Abstract The blend of butadiene and acrylonitrile copolymer (NBR) with natural poly-cis-isoprene (NR) shows increased resistance to swelling in solvents in comparison to the individual components. In aerospace, NBR rubber is used as thermal protection for rockets and shall not contain other polymers, even in low contents, otherwise, it can affect the protection performance and rocket safety by causing detachment of the elastomer/propellant interface; therefore, this investigation presents methodologies to determine the NR/NBR contents. This study explores different analytical techniques, such as Raman spectroscopy and Fourier transform infrared (FTIR) spectroscopy, in the mid-infrared (MIR) by reflection and in the near-infrared by reflectance (NIRA) modes, Furthermore, quantification strategies by univariate, bivariate and multivariate (chemometric) models are evaluated and compared. A proposed methodology, based on multivariate Raman microscopy with partial least squares regression (PLS), showed high linearity (R2 > 0.99) and low error (< 0.82 %). The validation of FT-MIR data for the CH3, which presented lower error (1.3%) than vinylidene band (6%), showed that both methodologies (reflection and NIRA reflectance) can be used for the quantification of NR in NR/NBR. These results constitute a contribution to the state of the art in researching industrial and aerospace elastomeric applications. (NBR polycisisoprene poly cis isoprene (NR components polymers contents otherwise elastomerpropellant elastomer propellant interface therefore NRNBR techniques FTIR (FTIR midinfrared mid MIR (MIR nearinfrared near (NIRA modes Furthermore univariate chemometric (chemometric compared methodology PLS, PLS , (PLS) R2 R (R 0.99 099 0 99 < ( 082 82 0.8 %. % . %) FTMIR FT CH3 CH 1.3% 13 1 3 (1.3% 6%, 6 6% (6%) applications (PLS 0.9 09 9 08 8 0. 1.3 (1.3 (6% 1. (1. (6 (1

Abstract Quantification of elastomer content for the ethylene-propylene diene monomer/polybutadiene blend are seldom subjects in the literature, mainly due to rubber compatibility problems. However, suitable blend contents can lead to desirable properties. Infrared spectroscopy can quantify this type of blend even if some bands overlap, which can be resolved with the proper choice of spectrum obtaining mode and non-overlapping analytical bands. This study evaluates the ethylene-propylene diene monomer/polybutadiene blend quantification by transmission, reflection and transflectance infrared. Even though all of the methodologies showed satisfactory results, transmission mode provided better accuracy. The methodology is simple and suited for the rubber industry. The sample with the higher BR content provided the best result. The band at 743 cm-1 is weak and results in even weaker absorptions when measuring samples with low BR content. On the other hand, the developed methodologies provided an accurate determination of low EPDM contents. For infrared spectroscopy researchers, these results not only encourage using different spectra obtaining modes application, including less conventional ones such as transflectance in the near infrared region for quantitative determination, it also contributes to a wide discussion of errors in the developed methodologies, which are also seldom discussed in publications. ethylenepropylene ethylene propylene monomerpolybutadiene monomer polybutadiene literature problems However properties overlap nonoverlapping non overlapping accuracy industry result 74 cm1 cm 1 cm- hand researchers application publications 7

Abstract A considerable number of papers have been published to assess self-healing capacity of several materials, as well as several applications in different areas. However, the impact assessment of changing synthesis parameters of microcapsules, hollow fibers or microvascular systems in its final physicochemical properties are still an emerging research field. This current paper presents a synthesis process of PU microcapsules containing TDI as core agent and the characterization of microcapsules physicochemical properties. During the synthesis, the reaction parameter stirring speed was changed to assess the impact that this parameter has in the final microcapsules’ physicochemical properties. Microcapsules were characterized by FT-IR, TGA and image analysis (OM and SEM). Additionally, microcapsules were incorporated to an epoxy matrix (5% weight/weight) to assess the impact in the final physicochemical and mechanical matrix properties. Epoxy-based test specimens were also obtained within aramid and silica, which are traditional reinforcing loads in rubber synthesis. Final mechanical properties of matrixes within aramid and silica were compared to the properties of matrixes within microcapsules to determine what kind of behavior the microcapsules have when incorporated to epoxy matrixes. selfhealing self healing materials areas However field FTIR, FTIR FT IR, IR FT-IR OM SEM. SEM . SEM) Additionally 5% 5 (5 weight/weight weightweight weight Epoxybased Epoxy based (

Abstract This study describes a methodology to prepare and characterize PUF [poly(urea formaldehyde)] microcapsules containing 5-ethylidene-2-norbornene (ENB) as self-healing agent, as well as the compatibility evaluation of ENB in the presence of Grubb’s catalyst with an epoxy matrix. First, the results of an adhesion assay by lap shear proved chemical compatibility between the epoxy matrix and self-healing agent in the presence of Grubb’s catalyst. After evaluating the chemical compatibility, microcapsules with ENB were synthesized in an oil-in-water emulsion system. Thereafter, the microcapsules were morphologically, chemically and thermally characterized in which a granulometric dispersion between 30-140 μm and an average size of 69.8 ± 4.9 μm were observed. The SEM (scanning electron microscope) results showed that the average thickness of microcapsules shell was 3.6 ± 0.4 μm. The thermogravimetric analysis (TGA) showed that microcapsules are susceptible to rupture and consequent ENB release in temperatures greater than 230 °C, demonstrating that microcapsules are suitable for applications in materials with self-healing capacity. polyurea poly urea formaldehyde formaldehyde) 5ethylidene2norbornene ethylidenenorbornene 5 ethylidene 2 norbornene (ENB selfhealing self healing Grubbs Grubb s First oilinwater oil water system Thereafter morphologically 30140 30 140 30-14 698 69 8 69. 49 4 9 4. observed scanning microscope 36 3 6 3. 04 0 0. TGA (TGA 23 C °C capacity 3014 14 30-1 301 1 30-

Abstract Epoxy systems are widely applied as adhesives in the aerospace industry. They have excellent adhesion properties, however, being thermosetting, epoxy systems show fracture brittleness characteristics. Polysulfide and polymercaptans are good options to increase the flexibility of the epoxy adhesive. Thermal analysis techniques are generally used to evaluate the curing degree of epoxy systems. In most cases, when infrared (IR) analysis is used, it is employed qualitatively. This paper presents the reaction study of a DGEBA epoxy prepolymer with diethylenetriamine (DETA) and linear and branched dodecyl mercaptans as flexibilizers. Conversion data and curing time were assessed qualitatively and quantitatively by Fourier Transform Infrared Spectroscopy (FT-IR) in the medium infrared region (MIR) and in the near infrared region, using near infrared reflectance accessory (NIRA). NIRA methodology showed satisfactory results, with errors between 3 and 7%, especially in samples with lower amine contents. Mechanical tests confirmed the flexibilization of the cured epoxy system by the addition of mercaptans, indicating a lower crosslinking degree in the matrix. Young’s modulus (E) significantly decreased from 2017 MPa to 578 MPa with the addition of approximately 20 wt% of normal dodecyl mercaptan to the epoxy system.

Abstract Insulations for rocket motors such as Flexible Thermal Protections (FTPs) and Rigid Thermal Protection (RTPs) act as thermal barriers against the hyperthermal environment from the solid propellant combustion. FTPs present dual function: to extend RTPs performance, and to attenuate the propellant contraction. FTPs used in the Brazilian Space Program have asbestos in their composition since the 70´s; however, they are hazardous for human health. In this context, a mixture of Expanded Perlite (PExp) and Cork Powder (CP) was investigated as a replacement for asbestos. Results showed reduction about 21 % in density and an increase of 13 % in the ablative properties. The low mechanical properties not interfere in this type of FTP due to your function of attenuate the propellant contraction.

Abstract: Copper chromites are well known as burning rate catalysts for the combustion of composite solid propellants, used as a source of energy for rocket propulsion. The propellant burning rate depends upon the catalyst characteristics such as chemical composition and specific surface area. In this work, copper chromite samples from different suppliers were characterized by chemical analysis, FT-IR spectroscopy and by surface area measurement (BET). The samples were then evaluated as burning rate catalyst in a typical composite propellant formulation based on HTPB binder, ammonium perchlorate and aluminum. The obtained surface area values are very close to those informed by the catalyst suppliers. The propellant processing as well as its mechanical properties were not substantially affected by the type of catalyst. Some copper chromite catalysts caused an increase in the propellant burning rate in comparison to the iron oxide catalyst. The results show that in addition to the surface area, other parameters like chemical composition, crystalline structure and the presence of impurities might be affecting the catalyst performance. All evaluated copper chromite samples may be used as burning rate catalyst in composite solid propellant formulations, with slight advantages for the SX14, Cu-0202P and Cu-1800P samples, which led to the highest burning rate propellants.

Abstract: 2,2’, 4,4’, 6,6’- hexanitrostilbene (HNS) is an energetic material, a nitroaromatic compound, with thermal and chemical stabilities, which is employed in the aerospace industry. In this work, the Arrhenius parameters (activation energy and pre-exponential factor) of thermal decomposition reaction were studied and the results were compared with the values reported in the literature. The Kissinger method, applied to DSC’s nonisothermal data of the decomposition temperature was chosen for this study. The activation energy determined for the thermal decomposition of HNS revealed values from 428 kJ.mol-1 to 477 kJ.mol-1, under the experimental conditions employed.

Abstract: A new methodology was developed to characterize and to quantify the polymer content in PBX (HMX/Viton) by Fourier Transform Infrared Spectroscopy (FT-IR), using the Termogravimetric analysis (TG) as reference techniques for the quantitative method. The quantification methodology, proposed by us, using the Fourier transform infrared-attenuated total reflectance (FT-IR/ATR) showed excellent results, being faster than the usual methodologies and can eliminate the generation of chemical residues.

Resumo: Reações para obtenção de derivados de hidantoína foram conduzidas a partir de aldeídos de cadeia curta e da 5,5-dimetilhidantoína. O acompanhamento das reações foi realizado por espectroscopia na região do infravermelho médio (MIR) por meio da formação de novas bandas características da estrutura do composto desejado. A análise MIR revelou que estas alterações espectrométricas ocorrem somente na reação com o formaldeído, indicando a formação do produto 1,3-bis(hidroximetil)-5,5-dimetilhidantoína, em presença de água. As bandas de absorção que confirmam a reação foram observadas em 3334 cm-1 (υ OH), 1770 e 1710 cm-1 (υ C=O) e em 1056 cm-1 (υ C-O), sendo esta última, atribuída ao grupo contendo hidroxila primária. A reação da 5,5-dimetil hidantoína com acetaldeído e com propanaldeído não ocorreu sob as condições adotadas neste trabalho.

Abstract: Reactions to obtain hydantoin derivatives were carried out with 5,5-dimethylhydantoin and short-chain aldehydes. Monitoring of the reactions was performed using qualitative mid-infrared spectroscopy (MIR) through the formation of new bands characteristic of the desired product. MIR analysis showed that these spectrometric alterations occur only in the reaction with the formaldehyde, indicating the formation of the desired product, 1,3-bis (hydroxymethyl) 5,5-dimethylhydantoin, in the presence of water. The absorption bands that confirmed the reaction were observed at 3334 cm-1 (υ OH), 1770 and 1710 cm-1 (υ C=O) and 1056 cm-1 (υ C-O), the last of which is assigned to the group containing primary hydroxyl.

Abstract: The search for a smokeless propellant has encouraged scientists and engineers to look for a chlorine-free oxidizer as a substitute for AP (ammonium perchlorate). Endeavors seemed to come to an end when ADN (ammonium dinitramide) appeared in the West in the early 1990s. Although some drawbacks soon became apparent by that time, the foremost obstacle for its use in rocket-motors came from the patent originally applied for in the United States in 1990. Furthermore, environmental concerns have also increased during these two decades. Ammonium perchlorate is believed to cause thyroid cancer by contaminating soil and water. In addition, AP produces hydrogen chloride during burning which can cause acid rain and ozone layer depletion. Unlike AP, ADN stands for both smokeless and green propellant. Since then, much progress has been made in its development in synthesis, re-shaping, microencapsulation and solid propellant. The high solubility of ADN in water has also allowed its application as liquid monopropellant. Tests have revealed Isp (specific impulse) superior to that normally observed with hydrazine, one of the most harmful and hazardous liquid propellants. With constraints of use, along with the patent near to expiry, scientists and engineers are rushing to complete developments and patents until then.

Resumo: Um novo método de análise por via úmida e instrumental foi desenvolvido para avaliação da abertura do anel aziridínico do óxido de tris(l-(2-metil)aziridinil) fosfina (MAPO), agente de ligação usado em propelente compósito. Foi observada redução de intensidade das bandas de absorção em 1400 e 1040 cm-1, que são características do anel aziridínico. Em alguns casos, observou-se que, quando o número de anéis abertos aumenta, a banda de absorção do grupo NH, na região 3400 e 3300 cm-1, que aparece com a abertura do anel, está localizada na região de menor número de onda. O estudo de síntese do derivado do MAPO evidenciou reações secundárias com a hidroxila do ácido 12-hidroxiesteárico, homopolimerização e reação com a umidade existente na amostra.

Abstract: A new method using wet chemistry and instrumental analysis has been developed for evaluating the ring-opening of aziridine tris [l-(2 methyl) aziridinyl] phosphide oxide (MAPO) of the bonding agent used in composite propellant. A reduction was observed in the intensity absorption bands in 1400 and 1040 cm-1, characteristic of aziridinic ring. It was also observed, in some cases, that when the number of open aziridinyl ring increases, the NH band in the range 3400-3300 cm-1, that appears with ring-opening, is located in the region of lower wave numbers. The study of the synthesis of MAPO derivative indicated side reactions such as homopolymerization of rings and also, with secondary hydroxyl of the 12-hydroxy stearic acid and probable humidity existent in the original sample.

Abstract: Synthesis and characterization of energetic ABA-type thermoplastic elastomers for propellant formulations has been carried out. Following the working plan elaborated, the synthesis and characterization of Poly 3-bromomethyl-3-methyl oxetane (PolyBrMMO), Poly 3- azidomethyl-3-methyl oxetane (PolyAMMO), Poly 3,3-bis-azidomethyl oxetane (PolyBAMO) and Copolymer PolyBAMO/AMMO (by TDI end capping) has been successfully performed. The thermoplastic elastomers (TPEs) were synthesized using the chain elongation process PolyAMMO, GAP and PolyBAMO by diisocyanates. In this method 2.4-toluene diisocyanate (TDI) is used to link block A (hardandmono-functional)) to B (soft and di-functional). For the hard A-block we used PolyBAMO and for the soft B-block we used PolyAMMO or GAP. This is ajoint project set up, someyears ago, between the Chemistry Division of the Institute of Aeronautics and Space (IAE) - subordinated to the Brazilian Ministry of Defense - and the Fraunhofer Institut Chemische Technologie (ICT), in Germany. The products were characterized by different techniques as IR- and (1H, 13C) NMR spectroscopies, elemental and thermal analyses. New methodologies based on FT-IR analysis have been developed as an alternative for the determination of the molecular weight and CHNO content of the energetic polymers.