide
- osmium tetroxide
- electron beam
- 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.)
- Expired
Links
- 238000000034 method Methods 0.000 claims description 17
- 229910000489 osmium tetroxide Inorganic materials 0.000 claims description 17
- 239000012285 osmium tetroxide Substances 0.000 claims description 17
- 238000010894 electron beam technology Methods 0.000 claims description 15
- 239000002861 polymer material Substances 0.000 claims description 8
- 238000010186 staining Methods 0.000 claims description 7
- 229920000642 polymer Polymers 0.000 claims description 6
- 238000001493 electron microscopy Methods 0.000 claims description 5
- 230000001678 irradiating effect Effects 0.000 claims description 3
- 239000000203 mixture Substances 0.000 description 14
- 229910001927 ruthenium tetroxide Inorganic materials 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- 238000004627 transmission electron microscopy Methods 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 7
- -1 polybutylene terephthalate Polymers 0.000 description 7
- 239000000523 sample Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 238000004043 dyeing Methods 0.000 description 5
- 229920001893 acrylonitrile styrene Polymers 0.000 description 4
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 229920001707 polybutylene terephthalate Polymers 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 238000007447 staining method Methods 0.000 description 3
- 229920000800 acrylic rubber Polymers 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229920000554 ionomer Polymers 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012472 biological sample Substances 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
Landscapes
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Sampling And Sample Adjustment (AREA)
- Microscoopes, Condenser (AREA)
Description
【発明の詳細な説明】
本発明は電子顕微鏡観察用高分子材料の染色方
法に関するものである。さらに詳しくは透過型電
子顕微鏡（以下電顕と略称する。）で観察する際
に、特定の官能基の有無に依存することなく、安
定した明瞭なコントラストでその構造を識別する
ことが可能な電顕観察用高分子試料の新規な調製
方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for staining polymeric materials for electron microscopy. In more detail, when observing with a transmission electron microscope (hereinafter referred to as electron microscope), it is possible to identify the structure with stable and clear contrast, regardless of the presence or absence of specific functional groups. This invention relates to a novel method for preparing polymer samples for microscopic observation.
二種以上の高分子物質からなる混合物または共
重合体の相分離構造および高分子物質の結晶構造
などを電顕により観察する場合には、各相間の電
子線散乱能の差が小さく、明瞭なコントラストを
得ることの困難な場合が多いため、通常は特定の
相に散乱能の大きな重合属元素を導入して相間の
電子線散乱能に差を与える、いわゆる電子線染色
が行なわれており、その具体的手段としては四酸
化オスミウム（OsO4）、四酸化ルテニウム
（RuO4）およびリンタングステン酸（ドデカウオ
ルフラモリン（）酸）などによる染色方法がよ
く知られている。 When observing the phase separation structure of a mixture or copolymer consisting of two or more types of polymeric substances, the crystalline structure of a polymeric substance, etc. using an electron microscope, the difference in electron beam scattering ability between each phase is small and the structure is clearly visible. Since it is often difficult to obtain contrast, so-called electron beam staining is usually performed, which involves introducing a polymeric group element with a large scattering ability into a specific phase to create a difference in the electron beam scattering ability between the phases. As specific means for this purpose, staining methods using osmium tetroxide (OsO 4 ), ruthenium tetroxide (RuO 4 ), phosphotungstic acid (dodecauroframoric acid), and the like are well known.
四酸化オスミウムは、従来、生物試料の染色に
用いられていたが、ゴムの染色に有効であること
が知見されて以来、多くの合成高分子物質に適用
されており、その詳細な反応のメカニズムは解明
されていないが、とくに二重結合、水酸基、エー
テル基、アミド基などを有する高分子物質の染色
に有効であるとされている。また、四酸化ルテニ
ウムも、反応のメカニズムは四酸化オスミウムに
類似と推定されており、たとえばアクリロニトリ
ル−スチレン共重合体とポリメチルメタアクリレ
ートとの混合物中のアクリロニトリル−スチレン
共重合体の染色などに有効であることが報告され
ている。 Osmium tetroxide has traditionally been used to stain biological samples, but since it was found to be effective in staining rubber, it has been applied to many synthetic polymer substances, and the detailed reaction mechanism has been investigated. Although not fully understood, it is said to be particularly effective for staining polymeric substances containing double bonds, hydroxyl groups, ether groups, amide groups, etc. Furthermore, the reaction mechanism of ruthenium tetroxide is estimated to be similar to that of osmium tetroxide, and it is effective, for example, in dyeing acrylonitrile-styrene copolymer in a mixture of acrylonitrile-styrene copolymer and polymethyl methacrylate. It has been reported that
さらに、四酸化オスミウムとの反応性が乏しい
高分子物質に適当な前処理を施したのち染色する
方法も検討されており、例えばアクリロニトリル
−スチレン共重合体とアクリルゴムの混合物を抱
水ヒドラジン（N2H4）で前処理したのち、四酸
化オスミウム処理することにより、アクリルゴム
を染色する方法などが知られている。 Furthermore, a method of dyeing a polymer material that has poor reactivity with osmium tetroxide after an appropriate pretreatment is being considered. For example, a mixture of acrylonitrile-styrene copolymer and acrylic rubber has been dyed with hydrazine hydrate (N A known method is to dye acrylic rubber by pre-treating it with 2 H 4 ) and then treating it with osmium tetroxide.
しかるに近年とくに高分子材料に対する要求が
多様化、複雑化するに伴い、多成分系材料の多様
化も著しく、上述の方法をはじめとする従来の染
色方法では構造の可視化が困難な材料が数多く出
現しており、それらの有効な染色方法の開発が期
待されている。 However, in recent years, as the requirements for polymeric materials have become more diverse and complex, multi-component materials have become increasingly diverse, and many materials have appeared whose structures are difficult to visualize using conventional staining methods, including the methods mentioned above. Therefore, the development of effective dyeing methods is expected.
そこで、本発明者らは、特定の官能基の有無に
依存しない、適用範囲の広い電顕観察用高分子試
料の染色方法について鋭意検討を行なつた結果、
高分子材料を四酸化オスミウムまたは四酸化ルテ
ニウムにより染色するに先立ち、予め電子線処理
を施こすことにより、安定した明瞭なコントラス
トでその構造を識別することが可能な高分子試料
が得られることを見出し本発明に到達した。 Therefore, the present inventors conducted extensive research on a staining method for polymer samples for electron microscopy that is applicable to a wide range of applications and does not depend on the presence or absence of specific functional groups.
By subjecting polymeric materials to electron beam treatment before staining them with osmium tetroxide or ruthenium tetroxide, it is possible to obtain polymeric samples whose structures can be identified with stable and clear contrast. Heading The present invention has been arrived at.
すなわち本発明は高分子材料に電子線照射を施
こした後、四酸化オスミウムおよび／または四酸
化ルテニウムによる染色処理を施こすことを特徴
とする電顕観察用高分子試料の調製方法を提供す
るものである。 That is, the present invention provides a method for preparing a polymer sample for electron microscopy, which comprises irradiating a polymer material with an electron beam and then staining it with osmium tetroxide and/or ruthenium tetroxide. It is something.
上記本発明によれば、高分子材料に対し予め電
子線を照射することにより、高分子材料の各相
に、各相固有の耐放射線性に対応した二重結合や
活性ラジカルなどの生成反応が進行するため、各
相に四酸化オスミウムまたは四酸化ルテニウムに
対する反応性の差が付与され、次いで行なわれる
染色処理においては前記の差に応じて各相に導入
される重合属元素（オスミウムまたはルテニウ
ム）の量が相違することになる。したがつて本発
明の方法で得た高分子試料を電顕観察する際には
各相間の電子線散乱能の差が増大され、安定し
た、明瞭なコントラストで各相を識別することが
可能となる。さらにまた本発明の方法によれば、
上記の如き化学組成の異なる高分子材料の相間識
別ばかりではなく、同一化学組成における凝集状
態の識別、たとえば同一高分子における結晶相と
非晶相を識別するための試料の調製にも有効であ
り、従来電顕による結晶微細構造の観察が不可能
であつた高分子物質についての観察をも可能にす
ることができる。 According to the present invention, by irradiating the polymeric material with an electron beam in advance, a reaction occurs in each phase of the polymeric material to generate double bonds and active radicals corresponding to the radiation resistance specific to each phase. As the process progresses, each phase is given a difference in reactivity to osmium tetroxide or ruthenium tetroxide, and in the subsequent dyeing process, a polymeric group element (osmium or ruthenium) is introduced into each phase according to the above-mentioned difference. There will be a difference in the amount of Therefore, when observing a polymer sample obtained by the method of the present invention with an electron microscope, the difference in electron beam scattering ability between each phase is increased, making it possible to identify each phase with stable and clear contrast. Become. Furthermore, according to the method of the present invention,
It is effective not only for phase discrimination between polymer materials with different chemical compositions as described above, but also for discrimination of agglomeration states in the same chemical composition, for example, in preparation of samples for discrimination between crystalline and amorphous phases in the same polymer. , it is also possible to observe polymeric substances whose crystal microstructures have conventionally been impossible to observe using an electron microscope.
本発明において使用される電子線の照射線量率
および照射線量は対象とする高分子材料の種類に
より適宜選択することができる。しかし照射線量
率や照射線量が小さすぎるとコントラストの付与
が不十分となり、一方大きすぎると各相ともに四
酸化オスミウムまたは四酸化ルテニウムとの反応
性が極めて大きくなり、コントラストが得られな
くなるばかりか、著しい場合には構造の破壊や劣
化を生ずるため注意を要する。また、照射雰囲気
は減圧下、大気中、不活性雰囲気下などを適宜選
択可能である。電子線を照射する高分子材料の形
態についても、塊状、切片状等いずれの形態もと
りうるが、実際の操作の効率を考慮すると、1000
Å以下の切片の形態の方が、電子線放射、ひきつ
づく四酸化オスミウムまたは四酸化ルテニウム処
理の効率上すぐれ、また、電子線照射も、電顕の
試料室中で電子線により行なうことが可能であ
り、簡便性のうえでもすぐれている。 The irradiation dose rate and irradiation dose of the electron beam used in the present invention can be appropriately selected depending on the type of the target polymer material. However, if the irradiation dose rate or irradiation dose is too small, contrast will not be imparted sufficiently, while if it is too large, the reactivity of each phase with osmium tetroxide or ruthenium tetroxide will become extremely large, and not only will contrast not be obtained, In severe cases, the structure may be destroyed or deteriorated, so care must be taken. Further, the irradiation atmosphere can be appropriately selected from reduced pressure, air, inert atmosphere, etc. The form of the polymer material to be irradiated with electron beams can be in any form, such as lumps or sections, but considering the efficiency of actual operation, 1000
Sections of Å or smaller are more efficient in electron beam irradiation and subsequent osmium tetroxide or ruthenium tetroxide treatment, and electron beam irradiation can also be performed in the sample chamber of an electron microscope. It is also excellent in terms of simplicity.
四酸化オスミウムまたは四酸化ルテニウム処理
の方法にも特に制限はなく、四酸化オスミウムま
たは四酸化ルテニウムを水または適当な溶媒に溶
解せしめた水溶液または溶液に高分子材料を浸漬
する方法、四酸化オスミウムまたは四酸化ルテニ
ウム蒸気に高分子材料をさらす方法およびこれら
を必要により加熱するなどが挙げられるが、これ
らに限定されるものではない。 There are no particular limitations on the method for treating osmium tetroxide or ruthenium tetroxide, such as a method of immersing the polymer material in an aqueous solution or a solution in which osmium tetroxide or ruthenium tetroxide is dissolved in water or an appropriate solvent, Examples include, but are not limited to, a method of exposing the polymeric material to ruthenium tetroxide vapor and heating it if necessary.
本発明の方法を適用する高分子材料には、特に
制限はないが、本発明の染色方法によりとくに濃
コントラスト化の著しいものとしては、例えばポ
リブチレンテレフタレート、ポリアクリロニトリ
ルなどが挙げられる。 There are no particular limitations on the polymeric material to which the method of the present invention is applied, but examples of materials that can be particularly markedly contrasted by the dyeing method of the present invention include polybutylene terephthalate and polyacrylonitrile.
次に、本発明を実施例により具体的に説明す
る。 Next, the present invention will be specifically explained using examples.
実施例 １
ポリブチレンテレフタレートと変性ポリオレフ
イン（住友化学(株)製“ボンド・フアスト−Ｅ”）
とを80対20の重量比で溶融混練した混合物から、
常法により切り出した厚さ約800Åの電顕観察用
の薄切片を、コロジオン膜補強した銅メツシユ上
に載置したものを、日立(株)製透過型電顕（HU−
11A）の試料室にセツトしたのち、加速電圧
75KV、電流密度12アンペア／cm2で電子線を約１
秒間照射した。次に照射後の試料を四酸化オスミ
ウム蒸気に約５時間さらしたのち、透過型電顕観
察に供した。約１万倍の倍率で得られた観察像
は、第１図の通りであり、濃コントラストのポリ
ブチレンテレフタレート相に、淡コントラストの
変性ポリオレフイン相が粒径1μ前後で分散した
海−島構造であり、コントラストは観察時の電子
線照射にも安定であり、かつ、極めて明瞭であつ
た。Example 1 Polybutylene terephthalate and modified polyolefin (“Bond Fast-E” manufactured by Sumitomo Chemical Co., Ltd.)
From a mixture melted and kneaded at a weight ratio of 80:20,
A thin section for electron microscopy with a thickness of approximately 800 Å cut out using a conventional method was placed on a copper mesh reinforced with a collodion film, and then placed on a transmission electron microscope (HU-
11A) in the sample chamber, then apply the accelerating voltage
75KV, current density 12 ampere/ cm2 , electron beam approximately 1
Irradiated for seconds. Next, the irradiated sample was exposed to osmium tetroxide vapor for about 5 hours, and then subjected to transmission electron microscopy. The observed image obtained at a magnification of about 10,000 times is as shown in Figure 1, and shows a sea-island structure in which a light contrast modified polyolefin phase with a grain size of around 1μ is dispersed in a dark contrast polybutylene terephthalate phase. The contrast was stable even under electron beam irradiation during observation, and was extremely clear.
比較例 １
実施例１で用いた混合物から切り出した厚さ約
800Åの薄切片を、そのまま透過型電顕観察に供
した。得られた観察像は、実施例１で得られた像
とコントラストの濃淡関係は同様であつたが、不
明瞭であり、かつ、観察時間の経過に伴い、数十
秒でコントラストが消滅した。Comparative Example 1 Thickness of cut from the mixture used in Example 1: approx.
The 800 Å thin section was directly subjected to transmission electron microscopy. Although the obtained observed image had the same contrast density relationship as the image obtained in Example 1, it was unclear, and the contrast disappeared in several tens of seconds as the observation time progressed.
さらに比較のため、上記と同様の薄切片を四酸
化オスミウム蒸気に５時間さらしたものについて
透過型電顕観察を行なつたところ、第２図のよう
にコントラストが不明瞭であり、観察経時ととも
に数十秒でコントラストが消滅した。 Furthermore, for comparison, when we performed transmission electron microscopy on a thin section similar to the one above that had been exposed to osmium tetroxide vapor for 5 hours, the contrast was unclear as shown in Figure 2, and as the observation progressed, The contrast disappeared within a few tens of seconds.
実施例 ２
実施例１で用いた混合物から溶融圧縮成形によ
り厚さ約0.5mmのシートを作成し、約２mm四方の
矩形片を切り出し、電顕試料室内で実施例１と同
様の方法で約20秒間電子線照射を行なつた。照射
後の試料を１％の四酸化オスミウム水溶液に浸漬
し、70℃で５時間処理し、10時間減圧乾燥したの
ち、約800Å厚の薄切片を切り出し、透過型電顕
観察に供した。得られた観察像は、実施例１と同
様、コントラストが明瞭であり、かつ、観察経時
に伴う変化も生じなかつた。Example 2 A sheet with a thickness of about 0.5 mm was created from the mixture used in Example 1 by melt compression molding, and a rectangular piece of about 2 mm square was cut out, and about 20 square pieces were cut out in the same manner as in Example 1 in an electron microscope sample chamber. Electron beam irradiation was performed for seconds. After irradiation, the sample was immersed in a 1% aqueous osmium tetroxide solution, treated at 70°C for 5 hours, dried under reduced pressure for 10 hours, and then cut into thin sections approximately 800 Å thick and subjected to transmission electron microscopy. The obtained observed image had clear contrast as in Example 1, and no change occurred over time.
実施例 ３
実施例１で用いた混合物のかわりに、ポリブチ
レンテレフタレート−ポリテトラメチレンオキシ
ドグリコール共重合体とアイオノマー（三井ポリ
ケミカル(株)製“ハイミラン”）とを90対10の重合
比で溶融混練した混合物を用いたことのほかは実
施例１と全く同様の方法で透過型電顕観察を行な
つた。得られた観察像は濃コントラストのポリブ
チレンテレフタレート−ポリテトラメチレンオキ
シドグリコール共重合体相中に、粒径0.5μ前後で
淡コントラストのアイオノマー相が分散する海−
島構造であり、コントラストが明瞭であり、か
つ、経時変化に伴う変化も生じなかつた。Example 3 Instead of the mixture used in Example 1, a polybutylene terephthalate-polytetramethylene oxide glycol copolymer and an ionomer (“Himilan” manufactured by Mitsui Polychemical Co., Ltd.) were melted at a polymerization ratio of 90:10. Transmission electron microscopy observation was carried out in exactly the same manner as in Example 1, except that the kneaded mixture was used. The observed image shows a sea in which a light contrast ionomer phase with a particle size of around 0.5μ is dispersed in a dark contrast polybutylene terephthalate-polytetramethylene oxide glycol copolymer phase.
It had an island structure, the contrast was clear, and no change occurred over time.
実施例 ４
実施例１で用いた混合物のかわりに、アクリロ
ニトリル−スチレン共重合体とエチレン−プロピ
レン−ジエン共重合体（三井石油化学(株)製
EPT3045）とを70対30の重量比で溶融混練した
混合物を用いたことのほかは、実施例１と全く同
様の方法で透過型電顕観察を行なつた。得られた
観察像は、濃コントラストのアクリロニトリル−
スチレン共重合体相中に、淡コントラストのエチ
レン−プロピレン−ジエン共重合体相が数μ前後
の粒径で分散する海−島構造であり、コントラス
トは明瞭であつた。Example 4 Instead of the mixture used in Example 1, acrylonitrile-styrene copolymer and ethylene-propylene-diene copolymer (manufactured by Mitsui Petrochemical Co., Ltd.) were used.
Transmission electron microscopy observation was carried out in exactly the same manner as in Example 1, except that a mixture obtained by melting and kneading EPT3045) at a weight ratio of 70:30 was used. The observation image obtained is a high-contrast acrylonitrile-
It had a sea-island structure in which a pale contrast ethylene-propylene-diene copolymer phase was dispersed in a styrene copolymer phase with a particle size of around several microns, and the contrast was clear.
実施例 ５
実施例４で用いた混合物について、実施例１で
四酸化オスミウムを用いたかわりに四酸化ルテニ
ウムを用いたことのほかは、実施例１と同様の方
法で透過型電顕観察を行なつたところ、実施例４
と同様明瞭なコントラストの海−島構造の観察が
可能であつた。Example 5 Transmission electron microscopy of the mixture used in Example 4 was performed in the same manner as in Example 1, except that ruthenium tetroxide was used instead of osmium tetroxide in Example 1. After getting older, Example 4
It was possible to observe a sea-island structure with a similar clear contrast.
実施例 ６
実施例１で用いた混合物のかわりに、ポリブチ
レンテレフタレート−ポリテトラメチレンオキシ
ドグリコール共重合体を用いたことのほかは、実
施例１と全く同様方法で、透過型電顕観察を行な
つた。７万倍の倍率で得られた観察像は、濃コン
トラストの非晶相の中に、幅約100Å、長さ数千
Åの淡コントラストの結晶ラメラが分散する構造
であり、結晶微細構造の観察が可能であつた。Example 6 Transmission electron microscopy was performed in exactly the same manner as in Example 1, except that polybutylene terephthalate-polytetramethylene oxide glycol copolymer was used instead of the mixture used in Example 1. Summer. The observation image obtained at a magnification of 70,000 times shows a structure in which crystalline lamellae with a light contrast of approximately 100 Å in width and several thousand Å in length are dispersed in a highly contrasting amorphous phase, and the observation of the crystal fine structure. was possible.
第１図および第２図はそれぞれ本発明の実施例
１（第１図）および比較例１（第２図）で得た高分
子材料（ポリブチレンテレフタレート変性ポリ
オレフイン）の薄切片について、透過型電顕によ
り約１万倍の倍率で観察した写真である。
FIGS. 1 and 2 show transmission-type electrophotography of thin sections of the polymer material (polybutylene terephthalate-modified polyolefin) obtained in Example 1 (FIG. 1) of the present invention and Comparative Example 1 (FIG. 2), respectively. This is a photograph taken under a microscope at a magnification of approximately 10,000 times.
Claims (1)
オスミウムおよび／または四酸化ルチニウムによ
る染色処理を施すことを特徴とする電子顕微鏡観
察用高分子試料の調製方法。1. A method for preparing a polymer sample for electron microscopy, which comprises irradiating a polymer material with an electron beam and then staining it with osmium tetroxide and/or rutinium tetroxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57181392A JPS5972040A (en) | 1982-10-18 | 1982-10-18 | Preparation of high polymer sample for electron- microscopic observation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57181392A JPS5972040A (en) | 1982-10-18 | 1982-10-18 | Preparation of high polymer sample for electron- microscopic observation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5972040A JPS5972040A (en) | 1984-04-23 |
| JPH0225447B2 true JPH0225447B2 (en) | 1990-06-04 |
Family
ID=16099935
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57181392A Granted JPS5972040A (en) | 1982-10-18 | 1982-10-18 | Preparation of high polymer sample for electron- microscopic observation |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5972040A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003279508A (en) * | 2002-03-25 | 2003-10-02 | Matsushita Electric Ind Co Ltd | Method of evaluating dispersion state of organic material |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1036612C (en) * | 1994-03-08 | 1997-12-03 | 中国人民解放军第304医院 | Super-thin section colouring liquid for electronic microscope and packing technology |
| JP5687299B2 (en) * | 2012-03-23 | 2015-03-18 | 株式会社住化分析センター | Observation sample, preparation method of observation sample, and observation method |
| US9051441B2 (en) * | 2012-03-29 | 2015-06-09 | Xerox Corporation | Process for chemical passivation of polymer surfaces |
-
1982
- 1982-10-18 JP JP57181392A patent/JPS5972040A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003279508A (en) * | 2002-03-25 | 2003-10-02 | Matsushita Electric Ind Co Ltd | Method of evaluating dispersion state of organic material |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5972040A (en) | 1984-04-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Vargo et al. | Monolayer chemical lithography and characterization of fluoropolymer films | |
| DE2628467A1 (en) | PROCESS FOR CREATING A POSITIVE PAINT IMAGE | |
| DE3315118C2 (en) | ||
| Watson et al. | Methods for the use of indium as an electron stain for nucleic acids | |
| DE69222421T2 (en) | POLYMER FILM | |
| EP2427265B1 (en) | Perforated membranes | |
| DE2735377A1 (en) | PROCESS FOR MANUFACTURING MODIFIED SUBSTRATES AND INTERMEDIATE PRODUCTS OF THIS PROCESS | |
| EP0797768B1 (en) | Sample holder with processed surface portion for altering the contact angle | |
| JPH0225447B2 (en) | ||
| DE60218869T2 (en) | PROCESS FOR PREPARING GRAFT COPOLYMER MEMBRANES | |
| US20180217033A1 (en) | Kit, Composition and Method for Preparing a Specimen for Imaging and Method for Diagnosing a Disease | |
| Hofer et al. | New high‐resolution charge transfer x‐ray and electron beam negative resist | |
| Levin | Electron microscopic investigations of the subunit of haemoglobin and the myoglobin molecule | |
| WO2019140089A1 (en) | Conductive fixation for electron microscopy | |
| Ottewill et al. | Studies on the mechanism of coagulation: Part 3. The formation of positive silver iodide sols in the presence of anionic surface active agents | |
| DE69211272T2 (en) | Process for the grafting of hydrophilic monomers containing double bonds on shaped bodies with polymer surfaces | |
| DE102013204968B4 (en) | PROCESS FOR PASSIVATION OF A POLYMERIC MATERIAL ON THE SURFACE OF TONER PARTICLES | |
| Trent et al. | Transmission electron microscope studies of polymers stained with ruthenium and osmium tetroxide | |
| DE2450381B2 (en) | Radiation-sensitive material and its use | |
| JP4911915B2 (en) | Target decomposition method and decomposition apparatus | |
| JP2000266651A (en) | Preparation of analysis sample | |
| DE2321684C3 (en) | Method of generating patterns | |
| US2903589A (en) | Method for preparing an electron microscope specimen | |
| DE2421834A1 (en) | METHOD OF MANUFACTURING A PATTERNED LAYER SUPPORTED BY A SUBSTRATE | |
| JP7085421B2 (en) | Reaction observation method and layered partition wall type sealed article |