A ToF-SIMS study of the deuterium—hydrogen exchange induced by ammonia plasma treatment of polyolefins

Min, Hyegeun; Wettmarshausen, Sascha; Friedrich, Jörg; Unger, Wolfgang

doi:10.1039/c1ja10043b

Cited by 18 publications

(12 citation statements)

References 36 publications

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“…Polyethylene and polypropylene foils were measured with XPS and ToF-SIMS as described in part 1 [46]. Additionally, C, H, N-analysis and 1 H and 2 H-NMR were performed.…”

Section: Methodsmentioning

confidence: 99%

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Significance of Hydrogen–Deuterium Exchange at Polyolefin Surfaces on Exposure to Ammonia Low-Pressure Plasma

Wettmarshausen

Min

Unger

et al. 2011

Plasma Chem Plasma Process

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Since more than 40 years ammonia plasma exposure of polyolefins is used for introduction of primary amino groups. The selectivity of this reaction and the yield in primary amino groups was found to be low. Here, a prominent side-reactions of this process was investigated, the hydrogenation by NH 3 plasma. For identification of hydrogenation ammonia (NH 3 ) and deuterated ammonia (ND 3 ) were exposed to polyethylene (h-PE) and fully deuterated polyethylene (d-PE) as well as hexatriacontane (h-HTC) and fully deuterated hexatriacontane (d-HTC) as low-molecular weight model for PE. H-D exchange was assumed and detected by Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS), X-ray Photoelectron Spectroscopy (XPS), Attenuated Total Reflectance (ATR-FTIR) and 1 H and 2 H Nuclear magnetic Resonance. Results show a significant H-D exchange within the sampling depth of ATR (2.5 lm). However, N-and NH 2 introduction was limited to the topmost surface as shown by SIMS and XPS (a few nanometers).

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“…Polyethylene and polypropylene foils were measured with XPS and ToF-SIMS as described in part 1 [46]. Additionally, C, H, N-analysis and 1 H and 2 H-NMR were performed.…”

Section: Methodsmentioning

confidence: 99%

“…deuterated polyethylene (d-PE) foils exposed to ammonia plasma was obtained from ToF-SIMS analysis (for details see [46]). The introduction of N-functionalities was also studied by this approach.…”

Section: Specific Information On H-d Exchange In Polypropylene (H-pp)mentioning

confidence: 99%

Significance of Hydrogen–Deuterium Exchange at Polyolefin Surfaces on Exposure to Ammonia Low-Pressure Plasma

Wettmarshausen

Min

Unger

et al. 2011

Plasma Chem Plasma Process

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“…This issue is illustrated in Figure with the peak at m/z 30.043, whose possible identifications are C 2 DH 4 + , C 2 D 2 H 2 + , and C 2 D 3 + because of the uncertainty on the H isotope content. The most probable structure for the ion is considered the one containing the lowest number of deuterium atoms . Second, the intensities of the characteristic molecular fragment ions of the pristine polymer, such as C 2 H 5 + , C 3 H 5 + , C 3 H 7 + , C 4 H 7 + , and C 4 H 9 + , decrease in the treated PEs.…”

Section: Resultsmentioning

confidence: 99%

“…In that investigation, H 2 O was replaced by D 2 O in order to discriminate the H contributions coming from the polymer itself and the atmospheric moisture from the water deliberately mixed to the plasmogen gas. This approach exploited the high sensitivity and selectivity of the SIMS technique for the detection of H isotopes contained in molecular ion fragments present in the outermost layer of the specimen, a capability that is out of reach of XPS . The H‐D exchange in the surface region was thoroughly studied.…”

Section: Introductionmentioning

confidence: 99%

Molecular Surface Analysis and Depth-Profiling of Polyethylene Modified by an Atmospheric Ar-D₂O Post-Discharge

Cristaudo

Collette

Tuccitto

et al. 2016

Plasma Process. Polym.

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The injection of water vapor into ambient “open air” plasmas for the treatment of polymers represents a promising functionalization route for industrial and medical applications. The present study reports a scientist‐independent methodology, based on the ToF‐SIMS (time‐of‐flight secondary ion mass spectrometry) technique coupled with PCA/Wavelet‐PCA (principal component analysis), to probe the (sub) surface chemical/structural modifications induced by an atmospheric Ar‐D2O post‐discharge on low density polyethylene (LDPE) films as a function of two external plasma parameters, namely sample‐torch distance and treatment time. The SIMS characterization identifies two different families of samples (type I and II) as a function of time and distance. The highest reactivity of the D2O vapors with the LDPE films is achieved for times of few tens of seconds at a distance of 5 mm from the plasma source.

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“…ToF–SIMS was chosen for the surface and in‐depth analysis because it is the only surface technique possessing sufficient sensitivity and selectivity to the hydrogen isotopes as elements and in molecular fragments . This capability has been already exploited in surface studies of deuterated or H–D exchanged polymer surfaces, where the group of Friedrich and Unger modified PE and deuterated PE using low pressure NH 3 and ND 3 plasma, but not upon molecular depth‐profiling. Here, capitalizing on the advent of Ar cluster ion beams for sample sputtering, the modifications of the polymer molecular structure will also be followed along the sample depth .…”

Section: Introductionmentioning

confidence: 99%

Surface Analysis and Ultra‐Shallow Molecular Depth‐Profiling of Polyethylene Treated by an Atmospheric Ar‐D₂O Post‐Discharge

Cristaudo

Collette

Poleunis

et al. 2015

Plasma Processes & Polymers

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In an original approach to trace water reactivity upon surface treatment by ambient “open air” plasma, the H–D exchange processes induced in polyethylene by an Ar‐D2O post‐discharge are investigated using time‐of‐flight secondary ion mass spectrometry, both at the surface and along the sample depth. The surface characterization points out the strong influence of the sample‐torch distance. The most important chemical modifications, excluding polymer overheating, occur at 5 mm of distance, with 25% of deuterated monomer units at the surface. For the first time, ultra‐shallow molecular depth‐profiling by Ar noble gas clusters shows the detailed variation of the deuteration of the polymer repeat unit in the topmost surface layer. Our results indicate that the fraction of deuterated monomer units is reduced by a factor >2 over a depth of ∼3 nm.

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A ToF-SIMS study of the deuterium—hydrogen exchange induced by ammonia plasma treatment of polyolefins

Cited by 18 publications

References 36 publications

Significance of Hydrogen–Deuterium Exchange at Polyolefin Surfaces on Exposure to Ammonia Low-Pressure Plasma

Significance of Hydrogen–Deuterium Exchange at Polyolefin Surfaces on Exposure to Ammonia Low-Pressure Plasma

Molecular Surface Analysis and Depth-Profiling of Polyethylene Modified by an Atmospheric Ar-D₂O Post-Discharge

Surface Analysis and Ultra‐Shallow Molecular Depth‐Profiling of Polyethylene Treated by an Atmospheric Ar‐D₂O Post‐Discharge

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A ToF-SIMS study of the deuterium—hydrogen exchange induced by ammonia plasma treatment of polyolefins

Cited by 18 publications

References 36 publications

Significance of Hydrogen–Deuterium Exchange at Polyolefin Surfaces on Exposure to Ammonia Low-Pressure Plasma

Significance of Hydrogen–Deuterium Exchange at Polyolefin Surfaces on Exposure to Ammonia Low-Pressure Plasma

Molecular Surface Analysis and Depth-Profiling of Polyethylene Modified by an Atmospheric Ar-D2O Post-Discharge

Surface Analysis and Ultra‐Shallow Molecular Depth‐Profiling of Polyethylene Treated by an Atmospheric Ar‐D2O Post‐Discharge

Contact Info

Product

Resources

About

Molecular Surface Analysis and Depth-Profiling of Polyethylene Modified by an Atmospheric Ar-D₂O Post-Discharge

Surface Analysis and Ultra‐Shallow Molecular Depth‐Profiling of Polyethylene Treated by an Atmospheric Ar‐D₂O Post‐Discharge