Mannich bases from dimethylamine, formaldehyde and phenol, m-cresol, eugenol, p-tent-pentylphenol, p-tert butylphenol, p-iso-propylphenol, 3,1,5-trimetbylphenol, resorcinol, 3-pentadecylphenol and the component phenols of cashew nut shell liquid (CNSL) have been prepared. Mannich bases have also been prepared from methylamine, formaldehyde with phenol and with m-cresol, from diethylenetriamine, formaldehyde and phenol, m-cresol, resorcinol, 3-pentadecylphenol and the component phenols of CNSL. A11 the Mannich bases were examined by H nuclear magnetic resonance, infra-red spectroscopy and by T. L. C. The coloured products formed from autoxidation of resorcinol, orcinol and hydrolr-ß-orcinol in presence of ammonia, methylamine and dimethylamine were isolated by column chromatography and preparative TLC and examined by 1H NMR, I. R, U. V. and mass spectroscopy. Structures of some of the products have been proposed based on chemical and spectroscopic evidence. A new technique for the separation of cardanol and cardol in cashew nut shell liquid by extractive distillation using bases has been devised.

CoordenaÃÃo de AperfeÃoamento de Pessoal de NÃvel Superior / O envelhecimento do Cimento AsfÃltico de PetrÃleo (CAP) à um processo natural causado, principalmente, por reaÃÃes de volatilizaÃÃo de fraÃÃes leves e de oxidaÃÃo. Sabe-se que, com o passar dos anos, as misturas asfÃlticas envelhecem e ganham rigidez. Esse enrijecimento pode contribuir para o surgimento de trincas por fadiga nos pavimentos asfÃlticos, assim como, pode tornÃ-los mais resistentes à deformaÃÃo permanente. O LÃquido da Castanha de Caju (LCC) à um âaditivo verdeâ, oriundo de fonte renovÃvel e biodegradÃvel e possui caracterÃsticas antioxidantes. No Brasil, alguns trabalhos publicados ressaltam as caracterÃsticas antioxidantes do LCC, no entanto, poucos sÃo os trabalhos que consideram a sua aplicaÃÃo na pavimentaÃÃo. Neste estudo, o LCC à proposto como modificador do CAP 50/70 com o intuito de avaliar o seu potencial antioxidante. As misturas asfÃlticas e os CAP convencionais e modificados com 2% de LCC foram analisados antes e apÃs diferentes processos de envelhecimento, em laboratÃrio e ao natural. As misturas asfÃlticas foram envelhecidas em diferentes condiÃÃes, amostras compactadas e soltas. ApÃs os processos de envelhecimento e de recuperaÃÃo dos CAP, estes foram avaliados em relaÃÃo as suas propriedades empÃricas e reolÃgicas, sendo estas comparadas aquelas obtidas para o CAP nÃo envelhecido. AlÃm disso, o efeito do envelhecimento oxidativo foi analisado por meio da espectroscopia no infravermelho - FTIR (Fourier Transform Infrared Spectroscopy) e de mudanÃas na composiÃÃo SARA (Saturados, AromÃticos, Resinas e Asfaltenos) dos ligantes atravÃs de cromatografia com o detector de ionizaÃÃo de chama - TLC - FID (Thin Layer Chromatography and Flame Ionization Detection). As misturas asfÃlticas contendo o CAP convencional e o CAP modificado com 2% de LCC, apÃs os citados processos de envelhecimento, foram caracterizadas mecanicamente utilizando-se os ensaios de MÃdulo de ResiliÃncia (MR), ResistÃncia a TraÃÃo (RT), Vida de Fadiga (VF), MÃdulo DinÃmico |E*| e Creep DinÃmico (CD). Os resultados encontrados para os ensaios realizados no CAP apontam que o LCC atua como antioxidante em amostras envelhecidas a curto prazo, porÃm nÃo apresenta o mesmo comportamento para amostras envelhecidas a longo prazo. ApÃs a anÃlise dos resultados realizados nas misturas asfÃlticas, pode ser dito que o LCC causou uma leve reduÃÃo da rigidez destas misturas asfÃlticas e que, possivelmente, polimerizou ao ser submetido ao envelhecimento em estufa e no PAV. O processo de envelhecimento mais agressivo foi o que submeteu a mistura solta ao envelhecimento em estufa durante nove dias. / The aging of petroleum asphalt cement (AC) is a natural process caused mainly by volatilization of lighter fractions and oxidation reactions. It is known that, over the years, the asphalt mixtures age and become more rigid. This stiffening may contribute to fatigue cracks in asphalt pavements, and thus, can make them more resistant to permanent deformation. The cashew nut shell liquid (CNSL) is a "green additive", coming from a renewable and biodegradable source and has antioxidant characteristics. In Brazil, some studies highlight the CNSL antioxidant characteristics, however, few are the works that consider their application in paving. In this study, the CNSL is proposed as a modifier for the AC 50/70 for the purpose of assessing its antioxidant potential. The asphalt mixes and the conventional AC and the one modified with 2% of CNSL were analyzed before and after various aging processes performed in the laboratory and in a natural state. The asphalt mixtures were aged in different conditions, compacted and loose samples. After the aging processes and the recovery of the AC, they were evaluated in relation to their empirical and rheological properties and compared to those obtained for the unaged state. Furthermore, the effects of oxidative aging was analyzed by infrared spectroscopy - FTIR (fourier transform infrared) and changes in the SARA (Saturates, Aromatics, Resins and Asphaltenes) composition through chromatography. The asphalt mixtures containing conventional AC and the AC modified with 2% of CNSL, after the aforementioned aging processes were characterized mechanically using of resilience modulus (RM), tensile strength (TS), fatigue life, dynamic modulus |E*| and dynamic creep (DC) hots. The results for the tests performed indicate that the CNSL acts as an antioxidant for the short term period, but it does not show the same behavior for the long-term aged samples. After analyzing the results achieved for the asphalt mixtures, it can be said that the CNSL caused a slight reduction in stiffness of these mixtures and, possibly, polymerized when subjected to aging. The most aggressive aging process was the one that subjected the loose mixture samples to the long term aging during nine days.

CoordenaÃÃo de AperfeiÃoamento de Pessoal de NÃvel Superior / O lÃquido da castanha de caju (LCC) à constituÃdo de uma mistura de fenÃis com uma longa cadeia alquilÃca na posiÃÃo meta, possuindo diferentes graus de insaturaÃÃes. O estudo cinÃtico da degradaÃÃo termooxidativa a 140ÂC de filme de poli(1,4-cis-isopreno) sintÃtico (PIS), na ausÃncia e presenÃa do LCC tÃcnico e natural e seus derivados (Ãcido anacÃrdico, cardol, cardanol, cardanol hidrogenado e cardanol hidrogenado e alquilado), foi monitorado por espectroscopia na regiÃo do infravermelho atravÃs do acompanhamento da absorbÃncia relativa das bandas em 3450 cm-1, 1720 cm-1 e 835 cm-1. O tempo de induÃÃo (τi) e as constantes aparentes de velocidade para a formaÃÃo de produtos contendo hidrÃxido (kOH) e carbonila (kC=O) e para o consumo das ligaÃÃes duplas da cadeia (kC=C) foram os parÃmetros utilizados. Todos os materiais estudados apresentaram efeito estabilizante na degradaÃÃo tÃrmica do PIS, evidenciado pelo aumento do tempo de induÃÃo e a diminuiÃÃo das constantes aparentes de velocidade. AnÃlise das variaÃÃes de kOH, kC=O, kC=C e τi indica que o mecanismo de aÃÃo independe dos derivados do LCC. A maior efetividade dos derivados do LCC tÃcnico à prÃxima a 3 % (m/m), com exceÃÃo do cardol e HAlqcardanol. Por outro lado, a maior efetividade dos derivados do LCC natural (cardol e cardanol) à prÃxima a 2 % (m/m), com exceÃÃo do Ãcido anacÃrdico e do prÃprio LCC. A atividade antioxidante dos derivados do LCC depende da quantidade de material polimerizado presentes neles. Baseado nos parÃmetros cinÃticos, a ordem de atividade antioxidante para os derivados do LCC tÃcnico foi: LCC > cardol >> cardanol ≅ cardanol hidrogenado e alquilado > cardanol hidrogenado. Para os derivados do LCC natural a ordem foi: cardol > cardanol >> LCC natural >> Ãcido anacÃrdico. AnÃlise termogravimÃtrica revela que a adiÃÃo de derivados do LCC provoca estabilizaÃÃo do PIS quando degradado tanto em atmosfera de nitrogÃnio, como em ar sintÃtico. Os antioxidantes comerciais testados: IPPD (N-isopropil-N-fenil-p-fenileno-diamina), DPPD (N,Nâ-fenil-p-fenileno-diamina), Banox H (2,2,4-trimetil-1,2-dihidroquinolina-polimerizado) e Banox S (fenol estirenado) apresentaram uma atividade bastante superior, com exceÃÃo do BHT (2,6-di-terc-butil-4-metil-fenol). Dentre os derivados do β-naftol, o AO-3 (1,6-diamino-β-naftol) apresentou uma atividade antioxidante similar ao IPPD, embora com menores valores de constantes aparentes de velocidade. Por outro lado, os derivados AO-1 (6-N-etil, N-etilamino-β-naftol) e AO-2 (6-N-etil,N-dietilamino-β-naftol) apresentaram uma atividade antioxidante um pouco superior que os derivados do LCC, mas inferior ao AO-3. / Cashew nut shell liquid (CNSL) is a mixture of meta-alkyl-phenols which varies on its degree of unsaturation attached to the benzene nucleus. The kinetic study of the thermal degradation at 140ÂC of synthetic cis-1,4-polyisoprene film, in the absence and presence of technical and natural CNSL and some derivatives (anacardic acid, cardol, cardanol, hydrogenated cardanol and alkylated hydrogenated cardanol) was carried out by infrared spectroscopy through the evolution of the relative absorbance of the bands in 3450 cm-1, 1720 cm-1 and 835 cm-1. The amount of hydroxyl and carbonyl group formed and also of carbon double bond consumed during the degradation was determined. All material studied showed antioxidant activity that was verified by an increase in the induction period and a decrease in the apparent rate constants of thermal-oxidation. The antioxidant effectiveness is higher for the addition of 3% (w/w) of technical CNSL derivatives, except for alkylated cardanol. The antioxidant effectiveness is higher for the addition of 2% (w/w) of natural CNSL derivatives, except for anacardic acid and pure. Based on kinetic parameters the order of antioxidant activity for technical CNSL derivative was: CNSL >> cardanol ≅ hydrogenated and alkylated cardanol >> hydrogenated cardanol. For natural CNSL components the order was: cardol > cardanol >> CNSL >> Anacardic acid. Thermogravimetric analyses reveals that the addition of LCC derivatives provide stabilization of PIS in atmosphere of nitrogen, as well as in synthetic air. The commercial antioxidants: IPPD (N-isopropyl-N-phenil-p-phenilene-diamine), DPPD (N,Nâ-phenil-p- phenilene-diamine), Banox H (2,2,4-trimethyl-1,2-dihidroquinoline-polimerizade) and Banox S (phenol styrened) presented a quite superior activity, except for BHT (2,6-di-terc-buthyl-4-methyl-phenol. Among β-naftol derivatives, AO-3 (1,6-diamine-β-naftol) presented a similar antioxidant activity to IPPD, although with smaller values of the apparent rate constants. On the other hand, the derivatives AO-1 (6-N-ethyl, N-ethylamine-β-naftol) and AO-2 (6-N-ethyl,N-diethylamine-β-naftol) presented a quite superior antioxidant activity when compared to LCC derivatives, but inferior to AO-3.

O dano por umidade à um defeito frequente e um dos principais responsÃveis pelo desgaste prematuro de pavimentos. Esta pesquisa apresenta uma avaliaÃÃo do potencial do LCC como modificador de ligante asfÃltico com relaÃÃo à resistÃncia ao dano por umidadeem misturas asfÃlticas.Propriedades fÃsico-quÃmicas do LÃquido da Castanha de Caju (LCC) mostram-se potencialmente Ãteis para conferir ao Cimento AsfÃltico de PetrÃleo (CAP) maior adesÃo com os agregados.Utilizou-se um CAP convencional classificado por penetraÃÃo como 50/70 e um CAP modificado com 2% de LCC caracterizados quÃmica e reologicamente. Os agregados foram caracterizados atravÃs da fluorescÃncia de Raio-X e com relaÃÃo à forma. Foram dosadas, segundo o mÃtodo Superpave, diferentes misturas asfÃlticas contendo como ligante: CAP, CAP modificado com LCC e CAP e cal como fÃler. A caracterizaÃÃo mecÃnica das misturas foi realizada atravÃs dos ensaios Lottman modificado, MÃdulo de ResiliÃncia (MR) e desgaste CÃntabro. Utilizou-se o Processamento Digital de Imagens (PDI) para verificar o deslocamento da pelÃcula de CAP. Constatou-se que o LCC diminuiu a viscosidade e reduziu as Temperaturas de Usinagem e CompactaÃÃo (TUC) do CAP. Ambas as amostras, CAP e CAP modificado com 2% de LCC, foram classificadas como PG 70-28. Os agregados foram classificados como granÃticos, sub-arredondados, com baixa esfericidade e de textura lisa. Os resultados mostraram que a mistura com CAP modificado com LCC apresentou menor percentual de descolamento da pelÃcula de CAP e desempenho mecÃnico satisfatÃrio se comparada Ãs outras misturas analisadas. Espera-se que o LCC possa ser utilizado como aditivo gerando misturas asfÃlticas menos suscetÃveis à aÃÃo deletÃria da Ãgua. / Moisture damage is a frequent distress on pavements and is considered a major contributor to premature deterioration. Physicochemical properties of the Cashew Nut Shell Liquid (CNSL) showed to be potentially useful to improve the adhesion between asphalt binder and aggregates.The main objective of this study is to evaluate the potential of the CNSL modified asphalt binder to increase the hot mixture asphalt (HMA) resistance to moisture damage, and as a promoter of adhesiveness between binder and aggregates.Pure and modified asphalt binders with different CNSL contents were characterized chemically and rheologically. The aggregates were characterized by X-ray fluorescence and using Aggregate Imaging Measurement System (AIMS). HMAs with binders modified with CNSL were designed using the Superpave methodology. HMA mechanical characterization consisted of modified Lottman test, Resilient Modulus and Cantabro. Results were compared with those obtained using two different HMAs: (i) one with conventional asphalt binder and natural aggregates, and (ii) another one using 2% of lime as a filer. The stripping resistance of asphalt binderswere characterizedthrough digital image processing (DIP). The findings showed the CNSL decreased the asphalt binder viscosity. Both, the pure and the modified asphalt binder, were classified as PG 70-28. The granitic aggregates were classified as sub rounded, with low sphericity and smooth texture. The findings showed that the HMA contain binder modified with CNSL had better stripping resistance and behavior mechanical performance than other evaluated HMAs. Itâs expected that the effectiveness of the CNSL can be used as an additive to prevent striping in asphalt mixtures and to provide a greater resistance to breakdown caused by water.

Currently, the production of most non-asbestos organic (NAO) friction materials depends on a long and energy intensive manufacturing process and an unsustainable supply of synthetic resins and fibres; it is both expensive and bad for the environment. In this research, a new, more energy efficient, manufacturing process was developed which makes use of a naturally derived resin and natural plant fibres. The new process is known as 'cold moulding' and is fundamentally different from the conventional method. It was used to develop a new brake pad for use in low temperature (<400 °C) applications, such as rapid urban rail transit (RURT) trains. A commercially available resin based upon cashew nut shell liquid (CNSL) was analysed and found to have properties suitable for cold moulding. In addition, hemp fibre was identified as a suitable composite reinforcement. This was processed to improve its morphology and blended with aramid to improve its thermal stability. Each stage of cold mould manufacture was thoroughly investigated and the critical process parameters were identified. The entire procedure was successfully scaled up to produce an industrially sized 250 kg batch of material and the resultant composites were found to have appropriate thermal and mechanical properties for use in a rail brake pad. The tribological performance of these composites was iteratively developed through a rigorous testing and evaluation procedure. This was performed on both sub- and full-scale dynamometers. By adding various abrasives, lubricants, and fillers to the formulation it was possible to produce a brake pad with similar friction characteristics to the current market material, but with a 60% lower wear rate. In addition, this brake pad caused 15% less wear to the brake disc. A detailed examination of both halves of the friction couple found that cold moulded composites exhibit a different wear mechanism from the current market material, which was suggested to be the reason for their superior properties. Cold moulding is 3.5x faster and uses 400% less energy than the conventional method.