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要旨集●Vol.39 No.3（2004年9月発行）
特集：Surface and Micro-Analysis of Organic Materials
（有機材料のミクロ・表面分析）
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Review
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P.1
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This paper is
a review of the technical approaches taken at Toyota
Central R&D Labs. (TCRDL) toward the surface and
micro-analysis of organic materials. For organic microanalysis
techniques, which are suitable for analysis of the degradation
of organic materials, a depth analysis technique using
micro-IR and a distribution analysis technique using
derivatization-XMA have been developed. The former technique
provides a great deal of information about organic chemical
structure and the latter has higher sensitivity and
higher lateral resolution than micro-IR. For organic
surface analysis techniques, which are suitable for
the analysis of adhesion and lubrication, a new method
for time-of-flight mass spectrometry (TOF-SIMS) and
a new type of surface analysis using a combination of
SEIRA and ATR have been developed. Looking ahead to
future trends, it is anticipated that "organic
surface and micro-analysis" will evolve into "organic
nanoanalysis", which will permit nanometer-order
lateral and depth resolution, via the application of
two approaches for extending the applicability of conventional
organic analysis techniques to smaller scales, and for
extending the applicability of nanometer scale analysis
techniques to organic chemical analysis.
有機材料のミクロ表面分析技術に関する当社での取り組み状況についての概況を述べる。特に有機材料の劣化解析に適した有機ミクロ分析技術として，有機化学構造情報が豊富な顕微IRを利用した深さ方向分析技術と，特定の官能基に対する感度と面分解能が顕微IRよりも優れた誘導体化−XMA法を開発した。接着や潤滑の解析に適した有機表面分析技術として，TOF-SIMSを利用した解析技術，銀蒸着TOF-SIMS法，SEIRAとATRとを組み合わせた新しい表面赤外分析技術の開発を行っている。将来は，2種類のアプローチ，すなわち有機分析技術のナノスケール化およびナノ観察技術で有機化学構造情報を得るための技術開発により，「有機ミクロ・表面分析技術」から面方向と深さ方向でnmレベルの分解能を持つ「有機ナノ分析技術」へと進化していくものと期待される。
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Research
Report
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P.7
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A new analytical method, referred to as "Derivatization-Electron
Probe X-ray Micro-analysis (Derivatization-XMA)",
has been developed to determine the distribution of
0.1 % order functional groups in polymers with μm
level lateral resolution. Also, the optimal reaction
conditions that make it possible to selectively derivatize
the vinyl groups, carboxyl groups, carbonyl groups,
hydroxyl groups and epoxy groups have been found.
This method first derivatizes the functional groups
in a polymer using a reagent with an indicator element
highly sensitive to XMA, and moreover, with high selectivity
to the functional group, and then measures the distribution
of the indicator elemens by XMA, thus obtaining the
distribution of the original functional groups. The
fundamental performance of XMA in analyzing derivatized
polymers has been investigated. The results showed
that the detection limit was 0.05 % and the lateral
resolution was 3 μm. In addition, the depth profile
of the vinyl groups in an amine-degraded polyvinylchloride
sheet was analyzed using this method. Since the depth
profiles agreed well with those obtained by micro-IR
spectroscopy, the reliability of measuring the distribution
of functional groups by this method was confirmed.
By this method, the sensitivity was 30 times higher,
and the lateral resolution was 4 times higher than
those obtained by micro-IR spectroscopy. Actual application
to the depth analysis of degraded polymers has proved
that this method is useful for the characterization
of polymers and the study of polymer degradation.
高分子材料中に存在する0.1%オーダーの官能基の分布をμmオーダーの位置分解能で測定できる新しい分析法として，"誘導体化−電子線プローブマイクロアナリシス
( 誘導体化−XMA ) "が有効であることを見出した。また，官能基であるビニル基，カルボキシル基，カルボニル基，水酸基およびエポキシ基について，本法のキーとなる誘導体化が選択的に行える最適反応条件を見出した。本法はXMAに高感度な標識元素を持つ反応試薬で官能基を誘導体化した後，この標識元素の分布をXMAで測定することにより，元の官能基の分布を得るものであり，検出感度0.05％，位置分解能3μmであった。本法をアミンで劣化させた塩化ビニル樹脂中のビニル基の分布測定に適用したところ，本法による分布は顕微IR法による分布と良く一致し，本法による官能基の分布測定の信頼性が確認された。また，本法は顕微IR法に比べて検出感度が30倍，位置分解能が4倍高いことも分かった。さらに，劣化させた高分子材料に適用し，高分子材料の劣化機構の解析や劣化状態の評価に有効であることを示した。
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P.15
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The adsorption of model compounds
of lubricant additives onto ferrous materials was
investigated using time-of-flight secondary ion mass
spectrometry (TOF-SIMS). Nineteen types of model compounds,
including phosphates, carboxylic acids, alcohols,
amines, and esters, were subjected to lubrication
tests. The TOF-SIMS spectra of the friction surfaces
after hexane washing indicated that amines were physically
adsorbed, carboxylic acids and esters were chemically
adsorbed, and phosphates were tribochemically reacted
onto friction surfaces. For alcohols, which showed
no lubricity, no adsorbed component was detected on
the friction surfaces by TOF-SIMS. From the results
of investigation of correlation between the TOF-SIMS
data and lubrication properties, it was possible to
discuss the relationships between the results of TOF-SIMS
analysis and lubrication properties such as friction
coefficient and wear scar width when making comparisons
among similar types of lubricant additives or investigating
chemical changes of friction surfaces during lubrication
tests.
潤滑添加剤のモデル化合物の鉄表面への吸着について，飛行時間型二次イオン質量分析
(TOF-SIMS) によって研究した。リン酸エステル，カルボン酸，アルコール，アミン，エステルなど19種類のモデル化合物を潤滑試験に供した。潤滑面をヘキサンで洗浄した後，TOF-SIMS分析を行うことにより，鉄摩擦面に対してアミンは物理吸着，カルボン酸とエステルは化学吸着，リン酸エステルはトライボケミカルな反応を起こしていることが明らかになった。また，同タイプの潤滑剤同士での比較の場合，および潤滑試験における摩擦面の経時変化の追跡の場合には，TOF-SIMS分析結果と潤滑特性との関連を議論することが可能であることを示した。
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P.21
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A method for the direct detection of the molecular
ions of a very small amount of poly(dimethylsiloxane)(PDMS)
on a solid surface was investigated. It was found
that a TOF-SIMS analysis of silver-deposited surfaces
(silver deposition/TOF-SIMS) is useful for this purpose.
Molecular ions include information about structure
(end groups, functional groups, etc.) and molecular
weight, which are needed to evaluate organic substances.
Using this method, silver-cationized quasi-molecular
ions of PDMS were clearly detected on solid surfaces,
and their structure and molecular weight were evaluated.
In addition, their images obtained from the ions showed
no interference from the deposited silver. Application
of this method to the analysis of a paint defect allowed
determination of the cause of the defect. Silver-cationized
ions were detected on solid surfaces not only from
PDMS, but also from other organic materials, including
certain types of lubricant additives and fluorine
oils. Therefore, it was confirmed that this method
is useful for the analysis of ultrathin substances
on actual industrial materials.
固体表面に極微量付着したシリコーンオイル(PDMS)の分子量と分子構造を直接評価するため，分子構造や分子量分布の情報を含む分子イオンを検出する方法を検討し，試料表面に銀を蒸着してTOF-SIMSで分析する銀蒸着/TOF-SIMS法が有効であることを見出した。この方法により，固体表面に付着したPDMSから銀によってカチオン化された擬似分子イオンを検出することが可能となり，構造と分子量分布の評価および蒸着した銀に影響されない面分布の評価も可能となった。この方法を塗装のはじき解析に適用したところ，はじき原因となったPDMSが判別でき，原因が解明できた。この方法は，PDMSだけでなくオイル添加剤，フッ素オイルなど幅広く応用可能であることも確認し，固体表面上の極微量有機物の分析に有効であることを示した。
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