RESUMO A disponibilidade de novos materiais, processos e equipamentos sempre traz perspectivas favoráveis ao mercado. A busca por processos alternativos e pela redução do custo da obtenção de precursores de materiais de alto desempenho tem se tornado primordial para o desenvolvimento do setor industrial de produtos com valores mais acessíveis, visando suprir a demanda de fibras de carbono de uso geral em um mercado que vem apresentando contínua expansão. As fibras de poliacrilonitrila (PAN) obtidas pelo processo de extrusão mostra potencial na redução de custo como precursor de fibras de carbono, em relação ao processo via fiação a úmido utilizado atualmente. Essa tecnologia inovadora permite a fiação por fusão da PAN empregando a glicerina (proveniente da produção do biodiesel) como seu principal plastificante, e dispensando o emprego de solventes altamente tóxicos. Assim sendo, o presente trabalho visou obter copolímeros de PAN que fossem adequados ao processo de fiação por extrusão convencional. Para tanto, foi utilizado para a obtenção dos copolímeros de PAN o processo de polimerização em suspensão aquosa e a caracterização foi realizada por meio da técnica de Cromatografia de Permeação em Gel (GPC). Os resultados mostraram que a técnica de GPC foi apropriada para determinar as propriedades moleculares dos copolímeros de PAN e que o comonômero estireno (ES) foi adequado para a polimerização, gerando copolímeros de PAN-co-ES com Mn > 40.000 g/mol e Mw > 130.000 g/mol.

ABSTRACT The availability of new materials, processes and equipment always brings favorable perspectives to the market. The search for alternative processes and the precursor production cost reduction of high performance materials has become essential for the development of the industrial activity to produce the general purpose carbon fiber to supply the continuously expanding domestic market. The extrusion process of PAN fibers shows potential of cost reduction as it is a precursor of carbon fibers, in relation to the wet spinning method used up to now. This innovative technology enables spinning by melting PAN using glycerin (from biodiesel production) as the primary plasticizer, dispensing the use of highly toxic solvents. Thus, the present work aimed to obtain PAN copolymers that are suitable for the conventional extrusion spinning process. Therefore, PAN copolymer was copolymerized by aqueous suspension and the characterization was performed by Gel Permeation Chromatography (GPC) analysis. The results showed that GPC technique was suitable for determining of the PAN copolymers molecular properties and that styrene monomer was suitable for polymerization, generating PAN-co-ES copolymers with Mn > 40,000 g / mol and Mw > 130,000 g / mol.

ABSTRACT This paper presents the study and development of a firing test used to evaluate the behavior of a solid rocket motor. The motivation for the development of a subscale solid rocket motor with end burning propellant grain geometry arose from the need to evaluate the nozzle inserts of graphite for the possible replacement with the carbon fiber-reinforced carbon composite. These subscale solid rocket motors, simulating full scale motor operating time, but with mass flow far below, aim to determine the ablative characteristics of composite materials as a function of operating time. The objective was to correlate the mass flow between subscale solid rocket motors and full scale using insert data materials such as graphite and carbon fiber-reinforced carbon composites, which have ablative characteristics determined in subscale solid rocket motors used at the Instituto de Aeronáutica e Espaço. The critical section to evaluate the test device is rocket nozzle throat region. Analysis of the materials of the subsonic and supersonic nozzle insert parts was performed after the burning tests. It was found the formation of a thin layer of material deposited after the test. The deposited coating layer was analyzed by electron dispersive x-ray analysis and scanning electron microscopy. The results analyzed by these methods showed that there were aluminum and carbon in the coating. Finally, the material was analyzed by x-ray diffraction, and the results showed the presence of aluminum oxide. It was also noticed that, because of the unexpected coating deposition forming material in exit conical and throat of the insert that the effect of ablation was not observed.

ABSTRACT Carbon fiber/phenolic resin composites have long been used as ablative materials in rocketry. Ablation is a complex multiscale problem where radiative and convective heating leads to the pyrolysis of phenolic resin matrix, resulting in the formation of a porous insulation char as thermal protection. This study investigates the shear properties evolution during the heat treatment of a carbon fiber/phenolic resin nozzle extension entrance (exit cone) which is part of an integrated nozzle of launching and sounding vehicles, developed at the Instituto de Aeronáutica e Espaço (SP), Brazil. Specimens of the material (carbon fiber/phenolic resin composite) were subjected to heat treatment at 500, 1,000, 1,500 and 2,000°C, and measurements of shear strength and shear modulus were performed using the Iosipescu mode. Experimental data were compared with the results obtained theoretically. Also, morphological analysis was accomplished by optical microscopy and the observation of fractured surfaces, by scanning electron microscopy. Significant morphological changes in the microstructure after heat treatments were observed. The lowest value for shear strength obtained experimentally was 4.05 MPa, which is greater than the ultimate value obtained analytically (2.35 MPa), fulfilling its structural function during the propulsion time.

ABSTRACT Many dynamic engineering systems have interferences and interactions that causes wear under friction effect. Carbonaceous materials, such as polycrystalline graphites, are of great interest in engineering systems due to their inherent lubricant properties and their versatility as a material for applications in the areas of mechanics, transportation, energy systems and sensitive technologies. In this work the tribological behavior of three identical pairs, pin-on-disc, of commercial polycrystalline graphites were evaluated, in a controlled environment at 20 °C and 50 % RH. Results of tribological behavior were correlated considering the prevalence of basal plane, identified by polarized light optical microscopy, as a function of the tribological behavior, measured by tests with pin on disc tribometer. The results showed that the coefficient of friction behavior is directly related to the basal plane mosaic domain and the extension of the damage generated on this plane due to the contact between the tribological pair. The materials studied presented an increase in the friction coefficient values, 0,10; 0;13 and 0,23 with increasing area of the basal plane mosaic domain, respectively 55; 64 and 81% respectively.

A low cost and environmental friendly extrusion process of the Polyacrylonitrile (PAN) polymer was viabilized by using the 1,2,3-propanetriol (glycerol) as a plasticizer. The characterization of the fibers obtained by this process was the object of study in the present work. The PAN fibers were heat treated in the range of 200 °C to 300 °C, which is the temperature range related to the stabilization/oxidation step. This is a limiting phase during the carbon fiber processing. The characterization of the fibers was made using infrared spectroscopy, thermal analysis and microscopy. TGA revealed that the degradation of the extruded PAN co-VA fibers between 250 °C and 350 °C, corresponded to a 9% weight loss to samples analyzed under oxidizing atmosphere and 18% when the samples were analyzed under inert atmosphere. DSC showed that the exothermic reactions on the extruded PAN co-VA fibers under oxidizing synthetic air was broader and the cyclization started at a lower temperature compared under inert atmosphere. Furthermore, FT-IR analysis correlated with thermal anlysis showed that the stabilization/oxidation process of the extruded PAN fiber were coherent with other works that used PAN fibers obtained by other spinning processes.

Carbon fiber reinforced carbon (CFRC) composites, also called carbon/carbon (C/C) composites are materials with superior characteristics such as low density, good thermal shock resistance, high strength and low ablation under severe environments. Due to their properties, CFRC composites are ideal candidate in the high temperature fields. By pyrolysis process, carbon fiber phenolic resin composites are converted in C/C composites. The phenolic resin is a non-conductor (electrical resistivity of 1012Ω.m) and during heat treatment of carbon fiber phenolic resin composite, it is converted to a carbon matrix (a conductor). This conversion was accomplished by electrical resistivity measurements using four-probe method according to ASTM C611-98 with final electrical resistivity of 0.04 mΩ.m. Microstructure of carbon fiber phenolic resin composite was assessed by using optical microscopy and image analysis. Pore volume was evaluated and the results were compared with thermal gravimetric analyses. The values of activation energy (Ea) during pyrolysis were 1.153kJ.mol–1 and 10.860kJ.mol–1.

Polyacrylonitrile fiber encompasses a broad range of products based on acrylonitrile (AN) which is readily copolymerized with a wide range of ethylenic unsaturated monomers giving rise to polymers with different characteristics and applications. Such products can be designed for cost-effective, flame and heat resistant solutions for the textile industry, aircraft and automotive markets. In the present work acrylonitrile was copolymerized with vinylidene chloride (VDC) by conventional suspension polymerization process via redox system, with an initial content of 10%/mass of the VDC monomer. The copolymer average molecular weight was obtained by Gel Permeation Chromatography (GPC) and by intrinsic viscosity analysis. To control the polymerization process continuously, qualitative and quantitative analysis of the chloride content in the PAN AN/VDC copolymer structure was accomplished by using X-ray fluorescence and potentiometric titration techniques. A good correlation was found between these two techniques, leading to a straightforward verification of VDC in the polymer structure. The thermal behavior of PAN AN/VDC copolymer was performed by Differential Scanning Calorimetry (DSC) and Thermogravimetric Analysis (TGA). The results showed that VDC monomers exhibited a nearly stoichiometric reaction with acrylonitrile, copolymerizing about 90% of its initial mass. VDC changed significantly the polyacrylonitrile thermal behavior, decreasing the polymer degradation temperature by about 40-50°C.

Nano-carbon materials, such as carbon nanotubes and carbon nanofibers, are being thought to be used as multifunctional reinforcement in composites. The growing of carbon nanofiber at the carbon fiber/epoxy interface results in composites having better electrical properties than conventional carbon fiber/epoxy composites. In this work, carbon nanofibers were grown in situ over the surface of a carbon fiber fabric by chemical vapor deposition. Specimens of carbon fiber/nanofiber/epoxy (CF/CNF/epoxy) composites were molded and electrical conductivity was measured. Also, the CF/CNF/epoxy composites were tested under flexure and interlaminar shear. The results showed an overall reduction in mechanical properties as a function of added nanofiber, although electrical conductivity increased up to 74% with the addition of nanofibers. Thus CF/CNF/epoxy composites can be used as electrical dissipation discharge materials.

Abstract: Advanced carbon fiber hybrid carbon-ceramic matrix composites are realizing their potential in many thermostructural components for aerospace vehicles. This work presents ab-initio predictions of elastic constants and thermal properties for 2.5D carbon fiber reinforced carbon-silicon carbide hybrid matrix composites, by using the homogenization technique. The homogenization technique takes properties of individual components of the composites (fiber and matrix) and characteristics of the geometrical architecture of the preform to perform calculations. Ab-initio modeling of mechanical and thermal properties is very attractive, especially during the material development stage, when larger samples may be prohibitively expensive or impossible to fabricate. Modeling is also useful when bigger samples would be prohibitively expensive or impractical. Thermostructural composites made of 2.5D preforms are easy to manufacture in relation to 3D preforms. Besides, 2.5D preforms are also resistant to thermo cycling and have high resistance to crack propagation in relation to ply stacked composites such as unidirectional (1D) and bidirectional (2D) structures. The calculations were performed by setting an overall carbon fiber volume fraction at 40, 45 and 50 for a 2D stacked composite, and volume fraction in Z-direction of 2, 4 and 6.

Abstract: Phenolic resin has long been used as matrix for composites mainly because of its flame retardant behavior and high char yield after pyrolysis, which results in a self supporting structure. The addition of ceramic powders, such as SiC and B4C, as fillers to the phenolic resin, results in better thermo-oxidative stability, but as drawbacks, it has poor homogeneity, adhesion and processing difficulties during molding of the composites. The addition of single elements, such as boron, silicon and phosphorus in the main backbone of the thermo-set resin is a new strategy to obtain special high performance resins, which results in higher mechanical properties, avoiding the drawbacks of simply adding fillers, which results in enhanced thermo-oxidative stability compared to conventional phenol-formaldehyde resins. Therefore, the product can have several applications, including the use as ablative thermal protection for thermo-structural composites. This work describes the preparation of a boron-modified phenolic resin (BPR) using salicyl alcohol and boric acid. The reaction was performed in refluxing toluene for a period of four hours, which produced a very high viscosity amber resin in 90% yield.The final structure of the compound, the boric acid double, substituted at the hydroxyl group of the aromatic ring, was determined with the help of the Infrared Spectroscopy, 1H-NMR, TGA-DSC and boron elemental analysis. The absorption band of the group B-O at 1349 cm-1 can be visualized at the FT-IR spectrum. 1H-NMR spectra showed peaks at 4.97-5.04 ppm and 3.60-3.90 ppm assigned to belong to CH2OH groups from the alcohol. The elemental analysis was also performed for boron determination.The product has also been tested in carbon and silicon fibers composite for the use in thermal structure. The results of the tests showed composites with superior mechanical properties when compared with the conventional phenolic resin.

To address a critical aspect of the fast growing use of composites in aircraft and aerospace industry, the influence of the porosity on the shear strength of composites property was investigated as a mean for determining the critical values of porosity. Acid digestion techniques were applied to determine the void volume ratio of two families of carbon epoxy laminates (8 and 16 plies). Ultrasonic inspections revealed the corresponding attenuation coefficients. The void morphology was investigated by optical microscopy. Results from Interlaminar shear and Iosipescu shear tests were correlated with the attenuation coefficient to determine critical values of porosity using a modified Mar-Lin fracture criteria. It has been shown that the shear strength decrease with the increase of void volume ratio and the effects are more significant in thicker laminates. This work showed that by using the Mar-Lin criteria the singularity order, which is an indicative of the sensibility to voids in composites, is dependent of type of loading and void distribution.

Resumo: O presente trabalho descreve os processos de obtenção de compósitos termoestruturais de carbono reforçado com fibras de carbono. O processamento desses materiais tem início pela definição de uma arquitetura do reforço de fibras de carbono, seja na forma de empilhamento simples do reforço, de tecidos ou na forma de reforço multidirecional. A incorporação de matriz carbonosa no reforço de fibras, pelo preenchimento de vazios e interstícios, promove a densificação do material, e o incremento de massa específica. Duas rotas de processamento são predominantes na obtenção desses materiais, o processo via impregnação líquida e o processo via impregnação em fase gasosa. Em ambos os casos, processos térmicos levam à formação de matriz de carbono com propriedades específicas, que derivam de seus materiais precursores. Os processos diferem entre si, também, pelo rendimento, enquanto os processos executados por impregnação líquida apresentam rendimento de, aproximadamente, 45%, os processos por impregnação em fase gasosa apresentam rendimento em torno 15%.

Abstract: The present work describes the processes used to obtain thermostructural Carbon/Carbon composites. The processing of these materials begins with the definition of the architecture of the carbon fiber reinforcement, in the form of stacked plies or in the form of fabrics or multidirectional reinforcement. Incorporating fiber reinforcement into the carbon matrix, by filling the voids and interstices, leads to the densification of the material and a continuous increase in density. There are two principal processing routes for obtaining these materials: liquid phase processing and gas phase processing. In both cases, thermal processes lead to the formation of a carbon matrix with specific properties related to their precursor. These processes also differ in terms of yield. With liquid phase impregnation the yield is around 45 per cent, while gas phase processing yields around 15 per cent.

Resumo: O principal objetivo do presente trabalho foi a determinação do módulo de cisalhamento G12 e a máxima resistência ao cisalhamento (ô12) utilizando o ensaio de cisalhamento losipescu. Os testes foram conduzidos com dois tipos de compósitos, fibra de carbono/epóxi e fibra de vidro/epóxi utilizados na indústria aeroespacial e também uma matriz de resina moldada. Os resultados indicam a efetiva contribuição das fibras de reforço para a resistência ao cisalhamento (ô12) e para o módulo de cisalhamento (G12) comparado com a matriz polimérica sem reforço.

Abstract: The main aim of the present work was the determination of the shear modulus (GI2) and the maximum shear strength (ôI2) using the losipescu Shear Test. Tests were carried out on two types of composites, carbon fiber/epoxy and glass fiber/epoxy, used in the aerospace industry, and also a molded epoxy resin matrix. The results indicate the effective contribution of fiber reinforcements to the shear strength (ô12) and shear modulus (G12) compared to the no reinforcement polymer matrix.

Abstract. Quartz phenolic composites have been applied to thermal protection systems (TPSs) for reentry vehicles since the late fifties due to their excellent ablative resistance and mechanical performance. TPSs must withstand the aggressive reentry environment, such as atomic oxygen, when submitted to very high temperatures (> 1000° C) and heat flux. The ablative performance of composites is influenced by both base materiais and environmental parameters during the ablation process. For TPS systems phenolic resin is usually used as the base matrix due to its ability to form a stable char during decomposition. This charplays an important role in the absorption of the heat generated during the ablation process. During re-entry, parts of the charred matrix can be abrasively removed by shear force due to high pressure and velocity. In this work the ablative and mechanical properties of quartz phenolic composites were evaluated in order to identify the range of properties suitable for the use of these materiais as thermal protection systems for space vehicles. Quartz fabric having an areai weight of 680 g/m2 and a resole-typephenolic resin were used to prepare the composites. The resin has a viscosity of l65 MPa at 20°C. The prepreg material was cured by heating under pressure of 100 bar in a mold. The resin content of the prepreg obtained was about 50 per cent. The mechanical properties evaluated were, tensile, shear and flexural strength. The results obtained showed that this material has average values of 38.5 MPa, 52 MPa and 85 MPa for tensile, shear andflexural strength, respectively. The ablative tests were carried out in a high-energy air plasma in ambient atmosphere and the mass losses were measured for different exposure time.

Polycrystalline graphites are widely used in the metallurgical, nuclear and aerospace industries. Graphites are particulated composites manufactured with a mixture of coke with pitch, and changes in relative proportions of these materials cause modifications in their mechanical properties. Uniaxial tension tests must be avoided for mechanical characterization in this kind of brittle material, due to difficulties in making the relatively long specimens and premature damages caused during testing set-up. On other types of tests, e.g. bending tests, the specimens are submitted to combined stress states (normal and transverse shear stresses). The Iosipescu shear test, is performed in a beam with two 90° opposite notches machined at the mid-length of the specimens, by applying two forces couples, so that a pure and uniform shear stress state is generated at the cross section between the two notches. When a material is isotropic and brittle, a failure at 45° in relation to the beam long axis can take place, i.e., the tensile normal stress acts parallel to the lateral surface of the notches, controls the failure and the result of the shear test is numerically equivalent to the tensile strength. This work has evaluated a graphite of the type used in rocket nozzles by the Iosipescu test and the resulted stress, ~11 MPa, was found to be equal to the tensile strength. Thus, the tensile strength can be evaluated just by a single and simple experiment, thus avoiding complicated machining of specimen and testing set-up.