一般財団法人材料科学技術振興財団　MST List of Products and Services

Residue from adhesive tape can cause poor adhesion and peeling during the manufacturing process. When residue is suspected to be the cause of defects, TOF-SIMS, which can analyze the composition and distribution of surface contaminants, is effective. We will present a case where the surface of a silicon wafer was adhered with adhesive tape and measured with TOF-SIMS after peeling it off.

By combining TG-DTA (thermogravimetric-differential thermal) analysis with GC/MS analysis, it is possible to select optimal temperature conditions to identify unknown polymer materials and the volatile organic compounds they contain. By investigating the pyrolysis temperature of the plastic parts of commercial products and continuously performing GC/MS measurements under two conditions—gentle heating below the pyrolysis temperature (thermal desorption method) and subsequent rapid heating at high temperatures (pyrolysis method) using the double-shot method—it was determined that this plastic is AS resin and contains the antioxidant additive IRGANOX 1076.

Plastic consists of a crystalline portion where polymer chains are arranged in an orderly manner and an amorphous portion where polymer chains are randomly present. The mechanical strength, density, and thermal properties of crystalline plastics are greatly influenced by the degree of crystallinity, making it important to understand this degree. In this study, we investigated the changes in crystallinity of polypropylene films, which are crystalline plastics, by conducting XRD measurements while increasing the temperature.

Samples such as lithium-ion secondary battery materials that deteriorate when exposed to the atmosphere, and organic materials that change due to heat during processing and observation, are difficult to observe structurally using TEM under normal environmental conditions. Our organization has established a system that controls the atmosphere to minimize exposure to air, and further cools the samples for processing, observation, and analysis, allowing us to prepare TEM thin film samples while preserving the original structure of the samples for observation and analysis.

Samples such as lithium-ion secondary battery materials that deteriorate when exposed to the atmosphere and organic materials that change due to heat during processing and observation have made it difficult to observe their original structures using TEM and SEM. By observing them with a high-resolution SEM equipped with FIB under controlled atmospheres without exposure to the air, we can understand the original states of particles and electrolytes. Additionally, it is compatible with cooling, which helps to suppress deterioration caused by heat.

Pyrolysis GC/MS is a gas chromatography-mass spectrometer equipped with a pyrolysis device in the sample introduction section. For polymer materials that previously required complex pretreatment, samples can now be introduced into the GC for analysis without pretreatment by heating and decomposing them with the pyrolysis device. Additionally, by varying the temperature conditions of the pyrolysis device and the sampling conditions (double-shot method), it is possible to obtain two different types of information, such as additives and polymer materials, separately from the same sample, making the analysis of unknown polymer materials easier.

For the two-component mixed epoxy resin, we investigated the curing temperature and the glass transition temperature (Tg), which is an indicator of heat resistance, using Differential Scanning Calorimetry (DSC). When measuring the resin before curing with DSC, it was confirmed that a rapid exothermic reaction began around 103°C (Figure 1). This was due to the polymerization (curing) of the resin occurring as a result of the temperature increase. Furthermore, after air cooling the cured resin to room temperature, a second DSC measurement was conducted, which confirmed a shift of the baseline towards the endothermic side due to the glass transition of the resin, with Tg being approximately 116°C (Figure 2).

Chitosan is used in a wide range of fields such as medicine, food, cosmetics, and clothing due to its antibacterial and moisturizing properties. Some cotton swabs, which are everyday items, contain chitosan to provide antibacterial effects. Therefore, we evaluated the chitosan contained in cotton swabs using TOF-SIMS, which allows for visualization through mapping and component assessment through spectral measurement.

Polyimide is a material that is used in various fields, including electronic components, due to its high heat resistance and excellent electrical insulation properties. Since surface modification can enhance adhesion to other materials, it is important to understand the state of the modified layer. In this study, TOF-SIMS measurements were conducted under sputtering conditions that minimize the degradation of organic components, allowing for the evaluation of polyimide components in the depth direction. Using GCIB (Ar cluster) for sputtering enables the measurement of the targeted organic components in the depth direction. *GCIB: Gas Cluster Ion Beam

On the surface of cell culture dishes, treatments are performed to convert hydrophobic plastic surfaces to hydrophilic ones in order to enhance cell adhesion. In this study, the surfaces of dishes that underwent hydrophilic treatment were evaluated using XPS and TOF-SIMS, revealing an increase in OH and CHO groups. By conducting quantitative evaluations with XPS and qualitative evaluations with TOF-SIMS, it is possible to capture how the surface has changed.

XRF is an analytical method used to evaluate the composition and distribution of constituent elements. A notable feature is that it does not require any special pretreatment for measurements, and it can be performed non-destructively over a wide range from 1.2 mm to several centimeters. As an example of elemental analysis using XRF, we will introduce a case where measurements were conducted focusing on the metal components contained in polymer materials of chemical storage containers, investigating metal contamination that adhered to the container surface during the storage period.

PET bottles allow a small amount of air (oxygen) to permeate, making the beverages inside susceptible to the effects of oxygen intrusion from the outside, which leads to a deterioration in quality. To address this, various innovations have been made in PET bottles. For example, by inserting an oxygen-absorbing layer between the PET layers, as shown in Figure 1, the deterioration of beverages is prevented, preserving their taste. This document presents the results of analyses conducted using TOF-SIMS to confirm what the oxygen-absorbing layer is composed of.

The surface shape of foundation puffs and the adhesion of cosmetics were evaluated using a digital microscope. The digital microscope has a greater depth of field compared to optical microscopes, allowing for accurate observation of large uneven objects that could not be focused on with a microscope. The observation results of commercially available foreign puffs are shown in Figures 1 to 4. The surface shape of the puffs and the adherence of the foundation can be confirmed. Additionally, as shown in Figure 5, it is also possible to directly observe the surface of the hand.

The functionality of films is known to be determined by factors such as material, thickness, and layer structure. In this study, we evaluated the layer structure of polyethylene-based multilayer films commonly used as food wrap. By confirming that the film is primarily composed of polyethylene using FT-IR, and employing GCIB (Ar cluster) for sputtering, we were able to clearly visualize the structure where polyethylene and nylon 6 are layered within a thickness of 10μm through depth profiling with TOF-SIMS.

Ion chromatography is a method for detecting ionic components in liquid samples. Additionally, these components that adhere to the surface of solids (materials) are measured by extracting them by immersing in pure water. MST enables qualitative and quantitative analysis of ions and organic acids contained in liquid samples, evaluation of the amount of ions eluted from material surfaces, and investigation of the causes of material corrosion.

Acrylic resin has superior processability, transmittance, and safety compared to silicate glass, making it widely used as organic glass for windows in aircraft and automobiles, optical instruments such as lenses and prisms, medical materials, daily necessities, and crafts. Mass spectra of representative standard acrylic reagents were obtained using TOF-SIMS. In MST, by comparing the mass spectrum of the analyte with that of the standard reagent, it is possible to estimate the acrylic resin from the detected fragment ions.

Polycarbonate (PC) is a type of thermoplastic that has excellent transparency, impact resistance, and heat resistance. It has been reported that degradation occurs due to hydrolysis, leading to the generation of the raw material bisphenol A (BPA). Particularly in solar panels, it is important to understand how the surface of the material changes under UV (ultraviolet) irradiation. Below, we present a case study that evaluated the degree of degradation of the PC surface due to UV irradiation using TOF-SIMS.

In controlling properties such as adhesion and wettability of polymer films, it is very important to quantitatively evaluate the polar functional groups (alcohol groups) present on the surface. XPS is optimal for quantitative evaluation; however, it is difficult to separate and quantify the adjacent oxidation state (C-O-C) and hydroxyl state (C-OH). In MST, after selectively reacting only the alcohol groups using a chemical modification method on polyvinyl alcohol (PVA), it is possible to quantify them using XPS. We present a case where the alcohol groups in PVA were chemically modified and evaluated using trifluoroacetic anhydride (TFAA). Measurement method: XPS, chemical modification Product fields: Electronic components, daily necessities Analysis purpose: Composition evaluation, identification, chemical bonding state evaluation For more details, please download the materials or contact us.

The state of the water-repellent surface in water-repellent treatment differs based on whether fluorine-based compounds are distributed in an island-like manner or uniformly. Therefore, we conducted observations of the distribution of fluorine-based compounds using TOF-SIMS. As a result, it was found that they are distributed unevenly. Additionally, by performing qualitative analysis in a 1μm square area, it was determined that the fluorine-based film is Krytox. Measurement method: TOF-SIMS Product field: Electronic components and daily necessities Analysis purpose: Composition evaluation, identification, composition distribution evaluation For more details, please download the materials or contact us.

Organic acids such as citric acid and malic acid are widely used in various fields, including the semiconductor industry as additives in etching and plating solutions, as well as in food as sour agents and emulsifying stabilizers. In particular, the concentration of organic acids in plating solutions changes over time during use, and this balance affects the quality of the plating, making precise control important. Here, we will introduce a case study of organic acid analysis using IC (ion chromatography).

Polycarbonate (PC) is a type of thermoplastic that has excellent transparency, impact resistance, and heat resistance, and is widely used as a material for solar panels, eyeglass lenses, CDs, automotive parts, and medical devices. In this study, TOF-SIMS analysis was conducted using GCIB (Ar cluster) with a sputter ion beam to evaluate the degradation layer on the surface of PC. *Note: GCIB stands for Gas Cluster Ion Beam.*

Linear alkylbenzene sulfonic acid and its salts (LAS) are considered substances of concern due to their potential impact on living organisms. Therefore, they have been added to the environmental standards related to the conservation of aquatic organisms within the environmental standards concerning the preservation of living environments affected by water pollution, and a standard value has been established (March 27, 2013). Since approximately 90% of the usage of LAS is for household detergents, measurements were conducted on existing household detergents and household wastewater, and a comparison of the distribution of LAS alkyl chain lengths (C10 to C14) was performed.

Geosmin and 2-methylisoborneol (2-MIB) are produced by cyanobacteria or actinomycetes and are considered substances that cause odor and taste disturbances in drinking water sourced from surface water such as dams, lakes, and rivers, as well as being known as substances that cause musty odors. This case presents the results of measuring geosmin and 2-MIB contained in water. Detection at ppt (ng/L) levels is possible using GC/MS.

Food wrap films may use additives to ensure stability against thermal exposure during the manufacturing process and to impart plasticity. These additives are required to remain stable under cooking conditions without changing. In this case, we present the results of an investigation using TOF-SIMS to examine whether the state of one of the additives, Irgafos168, changes (bleeds out) before and after heating. *GCIB: Gas Cluster Ion Beam

Regarding foreign substance analysis, it has traditionally been difficult to analyze using microscopic FT-IR analysis or Raman analysis due to the influence of the substrate. However, with the introduction of micro-sampling tools, it has become possible to reduce that influence. We will introduce examples of analysis for two types of foreign substances.

DLC (diamond-like carbon) films, which are widely used as coating materials in various fields, are composed of a mixture of carbon elements with sp3 hybrid orbitals corresponding to a diamond structure and carbon elements with sp2 hybrid orbitals corresponding to a graphite structure when viewed from a microscopic perspective. One indicator that determines the properties of DLC films is the sp2/(sp2+sp3) ratio. High-precision quantification of the sp2/(sp2+sp3) ratio in DLC films is possible using XAFS.

Due to its characteristics such as high hardness and high wear resistance, DLC (diamond-like carbon) films are utilized in a wide range of fields. These films are materials that lie between graphite and diamond, and the separation of sp2 (graphite structure) and sp3 (diamond structure) within the film to obtain the sp2/(sp2+sp3) ratio is one of the important factors that determine the properties of the film. Here, we will introduce an example of evaluating this sp2/(sp2+sp3) ratio by analyzing the C1s spectrum using XPS.

In XPS analysis, the binding state evaluation of the material surface is conducted by observing the energy of photoelectrons obtained through X-ray irradiation. It allows for the assessment of whether metal elements are in an oxidized state, and for elements with significant energy shifts (chemical shifts) due to oxidation, it also enables the evaluation of the presence and proportion of multiple valences. Below are the main metal elements and oxides for which multiple valence evaluations are possible.

In this case, we used fabric that had absorbed tobacco odor and measured the differences in odor components with and without the use of deodorant spray using GC/MS. Since tobacco odor is composed of many components, we focused on the peaks that were reduced by the deodorant among the detected peaks for analysis. As a result, a decrease in three odor components characteristic of tobacco odor was confirmed. Additionally, it is possible to verify the effectiveness of deodorants and air purifiers against various other odors beyond this case.

Self-assembled monolayers (SAMs), which are oriented organic films, have their functions and properties, such as surface wettability and adsorption, altered by orientation and orientation angle. Using XAFS with synchrotron radiation, it is possible to evaluate the orientation and orientation angle of organic film materials by analyzing the X-ray incidence angle dependence of peak intensity.

The electron diffraction method using an electron microscope is classified into three types based on the way the electron beam is incident on the sample. The characteristics of each type and examples of data are presented. It is necessary to choose the appropriate method according to the size of the evaluation object and the analysis purpose.

Volatile organic compounds (VOCs) are used during the cleaning of semiconductors and industrial products and may be present in trace amounts in cleaning water, etc. VOCs in water are a concern because even in trace amounts, they can cause odors and health issues. Therefore, environmental standards and discharge standards have been established, and methods capable of measuring low concentrations are required. This case presents an example of detecting trace VOC components (sub-ppb level) in water by introducing components concentrated by P&T (Purge & Trap) into GC/MS.

Nitrogen is utilized in various forms across a wide range of fields including chemistry, materials, food, and pharmaceuticals. Nitrogen compounds consist of inorganic nitrogen compounds such as nitrates, nitrites, and ammonia, as well as organic nitrogen compounds like amino acids. In the case of samples in aqueous solution, inorganic nitrogen compounds such as nitrate ions, nitrite ions, and ammonium ions can be evaluated using ion chromatography, while organic nitrogen can be assessed using HPLC or LC/MS. Total nitrogen, which includes both inorganic and organic nitrogen compounds, can be evaluated using spectrophotometry.

Coatings are used for various purposes such as coloring, protecting, and imparting functions by applying them to the surface of the target material. In any case, it is required that the coating is applied to the target material without poor adhesion. In this document, we applied conductive paint on two types of substrates: stainless steel and organic film, and observed the state of the paint-substrate interface using cryo-SEM.

Conductive paints are used to impart conductivity to insulating materials. Additives are included in the paint to give conductivity to the originally insulating paint itself. This document evaluates two types of conductive paints with different conductivities, focusing on the shape and composition of the additives in the paint, as well as the dispersion state of the additives.

When conducting structural analysis of condensation-type polymers such as polyurethane, information may not be sufficiently obtained using only thermal decomposition GC/MS. In such cases, performing chemical decomposition using methanol can provide more detailed structural information. This case presents the results of decomposing polyurethane-based lightweight aggregate with methanol and conducting GC/MS measurements. Diphenylmethane diisocyanate, dimethyl phthalate, trimethylolpropane, and propylene glycol compounds were detected, leading to the conclusion that this product is composed of polyester urethane made from these materials.

The ionization method for LC/MS is commonly ESI (Electrospray Ionization). In ESI, if low-polarity components cannot be ionized, APCI (Atmospheric Pressure Chemical Ionization) is available as a highly sensitive detection method. It is important to choose the optimal ionization method according to the target components in order to obtain data that aligns with the objectives.

Many additives, including plasticizers, are used in polymer materials such as resin products. We present a case study on the qualitative analysis of additives contained in commercially available PVC resin. The components eluted by immersion in an organic solvent were qualitatively analyzed using LC/MS. As a result, components estimated to be DEHP (DOP) as a plasticizer and epoxy fat (plasticizer/stabilizer) were detected. By using standard samples, it is also possible to quantify each detected additive component.

When analyzing additives used in polymer materials such as resin products, it is necessary to separate the polymer materials from the additives. We will introduce a case where a sample pre-treated using the "dissolution-reprecipitation method," which involves dissolving commercially available resin products in a solvent and then precipitating the polymer components to extract the additive components, was analyzed. The results of the LC/MS analysis indicated that a component with a high abundance (m/z=548.50) was estimated to be a type of phenolic antioxidant through LC/MS/MS analysis.

Color printers use ink to print on the surface of paper. The ink contains dyes and pigments, which have characteristic molecular information based on their colors. By visualizing this molecular information, it becomes possible to obtain information about the distribution of ink components on the paper surface and how deeply the ink components penetrate into the paper cross-section. Below, I will summarize the "imaging results of the paper surface" visualized by TOF-SIMS. TOF-SIMS can perform image analysis of molecular information ranging from 10 μm to 3 cm square.

The sample concentration needle is a device that concentrates volatile components by sucking them from vials or sampling bags and adsorbing the volatile components passing through the needle onto an adsorbent medium, which is then introduced into GC/MS. There are different adsorbent media available, such as "for organic solvents," "for fatty acids," and "for amines," which are used depending on the target components. In the headspace method used for the analysis of volatile components, it is common to heat the sample to obtain sensitivity; however, in analyses using the sample concentration needle, heating is not necessary, allowing only the volatile components to be supplied for GC/MS analysis at room temperature.

When conducting structural analysis of condensation-type polymers such as polyester, the conventional thermal decomposition GC/MS method may result in complex decomposition products that do not allow for structural estimation. In such cases, the reactive thermal decomposition GC/MS method, which involves the coexistence of derivatization reagents during thermal decomposition, is effective. This example introduces the thermal decomposition of polyethylene terephthalate (PET) in the presence of tetramethylammonium hydroxide. While numerous peaks were observed with the conventional thermal decomposition method, the reactive thermal decomposition method detected simpler decomposition products that reflected the monomer structure.

TOF-SIMS is a highly effective method for investigating the causes of foreign substances, contamination, and discoloration in various processes, as it allows for localized analysis of specific areas and simultaneous analysis of elemental composition and molecular information of organic and inorganic substances through the obtained mass spectrum. Additionally, it enables image analysis, making the visualization of molecular information of organic substances possible. This document summarizes the analysis results of discoloration in clean suits, which are textile products. From the qualitative results obtained by TOF-SIMS, it was inferred that the discolored areas may be due to sebum.

One method to obtain the temperature profile of gases generated during sample heating is the EGA-MS method. However, this method introduces the generated gases into the mass spectrometer as a mixture without passing through a GC column, making it difficult to identify the compounds. In such cases, by trapping the gases once and performing GC/MS measurements using the heart-cut EGA method, it becomes possible to separate and identify the compounds. This example presents a case where polyvinyl acetate was measured using the heart-cut EGA method, revealing differences in the decomposition mechanisms depending on the heating temperature.

TOF-SIMS is an effective method for evaluating distribution, as it can simultaneously analyze elemental composition and molecular information of organic and inorganic substances, as well as perform imaging analysis. This document presents a case study analyzing the inner wall of a nozzle. The distribution of the nozzle surface and inner wall was confirmed, and the presence or absence of peaks at various locations was verified. Measurement method: TOF-SIMS Product field: Manufacturing equipment, parts, daily goods Analysis purpose: Composition distribution evaluation For more details, please download the document or contact us.