Rita de Cássia Lazzarini Dutra

TG/FT-IR characterization of additives typically employed in EPDM formulations

Thermogravimetric analysis coupled to Fourier transform infrared spectroscopy (TG/FT-IR) is a very popular technique for rubbers characterization. It involves analyses of the base polymer and additives. Ethylene–propylene–diene (EPDM) rubbers are frequently investigated by TG/FT-IR; however, the focus has been the degradation temperature range of the polymer. In this study, unvulcanized and vulcanized EPDM rubber and its additives were investigated by TG/FT-IR, without solvent extraction, and in a wide temperature range. Initially, the additives were individually characterized. TG/FT-IR identified the characteristic groups of all the additives analyzed and distinguished them from each other. Afterwards, unvulcanized and vulcanized EPDM rubbers were investigated without prior extraction.TG/FT-IR detected absorptions due to the additives tetramethylthiuram monosulfide and 2-mercaptobenzothiazole. Both of these sulfur-containing additives were present in the EPDM formulation at concentrations of 0.7 phr (0.63 wt %). The TG/FT-IR technique had some limitations, because not all the additives in EPDM rubber were detected. Paraffin oil, stearic acid and 2,2,4-trimethyl-1,2-dihydroquinoline functional groups were not observed in either the unvulcanized or vulcanized EPDM. Nevertheless, in addition to the ability of this method to detect sulfur-containing groups, the lack of a pre-extraction reduces the time and effort required for additive analysis in rubbers.

Determination of CHN content in energetic binder by MIR analysis

Azide polymers samples were analyzed by FT-MIR in order to develop a quantitative methodology to determine the C, H and N content in energetic polymers used in propellants. The elemental analysis data were used as reference. The FT-MIR results show a good agreement with CHN analysis. A good linear relationship was obtained suggesting that the methodology developed in the CTA laboratory can be used for quality control of these energetic polymers.

Determinação por FT-IR de transmissão e reflexão (UATR) de etileno e propileno em EPDM

Resumo: Foi desenvolvida uma metodologia para a determinacao dos teores de etileno (ET) e propileno (P) em amostras de borracha (elastomero puro, crua e vulcanizada), a base do copolimero de etileno-propileno-dieno monomero (EPDM), por espectroscopia no infravermelho com transformada de Fourier (FT-IR) de reflexao total atenuada universal (UATR) e de transmissao, sendo as amostras analisadas tal como recebidas ou apos pirolise, respectivamente. Embora ambas as tecnicas tenham apresentado boa precisao, com a analise UATR sendo mais adequada para o elastomero puro, a realizada por transmissao/pirolise mostrou-se mais adequada a analise de todos os tipos de EPDM (elastomero puro, crua e vulcanizada), podendo ser usada para formulacoes similares. Palavras-chave: EPDM, etileno, propileno, FT-IR, UATR, transmissao, pirolise, quantificacao. Determination of Ethylene and Propylene Content in EPDM by Transmission and Reflection FT-IR (UATR) Techniques

Separação e identificação de aditivos em tinta por TLC-IR/ UATR e extração seletiva

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.

UATR and NIRA evaluation in the quantification of ATBC in NC blends

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.

Sheath-core bicomponent fiber characterization by FT-IR and other analytical methodologies

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.

Characterization of additives in NR formulations by TLC-IR (UATR)

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.

Evaluation of Out-of-Autoclave (OOA) epoxy system

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.

Avaliação por FT-IR de Interações entre Polímero Energético e Oxidante: GAP/ADN e GAP/AP

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 NH 4 + groups from ADN or AP. Also noted were a decrease in band intensity for the N 3 group in GAP and an increased intensity of nitronium (NO 2 + ) of ADN, suggesting interaction between these groups in the GAP/ADN system.