Hydroxylation of the silica in microfabricated thin layer chromatography plates as probed by time‐of‐flight secondary ion mass spectrometry and diffuse reflectance infrared Fourier transform spectroscopy

Microfabricated silica thin layer chromatography (TLC) plates have previously been prepared on patterned carbon nanotube forests. The high temperatures used in their fabrication reduce the number of hydroxyl groups on their surfaces. Fortunately, silica can be rehydroxylated. In diffuse reflectance infrared Fourier transform spectroscopy (DRIFT), a silanol peak below 3740 cm^?1 indicates a well‐hydroxylated silica surface that is fit for chromatography. Hydroxylations of our materials with HF are so effective that it is not possible to discern the position of this peak. In contrast, this signal is discernable when the plates are treated with NH₄OH. To find a more convenient method for studying the surfaces of TLC plates, time‐of‐flight secondary ion mass spectroscopy (ToF‐SIMS) was considered. ToF‐SIMS is advantageous because multiple microfabricated TLC plates must be scraped to obtain enough silica for one DRIFT analysis, while static SIMS can be performed on very small regions (500 × 500 µm² or less) of individual plates. Ratios of the SiOH⁺ and Si⁺ ToF‐SIMS signals for microfabricated TLC plates correlated well with ~3740 cm^?1 silanol peaks from DRIFT. Thus, SIMS allows direct analysis of all of our treated and untreated plates, including those hydroxylated with HF. The best hydroxylation condition for HF, which was better than any studied for NH₄OH, was around 150 ppm at room temperature. The best hydroxylation condition for NH₄OH was 50 °C for 72 h. ToF‐SIMS versus DRIFT results of commercial TLC plates were also obtained and evaluated. Copyright © 2014 John Wiley & Sons, Ltd.     

Quantitative analysis of styrene‐pentafluorostyrene random copolymers by ToF‐SIMS and XPS

Poly(styrene) (PS), poly(2,3,4,5,6‐pentafluorostyrene) (5FPS) and their random copolymers were prepared by bulk radical polymerization. The spin‐cast polymer films of these polymers were analyzed using X‐ray photoelectron spectroscopy (XPS) and time‐of‐flight secondary ion mass spectrometry (ToF‐SIMS). The surface and bulk compositions of these copolymers were found to be same, implying that surface segregation did not occur. The detailed analysis of ToF‐SIMS spectra indicated that the ion fragmentation mechanism is similar for both PS and 5FPS. ToF‐SIMS quantitative analysis using absolute peak intensity showed that the SIMS intensities of positive styrene fragments, particularly C₇H₇⁺, in the copolymers are higher than the intensities expected from a linear combination of PS and 5FPS, while the SIMS intensities of positive pentafluorostyrene fragments are smaller than expected. These results indicated the presence of matrix effects in ion formation process. However, the quantitative approach using relative peak intensity showed that ion intensity ratios are linearly proportional to the copolymer mole ratio when the characteristic ions of PS and 5FPS are selected. This suggests that quantitative analysis is still possible in this copolymer system. Copyright © 2005 John Wiley & Sons, Ltd.     

Repair of defects created by Ar+ sputtering on graphite surface by annealing as confirmed using ToF‐SIMS and XPS

Defects were created on the surface of highly oriented pyrolytic graphite (HOPG) by sputtering with an Ar⁺ ion beam, then characterized using X‐ray photoelectron spectroscopy (XPS) and time‐of‐flight secondary ion mass spectrometry (ToF‐SIMS) at 500°C. In the XPS C1s spectrum of the sputtered HOPG, a sp³ carbon peak appeared at 285.3 eV, representing surface defects. In addition, 2 sets of peaks, the C_x⁻ and C_xH⁻ ion series (where x = 1, 2, 3...), were identified in the ToF‐SIMS negative ion spectrum. In the positive ion spectrum, a series of C_xH₂^+• ions indicating defects was observed. Annealing of the sputtered samples under Ar was conducted at different temperatures. The XPS and ToF‐SIMS spectra of the sputtered HOPG after 800°C annealing were observed to be similar to the spectra of the fresh HOPG. The sp³ carbon peak had disappeared from the C1s spectrum, and the normalized intensities of the C_xH⁻ and C_xH₂^+• ions had decreased. These results indicate that defects created by sputtering on the surface of HOPG can be repaired by high‐temperature annealing.     

Surface studies of polyethers with well‐defined segmental length

Two series of polyethers were synthesized by the polymerization of 1, n‐dibromoalkane (n = 4, 6, 8, 10, 12, 14 and 18) with bisphenol‐A (BA) and 4, 4'‐(hexafluoroisopropylidene) diphenol‐A. The length of the flexible aliphatic segment changes from 4 Å to 21 Å (corresponding to 4 to 18 CH₂ groups). X‐ray photoelectron spectroscopy (XPS), time‐of‐flight secondary ion mass spectrometry (ToF‐SIMS) and atomic force microscopy (AFM) were used to characterize the surfaces of the polyethers. The influence of the length of the flexible aliphatic segments on the surface composition of the BA and 6FBA polyethers was investigated. The intensity ratios of the characteristic SIMS peaks of the flexible segments to those of the rigid segments were related to the length of the flexible segments and the XPS results confirmed that the SIMS intensity ratios can be used to determine the surface compositions. AFM was utilized to investigate the crystallization process of the BA polymer with n = 8. The appearance of nuclei, the generation of primary lamellae and the formation of spherulites were observed dynamically. Nuclei appeared first as 10 nm dots, some disappeared and a few could grow into lamellae. The lamellae that developed from the nuclei bred more lamellae, which in turn induced secondary nucleation and branching of lamellae and finally led to a spherical appearance.     

Effects of Ar‐ and Ar/O2‐plasma‐treated amorphous and crystalline polymer surfaces revealed by ToF‐SIMS and principal component analysis

The effects of argon (Ar) and a mixture of Ar and oxgyen(Ar/O₂) plasmas on amorphous and semi‐crystalline poly(bisphenol A hexane ether) thin films were investigated by time‐of‐flight secondary ion mass spectroscopy (ToF‐SIMS) and principal component analysis (PCA). PCA results of the ToF‐SIMS spectra indicate that an Ar/O₂ plasma produced less physical sputtering and had a higher chemical reactivity than did an Ar plasma, regardless of whether an amorphous or a crystalline surface was involved. However, the chemical differences between the Ar‐ and Ar/O₂‐plasma‐treated semi‐crystalline films were much smaller. The observed results can be explained by the higher resistance of the polymer crystalline regions to physical sputtering and chemical etching. Copyright © 2013 John Wiley & Sons, Ltd.     

ToF‐SIMS multivariate characterization of surface modification of polymers by N2?H2 atmospheric pressure dielectric barrier discharge

Time of flight secondary ion mass spectrometry (ToF‐SIMS) is a powerful tool for the surface characterization of plasma‐modified surface. However, the SIMS fragmentation patterns of the resulting surface are quite complex and a full interpretation may be prohibitive. As a result, many studies are turning to multivariate statistical methods to simplify the interpretation. In this study, a principal component analysis (PCA) was used to obtain a more detailed interpretation of the surface modification of polymers by an atmospheric pressure plasma. The dataset was obtained from three polymers with different chemical compositions [namely, polyethylene, polyvinylidene fluoride, and poly(tetrafluoroethylene)], where each material was treated with an atmospheric pressure dielectric barrier discharge (DBD) in an atmosphere composed of different N₂/H₂ ratios. The results are discussed in terms of the suitability of ToF‐SIMS analysis combined with PCA for the discrimination between the three polymers and the possibility to create a predictive model that would describe the plasma surface modification, independent of the polymer substrate chemical composition. Copyright © 2010 John Wiley & Sons, Ltd.     

The initial oxidation of polycrystalline thorium

The initial oxidation of clean, polycrystalline α‐Th from background CO/CO₂ and saturation of the Th surface by O₂ has been examined by angle‐resolved Auger electron spectroscopy (ARAES) and time of flight secondary ion mass spectrometry (ToF‐SIMS). Following dissociative adsorption of very low doses of background CO/CO₂ (<1 L), the carbon surface population was dominant and spontaneously formed thorium carbide. The accompanying oxygen population increased at a rate roughly one‐third that of the carbon, suggesting simultaneous oxygen incorporation into the bulk. To further corroborate the surface kinetics of adsorbed oxygen, O₂ was admitted, following heating and sputter cleaning of the Th; some oxygen atoms continued to diffuse into the bulk until formation of stoichiometric ThO₂ at ～37 L. ARAES measurements showed an oxygen concentration gradient in the near‐surface region confirming rapid oxygen incorporation at low doses; however, once the surface is saturated, virtually no variation in the oxygen intensity is observed. AES and ToF‐SIMS depth profiling revealed complete oxide formation to a depth of 2 nm. Copyright © 2010 John Wiley & Sons, Ltd.     

Tailoring the surface chemistry of carbon fiber and E‐glass composites for improved adhesion

The main challenges in the manufacture of composite materials are low surface energy and the presence of silicon‐containing contaminants, both of which greatly reduce surface adhesive strength. In this study, carbon fiber (CF) and E‐glass epoxy resin composites were surface treated with the Accelerated Thermo‐molecular adhesion Process (ATmaP). ATmaP is a multiaction surface treatment process where tailored nitrogen and oxygen functionalities are generated on the surface of the sample through the vaporization and atomization of n‐methylpyrrolidone solution, injected via specially designed flame‐treatment equipment. The treated surfaces of the polymer composites were analyzed using XPS, time of flight secondary ion mass spectrometry (ToF‐SIMS), contact angle (CA) analysis and direct adhesion measurements. ATmaP treatment increased the surface concentration of polar functional groups while reducing surface contamination, resulting in increased adhesion strength. XPS and ToF‐SIMS showed a significant decrease in silicon‐containing species on the surface after ATmaP treatment. E‐glass composite showed higher adhesion strength than CF composite, correlating with higher surface energy, higher concentrations of nitrogen and C?O functional groups (from XPS) and higher concentrations of oxygen and nitrogen‐containing functional groups (particularly C₂H₃O⁺ and C₂H₅NO⁺ molecular ions, from ToF‐SIMS). Copyright © 2010 John Wiley & Sons, Ltd.     

ToF‐SIMS studies of the oxidation of Fe by D2O vapour: comparison with XPS

The oxidation of iron (Fe) by water (D₂O) vapour at low pressures and room temperature was investigated using time‐of‐flight (ToF) SIMS. The results supported those found previously using XPS and the QUASES^? program in that a duplex oxide structure was found containing a thin outer surface hydroxide (Fe(OD)₂) layer over an inner oxide (FeO) layer. The extraordinary depth resolution of the ToF‐SIMS profiles assisted in identifying the two phases; this resolution was achieved by compensation for surface roughness. A substantial concentration of deuterium was found in the subsurface oxide layer. This observation confirmed previous assessments that the formation of FeO was from the reaction of Fe(OD)₂ with outward‐diffusing Fe, leaving deuterium as a reaction product. Copyright © 2005 John Wiley & Sons, Ltd.     

Extraction of hidden information of ToF‐SIMS data using different multivariate analyses

Time‐of‐flight secondary ion mass spectrometry (ToF‐SIMS) is a powerful tool for determining surface information of complex systems such as polymers and biological materials. However, the interpretation of ToF‐SIMS raw data is often difficult. Multivariate analysis has become effective methods for the interpretation of ToF‐SIMS data. Some of multivariate analysis methods such as principal component analysis and multivariate curve resolution are useful for simplifying ToF‐SIMS data consisting of many components to that explained by a smaller number of components. In this study, the ToF‐SIMS data of four layers of three polymers was analyzed using these analysis methods. The information acquired by using each method was compared in terms of the spatial distribution of the polymers and identification. Moreover, in order to investigate the influence of surface contamination, the ToF‐SIMS data before and after Ar cluster ion beam sputtering was compared. As a result, materials in the sample of multiple components, including unknown contaminants, were distinguished. Copyright © 2014 John Wiley & Sons, Ltd.     

Perfluorinated polymer surfaces comprising SF5-terminated long-chain perfluoroacrylate

A new perfluorinated acrylate monomer containing the SF₅(CF₂)₆-perfluorinated side chain was synthesized and polymerized into films. Bulk monomer characterization is consistent with the molecular structure based on FTIR, mass spectrometry and NMR analyses. The surface properties of polymer coatings were studied with aqueous wetting (contact angle) and X-ray photoelectron spectroscopy (XPS) methods. The surface composition is shown to be highly enriched in the terminal side chain SF₅-chemistry and exhibits properties consistent with a highly apolar, non-wetting perfluorinated polymer surface. Depth-dependent XPS studies using angular-resolved methods (ADXPS) confirmed a non-stoichiometric enrichment of sulfur and fluorine at the film ambient interface, consistent with a surface presence of the terminal SF₅-group and possibly film structural anisotropy in the surface zone. Time-of-flight (TOF) secondary ion mass spectrometry (SIMS) analysis supplements the XPS data by showing the presence of all expected SF₅-acrylate chemistry components in the outer 15 Å of the film surface.     

Photodegradation of poly(ether sulphone) Part 1. A time‐of‐flight secondary ion mass spectrometry study

An extensive study of the surface chemical changes to poly(ether sulphone) (PES) ultrafiltration membranes is made for the first time by the use of time‐of‐flight secondary ion mass spectrometry (ToF‐SIMS) after photoirradiation at 254 nm with irradiances varying from 10 to 300 mJ cm^?2 in a nitrogen atmosphere. Complementary information is provided by analysis with x‐ray photoelectron spectroscopy (XPS) and attenuated total reflectance Fourier transform infrared spectroscopy (ATR‐FTIR). The versatility, superior specificity and sensitivity of using ToF‐SIMS to investigate degradation phenomena are highlighted. The combined results demonstrate that photoirradiation causes a number of chemical changes to the surface: incorporation of oxygen; degradation of the benzene rings and formation of oxidized carbon species; depletion of carbon; reduction of ? SO₂? to some extent; formation of ? OH, C?O and ? SO₃H groups; and probable formation of ? C₆H₄? O? C₆H₅ end‐groups. In addition, no ? OSO₃H groups are formed and no formation of SO₂ is detected. Also, it is shown that chain scission dominates below an irradiation dose of ～200 mJ cm^?2 (at 254 nm in a nitrogen atmosphere). At higher doses, cross‐linking becomes dominant. Copyright © 2004 John Wiley & Sons, Ltd.     

XPS and ToF‐SIMS characterization of a Finemet surface: effect of cooling

The surface composition of amorphous Finemet, Fe₇₃Si_15.8B_7.2Cu₁Nb₃, was studied by X‐ray photoelectron spectroscopy (XPS) and time‐of‐flight secondary ion mass spectrometry (ToF‐SIMS). The as‐received sample in the original state and after Ar⁺ sputter‐cleaning was analyzed at room temperature as well as after cooling to ? 155 °C. In the cooled state, the surface oxide layer composed of oxides of the alloy constituents was found to become enriched with elemental iron and depleted of elemental silicon, boron, oxygen and carbon as compared to the state at room temperature. Interaction of residual water vapor and hydrogen with the complex oxide layer occurring at low temperatures is believed to be responsible for the enhanced formation of surface hydroxides of the alloy constituents. The processes resulting in the observed redistribution of the elements on the surface of Finemet at low temperatures are discussed. Copyright © 2006 John Wiley & Sons, Ltd.     

Thermal desorption characteristics of ammonium nitrate and potassium perchlorate inorganic salts using particle mapping time‐of‐flight secondary ion mass spectrometry

To help optimize ion mobility spectrometry (IMS) for the detection of inorganic explosives, time‐of‐flight secondary ion mass spectrometry (ToF‐SIMS) was used to study the thermal desorption behavior of ammonium nitrate (NH₄NO₃) and potassium perchlorate (KClO₄) particles on surface. This was carried out by ToF‐SIMS chemical imaging analysis to identify the change in the number of particles and their size before and after exposure to desorption temperatures of 150, 200, 250, 300, 350 and 400 °C for durations of 3, 6, 9 and 12 s. It was found that particles less than 7.2 µm in diameter contributed to more than 50% of both the number and mass of the particles desorbed from the surface. Combining ToF‐SIMS particle mapping with the vapor collection experiment revealed that the technique could be used also to determine the optimum desorption temperatures of explosive particles; this was found to be approximately 200 and 300 °C for NH₄NO₃ and KClO₄ particles, respectively. Although work remains to validate this number for KClO₄, experiments using variable desorption temperature IMS suggest the optimum temperature of NH₄NO₃ desorption to be approximately 200 °C. Published 2016. This article is a U.S. Government work and is in the public domain in the USA     

ToF‐SIMS study of 1‐dodecanethiol adsorption on Au,Ag, Cu and Pt surfaces

Time‐of‐flight secondary ion mass spectrometry (ToF‐SIMS) has been used to perform a chemical analysis of long‐chain thiol (CH₃(CH₂)₁₁SH)‐treated gold, silver, copper and platinum surfaces. All the mass peaks from positive and negative ion spectra within the range m/z = 0–2000 u are studied. ToF‐SIMS data revealed that on gold, silver and copper substrates 1‐dodecanethiol form dense standing‐up phases, but on platinum being a catalytically active substrate, we were able to identify also surface‐aligned parallel lying molecules in addition to a standing thiolate layer. Our study shows that when ToF‐SIMS spectra are analyzed, not only the existence of oligomers but also metal + hydrocarbon fragments give information about the order of SAM. Copyright © 2008 John Wiley & Sons, Ltd.     

Detecting changes in arabidopsis cell wall composition using time‐of‐flight secondary ion mass spectrometry

Time‐of‐flight secondary ion mass spectrometry (ToF‐SIMS) was previously used to characterize lignocellulosic materials, including woody biomass. ToF‐SIMS can acquire both rapid spectral and spatial information about a sample's surface composition. In the present study, ToF‐SIMS was used to characterize the cell walls of stem tissue from the plant model organism, Arabidopsis thaliana. Using principal component analyses, ToF‐SIMS spectra from A. thaliana wild‐type (Col‐0), cellulose mutant (irx3), and lignin mutant (fah1) stem tissues were distinguished using ToF‐SIMS peaks annotated for wood‐derived lignocellulose, where spectra from the irx3 and fah1 were characterized by comparatively low polysaccharide and syringyl lignin content, respectively. Spatial analyses using ToF‐SIMS imaging furthermore differentiated interfascicular fiber and xylem vessels based on differences in the lignin content of corresponding cell walls. These new data support the applicability of ToF‐SIMS peak annotations based on woody biomass for herbaceous plants, including model plant systems like arabidopsis. Copyright © 2015 John Wiley & Sons, Ltd.     

Surface characterization of pre‐formed alginate fibres incorporated with a protein by a novel entrapment process

A novel physical entrapment process has been explored as an approach to surface incorporation of proteins within pre‐formed alginate fibres under mild conditions. Entrapment of the protein of choice was achieved by exposing the alginate fibres to a Na⁺‐rich NaCl/CaCl₂ mixture solution, which caused the formation of a moderate dissociation layer into which the protein could diffuse. Subsequent addition of a large excess of multi‐valent cations led to the collapse of the surface and entrapment of the protein within the surface. Bovine serum albumin (BSA) was used as a model protein to investigate the effect of process parameters on the entrapment efficiency. Scanning electron microscopy revealed that there was an increase in the surface roughness and a slight increase in the average diameter of the fibres after protein entrapment. The presence of the protein at the surface of alginates after the entrapment process was confirmed by means of confocal laser‐scanning microscopy, X‐ray photoelectron spectroscopy (XPS) and time‐of‐flight secondary ion mass spectrometry (ToF‐SIMS). The ion exchanges at the surface were evident, as detected by XPS and ToF‐SIMS. It was found that under fixed pre‐swelling conditions, the entrapment efficiency increased with increasing treatment time and, particularly, with protein concentration in the exposure solution. Copyright © 2005 John Wiley & Sons, Ltd.     

Degradation of poly(acrylates) under SF5+ primary ion bombardment studied using time‐of‐flight secondary ion mass spectrometry. 2. Poly(n‐alkyl methacrylates)

Polyatomic primary ions offer low penetration depth and high damage removal rates in some polymers, facilitating their use in the molecular depth profiling of these polymers by secondary ion mass spectrometry (SIMS). This study is the second in a series of systematic characterizations of the effect of polymer chemistry on degradation under polyatomic primary ion bombardment. In this study, time‐of‐flight SIMS (ToF‐SIMS) was used to measure the damage of ～90 nm thick spin‐cast poly(methyl methacrylate), poly(n‐butyl methacrylate), poly(n‐octyl methacrylate) and poly(n‐dodecyl methacrylate) films under extended (～2 × 10¹⁴ ions cm^?2) 5 keV SF₅⁺ bombardment. The degradation of the poly(n‐alkyl methacrylates) were compared to determine the effect of the length of the alkyl pendant group on their degradation under SF₅⁺ bombardment. The sputter rate and stability of the characteristic secondary ion intensities of these polymers decreased linearly with alkyl pendant group length, suggesting that lengthening the n‐alkyl pendant group resulted in increased loss of the alkyl pendant groups and intra‐ or intermolecular cross‐linking under SF₅⁺ bombardment. These results are partially at variance with the literature on the thermal degradation of these polymers, which suggested that these polymers degrade primarily via depolymerization with minimal intra‐ or intermolecular cross‐linking. Copyright © 2004 John Wiley & Sons, Ltd.     

Surface (XPS,SIMS) chemical investigation on poly(pyrrole‐3‐acetic acid) films electrosynthesized on Ti and TiAlV substrates for the development of new bioactive substrates

Electropolymerization of pyrrole‐3‐acetic acid was performed by cyclic voltammetry on titanium and Ti90Al6V4 substrates with the aim of developing a multilayer structure for applications in advanced biomaterials. The polymeric films obtained were characterized by both XPS and time‐of‐flight secondary ion mass spectrometry (ToF‐SIMS). Information on the poly(pyrrole‐3‐acetic acid) (PPy‐3‐acetic) surface structure was achieved by a detailed XPS analysis of C 1s and N 1s signals. The number of COOH groups was quantified by XPS coupled to a chemical derivatization reaction in which esterification with trifluoroethanol was exploited so that the presence of fluorine (or the CF₃ component in C 1s spectra) could be used as a marker for COOH groups. As a result, it was found that more than 90% of the monomer units along PPy‐3‐acetic chains bear carboxylic functionalities, of which 60% are protonated and 40% are present as carboxylate groups. Some decarboxylation occurs with film ageing. The PPy‐3‐acetic films were also investigated by ToF‐SIMS in the negative ion mode, thus obtaining, for the first time, interesting information on the structure of the top surface layers of a polymer belonging to the polypyrrole family. In particular, clusters of peaks related to PPy‐3‐acetic oligomers were detected and the decarboxylation phenomenon on top of the polymer surface was confirmed. Copyright © 2005 John Wiley & Sons, Ltd.     

ToF‐SIMS characterization of glyoxal surface oxidation products by hydrogen peroxide: A comparison between dry and liquid samples

As one of the simplest volatile organic compounds, glyoxal and its oxidation products were considered to be important precursors to aqueous secondary organic aerosol formation. Herein, we analyzed products from glyoxal oxidation by hydrogen peroxide in dry and liquid samples using time‐of‐flight secondary ion mass spectrometry (ToF‐SIMS). ToF‐SIMS spectra and spectral principal component analysis (PCA) were used to investigate surface oxidation products. Dry samples were prepared on clean silicon wafers. Liquid samples consisting of glyoxal and hydrogen peroxide (H₂O₂) were introduced to a vacuum compatible microfluidic reactor prior to UV illumination or dark aging followed by in situ liquid SIMS analysis. A number of reaction products were observed in both dry and liquid samples; different oligomers and carboxylic acids could be formed depending on reaction conditions. In addition, hydrolyzed products were observed in the liquid samples, but not in the dry samples. Although dry samples reveal some products of the aqueous process, they are not fully representative as results from those of the aqueous samples. Our findings suggest that the ability to characterize the liquid surface reaction products provides more realistic information of the reaction products associated with aqueous secondary organic aerosol formation in the atmosphere. Meanwhile, the high mass resolution spectra from the dry sample SIMS measurement are helpful to identify oxidation products in the liquid samples.