Abstract Composites are relevant to high-performance materials in the aerospace sector and have attracted the attention of the scientific and technological communities. Bentonites present very fine granulometry which enables their use in composites. This study showed the development of water absorbent composite based on sodium polyacrylate, bentonite coated by epoxy resin. Since there are gaps in the quantification of composite materials by near-infrared spectroscopy, especially by reflectance analysis (NIRA), this paper shows a quantification methodology (A7200/A5202) of sodium polyacrylate and bentonite. The methodology error found was 1.45% (95% of coefficient of determination). The effectiveness of the developed infrared methodology was verified showing that values are close to the nominal, especially for lower bentonite content. Besides, scanning electron microscopy (SEM) and universal attenuated total reflection (UATR) analysis evidenced the coating with the epoxy resin. Such development ensures rapid and precise methodologies that can be applied to the quality control of composite materials.

ABSTRACT Ethylene-propylene-diene elastomer (EPDM) is employed as thermal insulation for rocket motors, as well as EPDM blends with ethylene vinyl acetate (EVA) have been used in the aerospace industry. The quantification of these blends is more common using Fourier Transform Infrared Spectrometry (FT-IR) by transmission mode, but without discussing sample preparation and methodology error. Considering this fact, a methodology was developed for determining EVA content in binary blend with EPDM samples, by Universal Attenuated Total Reflection (UATR) technique, associated to thermogravimetric analysis (TGA). This last one, it was applied to determine Vinyl Acetate (VA) content in EVA and to identify differences between EPDM/EVA blends. Samples of the analyzed blends showed two VA contents and five proportions of EPDM/EVA: 90/10, 70/30, 50/50, 30/70, and 10/90. The carbonyl stretching vibration band C=O at 1740 cm-1 was used as analytical band in FT-IR quantification. Finally, the results presented excellent accuracy with a good linear correlation coefficient (R > 0.940) and with relative error values lower than 2%, respecting the precision limits of the FT-IR spectrometer.

ABSTRACT When some materials need to be characterized, the hydroxyl number (IOH) determination is especially useful, mainly for those applied in the aerospace field. Usually, this characterization is performed by wet chemistry, using methodologies involving several steps, such as derivatization. This is a time-consuming and costly step. On the other hand, when the analysis is performed by Fourier transform infrared (FT-IR) spectroscopy, the most used region is the medium infrared (MIR) and transmission techniques are usually employed. However, FT-IR methodology developed error is usually not discussed. FT-IR methodology was developed in near infrared (NIR) and MIR regions, including non-conventional techniques, such as universal attenuated total reflection (UATR) and transflectance (near infrared reflection accessory [NIRA]), and transmission, to determine IOH in surfactants, used in aerospace catalysts/cosmetic products, and polyesters, applied in paints. According to the samples’ characteristics, surfactants were analyzed by transmission/solution and, as received, by NIRA. Polyesters were analyzed by UATR and NIRA, as received. The IOH values for all samples were also measured by wet chemistry and/or potentiometry (supplier’s data) and used as reference. Good linear correlations were observed between 0.939 and 0.976, being considered with good precision, and between 88% (NIRA) and 98% (MIR) of the results were explained by developed methodologies.

Abstract Rubber blends are important materials in automotive industry, as well as in other sectors. However, there are implications when suitable use of a polymer in an artifact is not made. In the automotive area, for example, the use of an elastomer without the fuel resistance requirement would result in component degradation, potential fuel leakage, and danger of fire. The use of polymer blends may be the solution to this problem. Fourier transform infrared spectroscopy (FT-IR) can be used for the knowledge of the polymer content of these blends. Then, FT-IR quantitative methodologies for determining acrylonitrile-butadiene copolymer (NBR) copolymer and butadiene-styrene copolymer (SBR) contents were developed by the transflectance accessory, NIRA, and the transmission mode, being the sample analyzed by transmission and universal attenuated total reflection (UATR) in the medium infrared (MIR). UATR and NIRA methodologies showed better accuracy. However, the MIR analysis showed a detection limit between 10-20% of NBR.

Abstract The bicomponent fibers are a special class of fibers that consolidate two polymers in only one fiber in order to explore individual properties of each polymer and can be designed in a spatial configuration that allows the enhancement in application of this material. Thereby, an appropriate characterization of bicomponent fibers is very valuable to process monitoring, quality control and forensic investigation. The sheath-core bicomponent fiber composed by polyethylene (PE), polypropylene (PP) and titanium dioxide (TiO2) was analyzed by Fourier transform infrared (FT-IR) spectroscopy and other analytical methodologies. Results obtained by FT-IR using modern accessories showed efficiency to characterize the polymers of sheath (PE) and core (PP), moreover these polymers were confirmed by DSC (Differential Scanning Calorimetry). The morphology and elemental composition were also studied by scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM/EDS). The thermogravimetric analysis (TGA) and colorimetric analysis allowed characterize and quantify the concentration of TiO2.

Abstract The paint industry requires rapid and accurate methodologies of raw materials qualitiy controls. For example, the evaluation of the suitable ratio of binary mixtures of polymer/plasticizer such as nitrocellulose (NC)/acetyl tributyl citrate (ATBC) must be done, since this ratio is directly related to the performance of the final product. However, there is a small number of quantitative methodologies of such control in the literature. In this context, in this paper, the applicability of Infrared Fourier Transform Spectroscopy (FT-IR) techniques by using universal total attenuated reflection (UATR), in the middle infrared (MIR), and the reflectance analysis in the near infrared region (NIRA) is evaluated for the quantification of plasticizer ATBC in mixtures with NC. MIR and NIR methodologies presented good results such as: practicality of not requiring refined sample preparation, analysis time about 30 min and good accuracy, suitable data for using in the quality control laboratories of paint industry.

Abstract It is a well-established fact that rubber accelerator is essential to provide solution in different sectors. However, there is a reversal process which can reduce the material performance. Sulfur accelerators donors and organic peroxides have been presented as a solution to the problem. The methodology development that can separate or characterize those components is a challenge and still allows gaps, explained by the application of conventional technique to reach this goal. This study aimed at contributing to the use of off-line coupling of thin layer chromatography (TLC)/infrared spectroscopy (IR) by Universal Attenuated Total Reflection (UATR) for analysis of N-cyclohexyl-2-benzotiazolsulfenamide (CBS), tetraethylthiuram disulfide (TMTD) and dicumyl peroxide (DCP), in natural poly-cis-isoprene (NR) formulations, containing naphthenic oil. The best results were obtained for the plasticizer and DCP, in formulations that had a greater proportion of these compounds. The separation of CBS and TMTD was made with less effectiveness, due to bands overlapping.

Abstract When using Fourier transform infrared spectroscopy (FT-IR) under the qualitative aspect for characterization of polymer blends, often a simple identification of each one of the existing polymers in the blend does not justify the material failure since different amounts of each component may result in different mechanical properties, which should be a possible cause for of material failure when applied to an automotive part. Thus, seeking for a better justification in the understanding of material failure analysis, a new quantitative FT-IR methodology was developed in the mid-infrared region (MIR), using the transmission techniques and universal attenuated reflectance for the determination of Acrylonitrile Butadiene Styrene (ABS) and polycarbonate (PC). Transmission mode was more suitable. The relative band (A831 /A2237) was chosen for the preparation of the calibration curve that showed a 0.99% error methodology, which is within the FT-IR spectrometer accuracy limit (≤ 2%); therefore, it is accurate for the analysis of the system.

Abstract Epoxy resins (EP) usually cure in autoclave to minimize resin voids and to achieve the desired resin/fiber ratio. Cure parameters such as temperature, vacuum and pressure levels are controlled and monitored. Aiming time and cost optimization, new out-of-autoclave (OOA) cure processes have been developed lately. This study evaluated the cure cycle and the effect of non-programmed interruptions in an OOA process. Fourier Transform Infrared spectroscopy (FT-IR) results show similarities between the resin used and diglycidyl ether of bisphenol A (DGEBA) and also that the curing system is composed of cyan and sulfur hardeners, codified in industry, as Components of #2511 Resin System. The cure cycle and its interruptions were simulated by dynamic-mechanical analysis (DMA). The samples obtained were evaluated by FT-IR and differential scanning calorimetry (DSC), whose results show that the degree of cure varying between 0.8 to 0.85 was achieved at 120 °C.

Abstract The knowledge of the components that constitutes a rubber composition is important to justify the properties of the final device, particularly when it comes to elastomeric compositions used in the aerospace industry. The development of methodologies that can detect components, specially the smallest proportion of the rubbers composition is a constant challenge and an important gap in the studies of this nature. Therefore, methodologies by using standard techniques and/or of last generation are important in rubber industry and research laboratories, aiming application in related research. In this context, this study shows the coupling/association techniques (off-line) of thin layer chromatography and infrared spectroscopy (TLC/IR), being the IR spectra obtained by universal attenuated total reflection (UATR), applied to the analysis of additives in rubber compositions of ethylene-propylene-diene rubber (EPDM). Two EPDM compositions, a kind of eluent system and Gibbs' reagent, as developer, were used. Basically, all organic components were detected by this methodology, being possible to suggest that it can be applied for detecting additives of similar chemical structures, even though it's presents in small amounts in the composition.

ABSTRACT Carbon fibers have been widely used as structural reinforcement in aeronautical composites, because of their exceptional mechanical properties. However, carbon fibers present few polar groups on their surfaces inducing a weak interaction with some thermosetting and thermoplastic matrices. Surface treatments, such as thermal and electrochemical oxidation, are generally followed by sizing in order to improve interfacial adhesion between carbon fibers and some matrices. The precise surface characterization, by means of its chemical groups and radical identification, has been pointed out as an effective tool of carbon fibers finishing assessment process. Goniometry and Fourier transforminfrared spectroscopy are widely used to characterize some materials applied in industry, but not for carbon fibers, mainly because of their filamentary shape and the high concentration of carbon even in their near surface. In this paper, unsized and sized Torayca T300 carbon fibers were characterized by goniometry tests to evaluate hydrophilic or hydrophobic character. Qualitatively, it was noticed the effect of sizing on carbon fibers by their hydrophilic behavior, which has not been observed in unsized samples. Chemical analysis was performed by Fourier transform-infrared spectroscopy using different setups: photoacoustic, attenuated total reflectance and universal attenuated total reflectance. The Fourier transform-infrared spectroscopy/attenuated total reflectance/Germanium was shown to be the most promising technique to analyze carbon fibers surface, despite the low level of relative intensities of some bands. By this technique, it was possible to observe differences between unsized and sized carbon fibers spectra.

Resumo Vários aditivos são incorporados nas formulações de tintas para evitar defeitos no revestimento e melhorar o desempenho nas aplicações, constituindo, desse modo, um sistema complexo. A caracterização de uma composição pode ser realizada por separações física/ química e técnicas analíticas instrumentais. A análise de multicomponentes é utilizada no estudo de não conformidades, investigação forense e pesquisa e desenvolvimento de novos produtos. As pesquisas correlatas, em geral, utilizam metodologias convencionais, encontrando algumas limitações, o que motiva a utilização de técnicas alternativas, incluindo acoplamentos, para a análise de aditivos em tintas. Nesse contexto, foi avaliada a aplicabilidade do acoplamento (indireto ou off-line) das técnicas de cromatografia de camada fina (TLC) e espectroscopia no infravermelho com transformada de Fourier (FT-IR), denominado TLC-IR, e extração seletiva na análise de aditivos em tinta à base de resina poliuretânica (PU) e nitrocelulose (NC). Foi utilizada uma formulação, avaliados três sistemas de eluentes e um tipo de revelador, o de Gibbs. Os espectros FT-IR foram obtidos por Reflexão Total Atenuada Universal (UATR). Os principais resultados mostraram que o plastificante Acetil Tributil Citrato (ATBC), aditivo majoritário, foi facilmente identificado por TLC-IR. A metodologia permitiu detectar e diferenciar plastificantes do tipo ftalato, como dioctil ftalato (DOP) e dibutil ftalato (DBP), mesmo em pequena quantidade de amostra, e identificar a oleamida (aditivo promotor de deslize) por meio de extração seletiva e UATR.

Abstract Various additives are incorporated into the paint formulations to prevent coating defects and improving the application performance, so it is a complex system. The characterization of the components present in this system can be performed by physical/ chemical separation and instrumental analytical techniques. Multi component analysis is used in the study of non-compliance, forensic investigation and research and development of new products. The related research generally uses conventional methodologies, finding some limitations, which motivates the use of alternative techniques, including couplings, for additive analysis in paints. In this context, has been reported the coupling (off-line) of thin layer chromatography (TLC) and Fourier transform infrared spectroscopy (FT-IR) (TLC-IR) and selective extraction in the analysis of additives in ink containing polyurethane (PU) and nitrocellulose (NC) resin. One formulation was evaluated, by using three eluting systems, and one type of developer, Gibbs. The FT-IR spectra were obtained by Universal Attenuated Total Reflection (UATR). The main results showed that the plasticizer Acetyl Tributyl Citrate (ATBC), as the majority additive was easily identified by TLC-IR. The methodology allowed even detect and differentiate phthalates like dioctyl phthalate (DOP) and dibutyl phthalate (DBP), even in small amount of sample, and identify oleamide (slip promoter) by means of selective extraction and UATR.

Foi desenvolvida uma metodologia para a determinação do teor de 5-etilideno 2-norboneno (ENB) em amostras de borracha (elastômero puro), à base do copolímero de etileno-propileno-dieno (EPDM), por espectroscopia no infravermelho com transformada de Fourier (FT-IR) de transmissão, sendo as amostras analisadas, após pirólise controlada e em bico de Bunsen. Embora ambas as técnicas tenham apresentado boa precisão, a realizada por pirólise em bico de Bunsen, com uso de banda e concentração relativa, mostrou-se mais adequada à determinação e ao uso em cálculos complementares de teores de ET e P.

A methodology was developed for determining the 5-ethylidene-2-norbornene (ENB) content in unvulcanized (pure elastomer) ethylene-propylene-diene (EPDM) elastomer, by transmission Fourier Transform infrared spectroscopy (FT-IR), after pyrolysis with and without temperature (T) control. Although both techniques have shown good accuracy, the pyrolysis without T control technique, with relative bands and concentrations, was more suitable for the ENB content determination and for the complementary calculations of ET and P.

Foi desenvolvida uma metodologia para a determinação dos teores de etileno (ET) e propileno (P) em amostras de borracha (elastômero puro, crua e vulcanizada), à base do copolímero de etileno-propileno-dieno monômero (EPDM), por espectroscopia no infravermelho com transformada de Fourier (FT-IR) de reflexão total atenuada universal (UATR) e de transmissão, sendo as amostras analisadas tal como recebidas ou após pirólise, respectivamente. Embora ambas as técnicas tenham apresentado boa precisão, com a análise UATR sendo mais adequada para o elastômero puro, a realizada por transmissão/pirólise mostrou-se mais adequada à análise de todos os tipos de EPDM (elastômero puro, crua e vulcanizada), podendo ser usada para formulações similares.

We developed a methodology for determining the concentration of ethylene and propylene in rubber samples (raw, unvulcanized or vulcanized) based on the copolymer of ethylene, propylene and diene monomer (EPDM) by Fourier transform infrared spectroscopy (FT-IR), using universal attenuated total reflection (UATR) and transmission techniques. Pristine and pyrolized samples were analyzed. Although both techniques have shown good accuracy, UATR is the most suitable for the pure elastomer and the transmission/pyrolysis technique is more suitable for the analysis of all types of EPDM (raw, unvulcanized or vulcanized) and can be used for similar formulations.

A possibilidade de interação entre o sistema à base do polímero de azoteto de glicidila e da dinitramida de amônio (GAP/ADN) foi avaliada, por FT-IR, nas regiões do infravermelho médio (MIR) e infravermelho próximo (NIR). O sistema GAP e perclorato de amônio (GAP/AP), utilizando oxidante mais usual, foi analisado por MIR. Maiores alterações espectrométricas foram observadas para o sistema GAP/ADN. Foi observado um alargamento de bandas para ambos os sistemas na região entre 3100-3500cm-1, sugerindo interações entre os grupos OH do GAP e NH4+ do ADN ou AP. A diminuição da intensidade da banda do grupo N3 do GAP e o aumento de intensidade do nitroílo (NO2+) do ADN também foram notados, sugerindo interação entre esses grupos no sistema GAP/ADN.

FT-IR spectroscopy, in the mid-infrared (MIR) and near infrared (NIR) regions, was used to investigate possible interactions in the polymer system made with glycidyl azide and ammonium dinitramide (GAP/ADN). The GAP and ammonium perchlorate (GAP/AP) system with the most usual oxidizer was studied by MIR. Major spectrometric changes were observed for the GAP/ADN system, with a broadening of the bands in the region between 3100-3500cm-1, pointing to interactions between OH groups from GAP and NH4+ groups from ADN or AP. Also noted were a decrease in band intensity for the N3 group in GAP and an increased intensity of nitronium (NO2+) of ADN, suggesting interaction between these groups in the GAP/ADN system.