Relevant bibliographies by topics / Controled radical polymerization

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Academic literature on the topic 'Controled radical polymerization'

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Published: 25 May 2024

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Journal articles on the topic "Controled radical polymerization"

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Chen, Mao, Honghong Gong, and Yu Gu. "Controlled/Living Radical Polymerization of Semifluorinated (Meth)acrylates." Synlett 29, no. 12 (April 18, 2018): 1543–51. http://dx.doi.org/10.1055/s-0036-1591974.

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Fluorinated polymers are important materials for applications in many areas. This article summarizes the development of controlled/living radical polymerization (CRP) of semifluorinated (meth)acrylates, and briefly introduces their reaction mechanisms. While the classical CRP such as atom transfer radical polymerization (ATRP), reversible addition-fragmentation chain transfer (RAFT) polymerization and nitroxide-mediated radical polymerization (NMP) have promoted the preparation of semifluorinated polymers with tailor-designed architectures, recent development of photo-CRP has led to unprecedented accuracy and monomer scope. We expect that synthetic advances will facilitate the engineering of advanced fluorinated materials with unique properties.1 Introduction2 Atom Transfer Radical Polymerization3 Reversible Addition-Fragmentation Chain Transfer Polymerization4 Nitroxide-Mediated Radical Polymerization5 Photo-CRP Mediated with Metal Complexes6 Metal-free Photo-CRP7 Conclusion
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Jenkins, Aubrey D., Richard G. Jones, and Graeme Moad. "Terminology for reversible-deactivation radical polymerization previously called "controlled" radical or "living" radical polymerization (IUPAC Recommendations 2010)." Pure and Applied Chemistry 82, no. 2 (November 18, 2009): 483–91. http://dx.doi.org/10.1351/pac-rep-08-04-03.

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This document defines terms related to modern methods of radical polymerization, in which certain additives react reversibly with the radicals, thus enabling the reactions to take on much of the character of living polymerizations, even though some termination inevitably takes place. In recent technical literature, these reactions have often been loosely referred to as, inter alia, "controlled", "controlled/living", or "living" polymerizations. The use of these terms is discouraged. The use of "controlled" is permitted as long as the type of control is defined at its first occurrence, but the full name that is recommended for these polymerizations is "reversible-deactivation radical polymerization".
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Lowe, A. B., and C. L. McCormick. "Homogeneous Controlled Free Radical Polymerization in Aqueous Media." Australian Journal of Chemistry 55, no. 7 (2002): 367. http://dx.doi.org/10.1071/ch02053.

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The ability to conduct controlled radical polymerizations (CRP) in homogeneous aqueous media is discussed. Three main techniques, namely stable free radical polymerization (SFRP), with an emphasis on nitroxide-mediated polymerization (NMP), atom transfer radical polymerization (ATRP) and reversible addition-fragmentation chain transfer polymerization (RAFT) are examined. No examples exist of homogeneous aqueous NMP polymerization, but mixed water/solvent systems are discussed with specific reference to the NMP of sodium 4-styrenesulfonate. Aqueous ATRP is possible, although monomer choice is limited to methacrylates and certain styrenics. Finally, homogeneous aqueous RAFT polymerizations are examined. We demonstrate the greater versatility of this technique, at least in terms of monomer variety, by discussing the controlled polymerization of charged and neutral acrylamido monomers and of a series of ionic styrenic monomers. Many of these monomers cannot/have not been polymerized by either NMP or ATRP.
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Save, Maud, Yohann Guillaneuf, and Robert G. Gilbert. "Controlled Radical Polymerization in Aqueous Dispersed Media." Australian Journal of Chemistry 59, no. 10 (2006): 693. http://dx.doi.org/10.1071/ch06308.

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Controlled radical polymerization (CRP), sometimes also termed ‘living’ radical polymerization, offers the potential to create a wide range of polymer architectures, and its implementation in aqueous dispersed media (e.g. emulsion polymerization, used on a vast scale industrially) opens the way to large-scale manufacture of products based on this technique. Until recently, implementing CRP in aqueous dispersed media was plagued with problems such as loss of ‘living’ character and loss of colloidal stability. This review examines the basic mechanistic processes in free-radical polymerization in aqueous dispersed media (e.g. emulsion polymerization), and then examines, through this mechanistic understanding, the new techniques that have been developed over the last few years to implement CRP successfully in emulsion polymerizations and related processes. The strategies leading to these successes can thus be understood in terms of the various mechanisms which dominate CRP systems in dispersed media; these mechanisms are sometimes quite different from those in conventional free-radical polymerization in these media.
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Braun, Dietrich. "Origins and Development of Initiation of Free Radical Polymerization Processes." International Journal of Polymer Science 2009 (2009): 1–10. http://dx.doi.org/10.1155/2009/893234.

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At present worldwide about 45% of the manufactured plastic materials and 40% of synthetic rubber are obtained by free radical polymerization processes. The first free radically synthesized polymers were produced between 1910 and 1930 by initiation with peroxy compounds. In the 1940s the polymerization by redox processes was found independently and simultaneously at IG Farben in Germany and ICI in Great Britain. In the 1950s the systematic investigation of azo compounds as free radical initiators followed. Compounds with labile C–C-bonds were investigated as initiators only in the period from the end of the 1960s until the early 1980s. At about the same time, iniferters with cleavable S–S-bonds were studied in detail. Both these initiator classes can be designated as predecessors for “living” or controlled free radical polymerizations with nitroxyl-mediated polymerizations, reversible addition fragmentation chain transfer processes (RAFT), and atom transfer radical polymerizations (ATRP).
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Monteiro, M. J., R. Bussels, S. Beuermann, and M. Buback. "High Pressure 'Living' Free-Radical Polymerization of Styrene in the Presence of RAFT." Australian Journal of Chemistry 55, no. 7 (2002): 433. http://dx.doi.org/10.1071/ch02079.

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Reversible addition-fragmentation chain transfer (RAFT) polymerization of styrene was studied at high pressure, employing two dithioester RAFT agents with an isopropylcyano (5) and a cumyl (6) leaving group, respectively. The high-pressure reaction resulted in low polydispersity polymer. It was found that controlled polymerizations can be performed at increased pressures with a high degree of monomer conversion, which signifies that high-pressure polymerizations can be utilized for the production of higher molecular weight polystyrene of controlled microstructure. Retardation of styrene polymerization was also observed at high pressure in the presence of RAFT agents (5) and (6). It is postulated that the retarding potential of these two RAFT agents is associated with an intermediate radical termination mechanism. High-pressure free-radical polymerizations open the way to producing living polymers with high rates, and thus lower impurities such as 'dead' polymer that are formed through bimolecular termination reactions.
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Matyjaszewski, Krzysztof. "Radical Nature of Cu-Catalyzed Controlled Radical Polymerizations (Atom Transfer Radical Polymerization)." Macromolecules 31, no. 15 (July 1998): 4710–17. http://dx.doi.org/10.1021/ma980357b.

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Zhang, Zhenghe, Pengcheng Zhang, Yong Wang, and Weian Zhang. "Recent advances in organic–inorganic well-defined hybrid polymers using controlled living radical polymerization techniques." Polymer Chemistry 7, no. 24 (2016): 3950–76. http://dx.doi.org/10.1039/c6py00675b.

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Controlled living radical polymerizations, such as ATRP and RAFT polymerization, could be utilized for the preparation of well-defined organic–inorganic hybrid polymers based on POSS, PDMS, silica nanoparticles, graphene, CNTs and fullerene.
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Ha, Nguyen Tran, and Duong Ba Vu. "Organic photo-catalyst for controlled synthesis of poly(methyl methacrylate) using spirooxazine initiator." Tạp chí Khoa học 14, no. 9 (September 20, 2019): 94. http://dx.doi.org/10.54607/hcmue.js.14.9.299(2017).

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Photoinitiated metal-free controlled living radical polymerization of methyl methacrylates was investigated using the nuclear aromatic compound of pyrene. In the presence of photoredox catalysts and UV irradiation, spirooxazine initiator was used as initiator for polymerization of methyl methacrylate with good control over molecular weight in range of 10000 – 14000 g/mol and polydispersity below 1.5. Moreover, the obtained polymer also exhibited photochromic properties under UV irradiation both in solution and in solid state film. We are reliable believe that organic-based photoredox catalysts will enable new applications for controlled radical polymerizations in both small molecules and polymer chemistry.
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Steenbock, Marco, Markus Klapper, and Klaus Müllen. "Triazolinyl radicals - new additives for controlled radical polymerization." Macromolecular Chemistry and Physics 199, no. 5 (May 1, 1998): 763–69. http://dx.doi.org/10.1002/(sici)1521-3935(19980501)199:5<763::aid-macp763>3.0.co;2-s.

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Dissertations / Theses on the topic "Controled radical polymerization"

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Autissier, Laurent. "Développement d'alcoxyamines pour l'ingénierie macromoléculaire." Electronic Thesis or Diss., Aix-Marseille, 2020. http://www.theses.fr/2020AIXM0323.

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La dissociation homolytique des alcoxyamines conduit à la formation de deux radicaux, un nitroxyde et un radical alkyle. Cette réaction réversible a été mise à profit pour contrôler les réactions de polymérisation radicalaire de monomères vinyliques ou pour réaliser des additions radicalaires intermoléculaires (IRA). Dans une première partie, notre but a été de développer une alternative plus économique au nitroxyde SG1 pour le contrôle de la polymérisation d’une large gamme de monomères y compris des méthacrylates. Nous avons développé plusieurs structures linéaires aliphatiques et aromatiques mais sans que celles-ci ne présentent les qualités du nitroxyde SG1 pour le contrôle de la polymérisation du styrène et de l’acrylate de n-butyle. Pour le contrôle de la polymérisation des méthacrylates, nous avons étudié des analogues du DPAIO qui se sont montrés aptes à la préparation de copolymères à blocs à base méthacrylate. Dans un second temps nous avons étendu l’IRA à la ligation peptidique et au couplage de polymères. Deux peptides pré-fonctionnalisés par une oléfine et par l’alcoxyamine MAMA-SG1™ ont été couplés par IRA avec de bons rendements. Cette méthode a été nommé Alcoxyamine Peptide Ligation (APL). Le développement de l’alcoxyamine activable 4-VP-SG1 a permis le couplage de type clic par IRA de polymères dans des conditions douces et sans catalyseur ou irradiation lumineuse. La synthèse d’un hydrogel encapsulant in situ une protéine tout en préservant son activité, a validé la compatibilité de cette méthode avec des applications biomédicales
Homolytic dissociation of alkoxyamines yields two radicals, a nitroxide and an alkyl radical. This reversible reaction was used to control radical polymerization of various olefins or to perform intermolecular radical addition (IRA). In a first part, we aimed at developing a cheaper alternative to SG1 radical able to control polymerization of a broad range of monomers including methacrylates. We developed several linear aliphatic and aromatic nitroxide structures. Contrary to SG1 nitroxide, theses structures were not suitable to control radical polymerization of styrene and n-butyl acrylate. As for the control of methacrylates, we studied DPAIO’s analogues, wich were suitable for the preparation of methacrylate based block copolymers. In a second part, we extended the field of IRA to peptide ligation and polymer coupling. Two peptides prefunctionnalized with an olefin and a MAMA-SG1 alkoxyamine were coupled by IRA with good yields. This method was called Alkoxyamine Peptide Ligation (APL). The development of triggered 4-VP-SG1 alkoxyamine allowed performing polymer clicking through IRA in mild conditions without any initiator/catalyst or irradiation source. The synthesis of an hydrogel allowing biological activity retention of in situ encapsulated biomolecule showed that this methodology is relevant for biomedical applications
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Wang, Aileen Ruiling Zhu Shiping. "Diffusion-controlled atom transfer radical polymerization." *McMaster only, 2005.

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Belincanta, Juliana. "Homopolimerização e copolimerização via radical livre controlada por radicais nitroxidos." [s.n.], 2008. http://repositorio.unicamp.br/jspui/handle/REPOSIP/266269.

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Orientador: Liliane Maria Ferrareso Lona
Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Quimica
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Resumo: A polimerização viva/controlada é uma área que vem se desenvolvendo rapidamente no escopo de polímeros e engenharia. A habilidade para preparar copolímeros bem definidos do tipo bloco, estrela, redes poliméricas, bem como outros materiais pelo mecanismo da polimerização via radical livre é talvez a principal razão para o crescente interesse pela academia cientifica e meio industrial neste tipo de polimerização viva/controlada. O interesse industrial se deve a aplicabilidade desta nova técnica em áreas como colas, adesivos, surfactantes, dispersantes, lubrificantes, gel, aditivos, elastômeros termoplásticos, bem como aplicações nas áreas de eletrônica e biomedicina. Vale citar a produção industrial de dispersantes pela polimerização mediada por nitróxidos, um caso de polimerização viva/controlada. Este trabalho tem como objetivo investigar experimentalmente e por modelagem a polimerização em massa via radical livre mediada por TEMPO (2,2,6,6-tetramethyl piperidinyl-1-oxy) de estireno e estireno com divinilbenzeno, sob diversas condições experimentais. Para o caso de homopolimerização foi avaliada uma análise de sensibilidade de como as constantes cinéticas afetam o desempenho do modelo. Reações, não incluídas no modelo original, foram adicionadas ao modelo e testadas. O efeito de diferentes concentrações de TEMPO foi avaliado experimentalmente. Foi observado que esta condição afeta significativamente os resultados. Para o caso de copolimerização, resultados experimentais foram obtidos em diversas temperaturas, e concentração inicial de DVB (divinilbenzeno) e TEMPO. O gel obtido pela polimerização mediada por TEMPO apresenta diferenças marcantes daquele preparado pelo sistema convencional, com relação ao perfil de conversão de monômero. O ponto gel para este caso novo foi obtido em tempos maiores daquele obtido em sistemas convencionais. A versatilidade da polimerização mediada por nitróxidos permite a síntese de um número significativo de novas arquiteturas poliméricas. Espera-se que o modelo proposto, bem como os dados experimentais obtidos neste trabalho, seja útil para um melhor conhecimento desta nova técnica de polimerização. Palavras-chave: polimerização viva/controlada, TEMPO, polimerização em massa, experimental, modelagem
Abstract: Controlled/living radical polymerization (CLRP) is one of the most rapidly developing areas of polymer science and engineering. The ability to prepare well-defined block and graft copolymers, gradient and periodic copolymers, stars, combs, polymer networks, end-functional polymers and many other materials by free-radical mechanisms is perhaps the main reason for the increased academic and industrial interest in CLRP. The industrial interest is triggered by the potential of CLRP in areas as coatings, adhesives, surfactants, dispersants, lubricants, gels, additives, thermoplastic elastomers as well as many electronic and biomedical applications. It is pointed out the industrial production of dispersants by nitroxide-mediated radical polymerization (NMRP), one case of CLRP. This study focus on the model and experimental investigation of TEMPO (2,2,6,6-tetramethyl piperidinyl-1-oxy) mediated free radical polymerization of styrene and styrene-co-divinylbenzene carried out in bulk under different experimental conditions. For homopolymerization case, a sensitivity analyses of how kinetic constants affect the model performance was carried out. Other reactions, not included in the previous model, were included and tested. The effect of different initial concentration of TEMPO was evaluated experimentally. It was shown that this condition affects significantly the results. For copolymerization case, experimental results were obtained for different temperature, and initial concentration of DVB and TEMPO. The gel prepared by NMRP showed remarkable differences from the one prepared in the conventional system, in regard to the monomer conversion profile. The gel point was delayed for the new process compared with conventional systems. The versatility of NMRP permits the synthesis of a number of novel architectures. In conclusion, the model proposed is expected to provide useful guidelines towards a better understanding of the NMRP process. Keywords: controlled/living polymerization, TEMPO, bulk polymerization, experimental, model
Doutorado
Desenvolvimento de Processos Químicos
Doutor em Engenharia Química
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Mochizuki, Shuto. "Controlled radical polymerization in designed porous materials." Kyoto University, 2019. http://hdl.handle.net/2433/242535.

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Vieira, Roniérik Pioli 1989. "Modelagem matemática para a otimização e scale up da polimerização radicalar controlada do estireno." [s.n.], 2013. http://repositorio.unicamp.br/jspui/handle/REPOSIP/266633.

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Orientador: Liliane Maria Ferrareso Lona
Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Química
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Resumo: O processo de polimerização radicalar via transferência de átomo (ATRP) consiste numa das técnicas de polimerização radicalar controlada para a síntese de materiais com estruturas macromoleculares específicas. Através desta técnica, podem-se sintetizar homopolímeros monodispersos (baixos índices de polidispersidade), polímeros com funcionalidades terminais ou numa determinada posição da cadeia, o que permite produzir diversos copolímeros (em bloco, gradiente, aleatório etc), possibilitando agregar aos materiais propriedades requisitadas na indústria automobilística e aeroespacial, cosméticos, tintas e adesivos, além de possibilitar a produção de materiais para a liberação controlada de drogas e outras aplicações biomédicas. Apesar de todo este potencial relacionado à ATRP, a maioria das pesquisas encarrega-se de desenvolver novos materiais em escala laboratorial, deixando de lado a condução do processo em escalas comerciais. Neste contexto, o presente trabalho encarrega-se de desenvolver uma modelagem cinética do processo ATRP, juntamente com uma análise dos resultados da simulação para proporcionar aos leitores uma compreensão geral do processo, além de uma ferramenta matemática para futuros trabalhos de otimização e Scale up. A modelagem matemática foi desenvolvida utilizando balanços materiais, para prever perfis de concentração no reator, e o método dos momentos, para prever as massas molares e polidispersidades dos polímeros formados. Os modelos foram resolvidos numericamente em um programa computacional desenvolvido em linguagem Fortran e validados através de dados de literatura utilizando gráficos de dispersão. Por fim, uma análise paramétrica foi realizada com o intuito de estudar o comportamento do processo sob situações práticas, como por exemplo, alterações na constante de equilíbrio do processo (Keq), influência das razões iniciais de catalisador e iniciador sobre as propriedades finais, influência das terminações e transferências de cadeia, além da influência da temperatura de operação do reator
Abstract: Atom transfer radical polymerization (ATRP) is one of controlled radical polymerization techniques for the synthesis of materials with specific macromolecular structures. Using this technique, one can synthesize monodisperse homopolymer (low polydispersity index), end groups polymers or polymers with functionality in a particular position in the chain, which allows to produce different copolymers (block, gradient, random, etc.), allowing aggregate materials properties required in automotive and aerospace industry, cosmetics, paints and adhesives, and enable the production of materials for the controlled delivery of drugs and other biomedical applications. Despite this potential related to ATRP, most research is responsible for developing new materials on the laboratory scale, leaving aside the conduct of proceedings at commercial scales. In this context, this paper undertakes to develop a kinetic modeling of the ATRP process, together with an analysis of the simulation results to give readers a general understanding of the process, as well as a mathematical tool for future work on optimization and Scale up. A mathematical model was developed using material balances to predict concentration profiles in the reactor, and the method of moments to predict the molecular weight and polydispersities of the polymers formed. The models were solved numerically on a computer program developed in Fortran and validated through literature data using scatter plots. Finally, the parametric analysis was performed in order to study the behavior of chemical species in practical situations, such as changes in the process equilibrium constant (Keq), the influence of the initial ratio of catalyst and initiator on the final properties, influence terminations and chain transfers, beyond the influence of the operating temperature of the reactor
Mestrado
Desenvolvimento de Processos Químicos
Mestre em Engenharia Química
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Yin, Meizhen. "Synthesis and controlled radical polymerization of multifunctional monomers." Doctoral thesis, Saechsische Landesbibliothek- Staats- und Universitaetsbibliothek Dresden, 2004. http://nbn-resolving.de/urn:nbn:de:swb:14-1091453146703-47835.

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Multifunctional monomers on the basis of acryl- and methacryl derivatives were synthesized and different protective groups were used. After polymerization the protective groups were removed by different methods. Various initiators for the NMP of the monomers were synthesized and the reaction conditions were optimized. The results showed that NMP was not a suitable method for multifunctional acryl- and methacryl derivatives to achieve well-defined homopolymers, although it was successful for control of polymerization of styrene and block copolymerization of multifunctional acryl- and methacryl derivatives with alkoxyamine terminated polystyrene. The ATRP of multifunctional acrylates and methacrylates has been successfully performed, as well as the block copolymerization of multifunctional acrylates and methacrylates. Relatively low polydispersities of the corresponding polymers (PD=1.18-1.36) and reasonably high rates of polymerization could be achieved when Me6TREN and PMDETA were used as ligands. However, the ATRP of multifunctional acrylamides and methacrylamides failed. The RAFT-polymerization of styrene, acrylamide and acrylate using BDTB as a CTA and AIBN as an initiator afforded polymers with narrow molecular weight distribution (PD=1.13-1.26). A kinetic investigation and the further synthesis of block copolymers using dithioester-terminated homopolymers as macroCTAs showed that the RAFT polymerization of acrylamide M9b proceeded in a living manner. However, BDTB does not control the reaction of methacrylic monomers, such as methacrylates and methacrylamides. The bulk phase behavior of the block copolymers were examined by means of DSC and the surface behaviors of block copolymers as thin layers were examined with AFM. Two-phase transitions in the block copolymers were observed clearly by DSC, indicative of the appearance of phase separations, which were seen in an AFM image. In conclusion, multifunctional acryl- and methacryl derivatives failed to achieve well-defined homopolymers by NMP. However, this method was successful for block copolymerization of multifunctional acryl- and methacryl derivatives with alkoxyamine terminated polystyrene. Multifunctional acrylates and methacrylates were successfully homopolymerized and block copolymerized by ATRP. Multifunctional acrylates and acrylamides were suitable for homopolymerization and block copolymerization by the RAFT process. Thus far, it is difficult to homopolymerize multifunctional methacrylamides in controlled way.
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Heredia, Karina Lynn. "Synthesis of polymer bioconjugates using controlled radical polymerization." Diss., Restricted to subscribing institutions, 2008. http://proquest.umi.com/pqdweb?did=1583873071&sid=37&Fmt=2&clientId=1564&RQT=309&VName=PQD.

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Qi, Genggeng. "Unconventional radical miniemulsion polymerization." Diss., Atlanta, Ga. : Georgia Institute of Technology, 2008. http://hdl.handle.net/1853/26547.

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Thesis (Ph.D)--Chemical Engineering, Georgia Institute of Technology, 2009.
Committee Chair: Jones, Christopher W.; Committee Chair: Schork, F. Joseph; Committee Member: Koros, William J.; Committee Member: Lyon, Andrew; Committee Member: Nenes, Athanasios. Part of the SMARTech Electronic Thesis and Dissertation Collection.
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Gonçalves, Maria Cecilia. "Estudo experimental da polimerização via radical livre controlada em presença de radicais nitroxido (NMRP)." [s.n.], 2006. http://repositorio.unicamp.br/jspui/handle/REPOSIP/266346.

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Orientador: Liliane Maria Ferrareso Lona
Dissertação (mestrado) - Universidade Estadual de Campinas. Faculdade de Engenharia Quimica
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Resumo: A polimerização via radical livre controlada mediante radicais nitróxido (NMRP) tem recebido cada vez mais atenção como uma técnica para produção de polímeros com estrutura altamente controlada. Distribuições de pesos moleculares estreitas são obtidas, com polidispersidades baixas. Neste trabalho, será estudado o processo NMRP, no qual ocorre a adição de um radical nitróxido estável, como o 2,2,6,6-tetrametil-l-piperidinoxil (TEMPO) para capturar o radical em crescimento. Embora o processo NMRP de ao polímero características controladas (polidipersidades baixas e pesos moleculares que aumentam linearmente com a conversão), ainda existe um desafio nos processos controlados, por apresentarem baixas velocidades de reação. O objetivo principal deste trabalho está focado num estudo experimental do processo NMRP visando aumentar a velocidade de reação sem perder as características principais do processo. O efeito de dois iniciadores BPO (peróxido de benzoíla) e TBEC (tert-butilperóxido-2-etilhexil carbonato) foi analisado. Observou-se que o TBEC (iniciador com constante de decomposição baixa) foi capaz de aumentar significativamente a taxa de polimerização do processo NMRP, quando comparado ao BPO, pois conversões mais altas foram obtidas, num mesmo tempo de reação, mantendo a característica controlada do sistema. O uso do TBEC apresenta uma vantagem frente ao BPO em processos controlados, não somente porque reduz o tempo de reação, mas também porque concentrações menores de iniciador e controlador foram usadas, obtendo uma taxa de reação ainda maior, o que reduz o custo operacional. Para as condições estudadas, comprovou-se experimentalmente que a taxa de reação é inversamente proporcional à concentração inicial de TEMPO, para uma mesma concentração de iniciador. A análise dos resultados através da aplicação da técnica de planejamento de experimento auxiliou numa melhor compreensão do sistema e na obtenção de condições ótimas de operação para se obter baixas polidispersidades e baixos tempos de polimerização
Abstract: NMRP process (Nitroxide Mediated Radical Polymerization) has received increasing attention as a technique for production polymers with highly controlled structures, narrow molecular weight distribution (MWD) and polydispersity index dose to 1.0. In this work 2,2,6,6-tetramethyl-l-piperidinoxyl (TEMPO) is used as the stable radical to reversibly terminate the growing polymer chain. Polymerizations were performed in ampoules, using TBEC (tert-butylperoxy-2-ethylhexyl carbonate) and BPO (benzoyl peroxide) as initiators. With the purpose of enhancing the reaction rate for NMRP process maintaining the controlled and living characteristics of the polymer synthesized (low polidispersity and molecular weights increasing linearly with conversion) an experimental study was done to evaluate the effect of two different initiators (BPO and TBEC). It was observed that TBEC (initiator with low decomposition rate) was able to enhance significant1y the polymerization rate compared to BPO, keeping the living and controlled characteristics of the system. The results show that TBEC seems to be a promising initiator that make the NMRP process more efficient, not only because it reduces the polymerization time, but also because it allows smaller amounts of controller and initiator to be used. For the operational conditions studied, experimental results with TBEC exposed that the polymerization rate in inversely proportional to the initial concentration of TEMPO, for the same amount of initiator. Using a statistical planning, it was possible to obtain a better understanding of the system and to search for operating conditions that bring low polydispersity and low reaction rates. Finally, the results are expected to have significant benefits for controlled polymerization on an industrial setting
Mestrado
Desenvolvimento de Processos Químicos
Mestre em Engenharia Química
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Minaux, Eric. "Controlled radical polymerization at pressures up to 2000 bar." Doctoral thesis, [S.l.] : [s.n.], 2001. http://deposit.ddb.de/cgi-bin/dokserv?idn=962677035.

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Books on the topic "Controled radical polymerization"

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Matyjaszewski, Krzysztof, ed. Controlled Radical Polymerization. Washington, DC: American Chemical Society, 1998. http://dx.doi.org/10.1021/bk-1998-0685.

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K, Matyjaszewski, American Chemical Society. Division of Polymer Chemistry., and American Chemical Society Meeting, eds. Controlled radical polymerization. Washington, DC: American Chemical Society, 1998.

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Matyjaszewski, Krzysztof, ed. Controlled/Living Radical Polymerization. Washington, D C: American Chemical Society, 2006. http://dx.doi.org/10.1021/bk-2006-0944.

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Matyjaszewski, Krzysztof, ed. Controlled/Living Radical Polymerization. Washington, DC: American Chemical Society, 2000. http://dx.doi.org/10.1021/bk-2000-0768.

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Matyjaszewski, Krzysztof, Brent S. Sumerlin, Nicolay V. Tsarevsky, and John Chiefari, eds. Controlled Radical Polymerization: Mechanisms. Washington, DC: American Chemical Society, 2015. http://dx.doi.org/10.1021/bk-2015-1187.

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Matyjaszewski, Krzysztof, Brent S. Sumerlin, Nicolay V. Tsarevsky, and John Chiefari, eds. Controlled Radical Polymerization: Materials. Washington, DC: American Chemical Society, 2015. http://dx.doi.org/10.1021/bk-2015-1188.

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Tsarevsky, Nicolay V., and Brent S. Sumerlin, eds. Fundamentals of Controlled/Living Radical Polymerization. Cambridge: Royal Society of Chemistry, 2013. http://dx.doi.org/10.1039/9781849737425.

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Matyjaszewski, Krzysztof, ed. Advances in Controlled/Living Radical Polymerization. Washington, DC: American Chemical Society, 2003. http://dx.doi.org/10.1021/bk-2003-0854.

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K, Matyjaszewski, American Chemical Society. Division of Polymer Chemistry, and American Chemical Society Meeting, eds. Advances in controlled/living radical polymerization. Washington, DC: American Chemical Society, 2003.

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K, Matyjaszewski, ed. Controlled/living radical polymerization: Progress in ATRP. Washington DC: American Chemical Society, 2009.

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Book chapters on the topic "Controled radical polymerization"

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Ambade, Ashootosh V. "Controlled Radical Polymerization." In Metal-Catalyzed Polymerization, 161–77. Boca Raton : CRC Press, 2018.: CRC Press, 2017. http://dx.doi.org/10.1201/9781315153919-5.

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Lefay, Catherine, and Julien Nicolas. "Controlled/Living Radical Polymerization in Aqueous Miniemulsion." In Miniemulsion Polymerization Technology, 173–210. Hoboken, NJ, USA: John Wiley & Sons, Inc., 2010. http://dx.doi.org/10.1002/9780470922354.ch7.

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Flores, Joel D., Brooks A. Abel, DeeDee Smith, and Charles L. McCormick. "Stimuli-Responsive Polymers Via Controlled Radical Polymerization." In Monitoring Polymerization Reactions, 45–58. Hoboken, NJ: John Wiley & Sons, 2014. http://dx.doi.org/10.1002/9781118733813.ch3.

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Reynaud, Stéphanie, and Bruno Grassl. "Microwave-Assisted Controlled Radical Polymerization." In Microwave-assisted Polymer Synthesis, 131–47. Cham: Springer International Publishing, 2014. http://dx.doi.org/10.1007/12_2014_302.

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Spanswick, James, and Bernard Pike. "Opportunities in Controlled Radical Polymerization." In ACS Symposium Series, 385–96. Washington DC: American Chemical Society, 2009. http://dx.doi.org/10.1021/bk-2009-1023.ch026.

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Klapper, Markus, Thorsten Brand, Marco Steenbock, and Klaus Müllen. "Triazolinyl Radicals: Toward a New Mechanism in Controlled Radical Polymerization." In ACS Symposium Series, 152–66. Washington, DC: American Chemical Society, 2000. http://dx.doi.org/10.1021/bk-2000-0768.ch011.

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Tasdelen, Mehmet Atilla, Mustafa Çiftci, Mustafa Uygun, and Yusuf Yagci. "Possibilities for Photoinduced Controlled Radical Polymerizations." In ACS Symposium Series, 59–72. Washington, DC: American Chemical Society, 2012. http://dx.doi.org/10.1021/bk-2012-1100.ch005.

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Ryan, Matthew D., Ryan M. Pearson, and Garret M. Miyake. "Chapter 13. Organocatalyzed Controlled Radical Polymerizations." In Polymer Chemistry Series, 584–606. Cambridge: Royal Society of Chemistry, 2018. http://dx.doi.org/10.1039/9781788015738-00584.

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Khabibullin, Amir, Erlita Mastan, Krzysztof Matyjaszewski, and Shiping Zhu. "Surface-Initiated Atom Transfer Radical Polymerization." In Controlled Radical Polymerization at and from Solid Surfaces, 29–76. Cham: Springer International Publishing, 2015. http://dx.doi.org/10.1007/12_2015_311.

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Tsarevsky, Nicolay V. "Degradable and Biodegradable Polymers by Controlled/Living Radical Polymerization: From Synthesis to Application." In Green Polymerization Methods, 235–61. Weinheim, Germany: Wiley-VCH Verlag GmbH & Co. KGaA, 2011. http://dx.doi.org/10.1002/9783527636167.ch11.

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Conference papers on the topic "Controled radical polymerization"

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Zhandong Yu, Xiren Zhao, and Tianyu An. "Adaptive Fuzzy Indirectly Quality-Control for Free-radical Polymerization Reactor." In 2006 6th World Congress on Intelligent Control and Automation. IEEE, 2006. http://dx.doi.org/10.1109/wcica.2006.1714284.

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Wylde, Jonathan J. "The Challenges Associated with Reaction Products Left in Scale Inhibitor Species after Radical Polymerization." In SPE International Oilfield Scale Conference and Exhibition. SPE, 2014. http://dx.doi.org/10.2118/spe-169778-ms.

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Abstract The use of polymeric scale inhibitors has been ubiquitously accepted by the oil and gas industry for many years. There are many benefits to the use of this type of chemistry that include aspects such as high performance, scale species selectivity, enhanced brine compatibility, favorable environmental properties and high thermal stability. A very common way to manufacture polymeric scale inhibitors is via free radical polymerization. Here an initiator is used to propagate the generation of free radicals from a species, such as hydrogen peroxide. The initiator chemistry can be very varied and usually comprises different types of transition metal salts, hypophosphite or persulfate species. Different monomer units can be polymerized using different initiator and free radical species to yield the same polymer. However, subtle differences can result, including poly-dispersity, average molecular weight and different residual composition. The implications for the end user of the chemistry can be profound regarding performance differences in aspects such as detectability, compatibility, thermal stability and sometimes even scale inhibition and adsorption efficacy. A case study has been presented where a very commonly used sulfonated copolymer species from four different sources was evaluated in a whole host of compatibility and performance tests. The different routes used different combinations of hydrogen peroxide and transition metal initiator or persulfate/hypophosphite combinations as the free radical source. There were major differences seen in the compatibility of these products with different scale inhibitors and then in performance. The tests performed highlighted the differences that can occur between the different radical polymerization synthetic routes mentioned above. The conclusions show that there are many benefits to being able to control the manufacturing process of scale inhibitor species in order to ensure the full composition is understood and can be quantified. The benefits to owning the supply chain are highlighted and lead to not only better control of quality and cost but, more importantly, to the overall risk reduction for the end user in the end use application.
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Gizzatov, D. R., A. A. Kornilova, G. K. Khisametdinova, and E. R. Gizzatova. "The Method of Basic Functions in the Analysis of Monomer Conversion in Radical Polymerization." In 2023 5th International Conference on Control Systems, Mathematical Modeling, Automation and Energy Efficiency (SUMMA). IEEE, 2023. http://dx.doi.org/10.1109/summa60232.2023.10349482.

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Yoshida, Jun-ichi, and Aiichiro Nagaki. "Flash Chemistry - Fast Chemical Synthesis in Micro Flow Systems." In ASME 2009 7th International Conference on Nanochannels, Microchannels, and Minichannels. ASMEDC, 2009. http://dx.doi.org/10.1115/icnmm2009-82157.

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Flash chemistry is a field of chemical synthesis where extremely fast reactions are conducted in a highly controlled manner. A key element of flash chemistry is the control of extremely fast reactions to obtain the desired products selectively. For extremely fast reactions, kinetics often cannot be used because of the lack of homogeneity of the reaction environment when they are conducted in conventional reactors such as flasks. Fast micromixing by virtue of short diffusion path solves such problems. Fast reactions are usually highly exothermic, and heat removal is an important factor in controlling such reactions. Heat transfer occurs very rapidly in micro flow systems by virtue of a large surface area per unit volume, making precise temperature control possible. Another important point is that fast reactions often involve highly unstable intermediates, which decompose very quickly, making reaction control difficult. The residence time can be greatly reduced in micro flow systems, and this feature is quite effective in controlling such reactions. The concept of flash chemistry has been successfully applied to various organic reactions for synthesis including (a) reactions in which undesired byproducts are produced in the subsequent reactions in conventional reactors, (b) highly exothermic reactions that are difficult to control in conventional reactors, and (c) reactions in which a reactive intermediate easily decomposes in conventional reactors. The concept of flash chemistry can be also applied to polymer synthesis. Cationic polymerization can be conducted with an excellent level of molecular-weight control and molecular-weight distribution control. Radical polymerization in micro flow systems leads to better molecular weight distribution control than macro batch systems. Anionic polymerization can also be carried out micro flow systems at higher temperatures than macro batch systems with high degree of molecular weight distribution control.
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Serra, Christophe, Nicolas Sary, and Guy Schlatter. "Numerical Simulations of Macromolecular Syntheses in Micro-Mixers: Towards a Better Control of the Polymerization." In ASME 3rd International Conference on Microchannels and Minichannels. ASMEDC, 2005. http://dx.doi.org/10.1115/icmm2005-75044.

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This paper investigates the modeling of styrene free radical polymerization in two different types of micro-mixer for which the wall temperature is kept constant. The simulations are performed with the help of the finite elements method which allows solving simultaneously partial differential equations resulting from the hydrodynamics, thermal and mass transfer (convection, diffusion and chemical reaction). The different micro-mixers modeled are on one hand an interdigital multilamination micro-mixer with a large focusing section and on the other hand a simple T-junction with three different radii followed by a tube reactor having the same radius. The results are expressed in terms of reactor temperature, polydispersity index, number-average degree of polymerization and monomer conversion for different values of the chemical species diffusion coefficient. Despite of the heat released by the polymerization reaction, it was found that the thermal transfer in such microfluidic devices is high enough to ensure isothermal conditions. Concerning the polydispersity index, the range of diffusion coefficients over which the polydispersity index can be maintained close to the theoretical value for ideal conditions increases as the tube reactor radius decreases. The interdigital multilamination micro-mixer was found to act as a T-junction and tube reactor of 0,72 mm ID but gives up to 15% higher monomer conversion. This underlines that the use of microfluidic devices can lead to a better control of the polymerization.
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Jian, Guoqing, Ashok Santra, Hasmukh A. Patel, and Ahmet Atilgan. "A Novel Star Polymer based Fluid Loss Control Additive for Non-Aqueous Drilling Fluids." In SPE International Conference on Oilfield Chemistry. SPE, 2023. http://dx.doi.org/10.2118/213791-ms.

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Abstract Non-aqueous fluids (NAF) are considered as efficient and reliable drilling fluid systems for challenging wellbore conditions, such as high-temperature drilling operations. NAFs require fluid loss control additives to reduce filtration loss into the formation with minimum filter cake thickness. Polymer developed in this work demonstrated exceptional properties such as high dispersibility, good thermal stability and low plastic viscosity, when compared with traditional natural and synthetic-based fluid loss control additives (e.g., gilsonite). We have utilized a synthetic molecular optimization process to precisely adjust the hydrophilic-lyophilic balance (HLB) by altering the ratio of hydrophilic to hydrophobic monomers. This has allowed us to achieve an HLB that facilitates easy dispersion within NAF formulations. The star polymer was produced using a controlled/radical polymerization technique called Reversible Addition Fragmentation Chain Transfer polymerization (RAFT). The properties of the NAFs, such as rheology, fluid loss, mud cake thickness, and emulsion stability, were evaluated and compared with commercially available fluid loss control additives under simulated downhole pressure and temperature conditions. The chemical structure and thermal stability of the star polymer were analyzed using spectroscopy and thermogravimetric analysis. The spectroscopic studies confirmed the formation of desired polymeric structures and the molecular weight desired. Star-polymer synthesized herein has excellent thermal stability up to 450 °F with great fluid loss control and ultrathin filter cake for NAF systems for mud weight ranging from 10 to 17 lbm/gal. The star polymer also improves emulsion stability. Plastic viscosity (PV) is usually increased with the addition of commercially available fluid loss control additives; however, star-polymer had a negligible effect on PV. Results for both diesel and mineral oil-based mud systems will be presented. High-temperature high-pressure viscometer (Fann 77) was used to study rheological properties at up to 350 °F and 10,000 psi. Our recent work has resulted in the creation of a cutting-edge star polymer (NSP) for use in the industry's next-gen high-performance fluid loss additives. The polymer network can be efficiently synthesized and scaled up for commercial production, providing engineers with an improved solution for drilling high-temperature wells (up to 350°F) with reduced plastic viscosity and increased emulsion stability, while also providing excellent fluid loss control.
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Guvendiren, Murat, and Jason A. Burdick. "Dynamic Mechanical Properties Control Adult Stem Cell Fate." In ASME 2012 Summer Bioengineering Conference. American Society of Mechanical Engineers, 2012. http://dx.doi.org/10.1115/sbc2012-80062.

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Stem cells respond to many microenvironmental cues towards their decisions to spread, migrate, and differentiate and these cues can be incorporated into materials for regenerative medicine.1 In the last decade, matrix stiffness alone has been implicated in regulating cellular functions such as migration, proliferation and differentiation. With this in mind, a variety of natural and synthetic polymer systems were used in vitro to mimic the elasticity of native tissues. Despite helping to develop this important field and gather valuable information, these substrates are primarily static and lack the dynamic nature that is observed during many cellular processes such as development, fibrosis and cancer. Thus, it is of great interest to temporally manipulate matrix elasticity in vitro to better understand and develop strategies to control these biological processes. In this work, we utilize a sequential crosslinking approach (initial gelation via addition reaction, secondary crosslinking through light-mediated radical polymerization) to fabricate hydrogel substrates that stiffen (e.g., ∼3 to 30 kPa) either immediately or at later times and in the presence of cells. We demonstrate the utility of this technique by investigating the short-term (several minutes to hours) and long-term (several days to weeks) stem cell response to dynamic stiffening
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Nakatsuka, Noriaki, Yasushi Imoto, Jun Hayashi, Miki Taniguchi, Kenichi Sasauchi, Mayumi Matsuda, and Fumiteru Akamatsu. "Decomposition of Toluene as a Biomass Tar Through Partial Combustion." In ASME/JSME 2011 8th Thermal Engineering Joint Conference. ASMEDC, 2011. http://dx.doi.org/10.1115/ajtec2011-44159.

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For the electric power generation by the woody biomass gasification, tar is incidentally formed at the same time. Tar means a compound of many kinds of aromatic hydrocarbons and causes some troubles, for example, clogging pipes when it is cooled and condensed before being supplied to the gas engine for electric power generation. One way for reducing tar is oxidative and thermal cracking by partial combustion of the producer gas in the gas reformer that is a stage subsequent to the biomass gasifier. During the partial combustion process of the producer gas, inverse diffusion flame is formed when oxidizer is supplied to producer gas. Cracking and polymerization of tar occur simultaneously at the proximity of the inverse diffusion flame. This polymerization of tar into soot is, however, a significant problem in the gas reformer. Experimental study was performed to clarify the effect of hydrogen concentration in the combustion region on soot formation and the growth of polycyclic aromatic hydrocarbons (PAHs) that is precursor of soot. In the present study, hydrogen concentration at the proximity of the inverse diffusion flame was controlled by the small amount of hydrogen addition to the oxidizer. The main results were as follows. Soot formation was suppressed by the small amount of hydrogen addition (approximately 0.5% to the total enthalpy of the producer gas). The suppression of soot formation was caused by higher concentration of hydrogen at the proximity of the combustion region since the aromatic radicals were neutralized before they could combine together or with acetylene. Carbon yield was increased with the increase in the amount of hydrogen added to the oxidizer as carbon content in the undetectable components by the integrated gas chromatograph such as the soot was decreased. In addition, the increase of carbon yield resulted mainly from the increase in carbon monoxide stemmed from reforming of high-boiling components such as soot.
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Reports on the topic "Controled radical polymerization"

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Matyjaszewski, K., S. Gaynor, D. Greszta, D. Mardare, and T. Shigemoto. Unimolecular and Bimoleculare Exchange Reactiions in Controlled Radical Polymerization. Fort Belvoir, VA: Defense Technical Information Center, June 1995. http://dx.doi.org/10.21236/ada295862.

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Hu, S., J. H. Malpert, X. Yang, and D. C. Neckers. Exploring Chromophore Tethered Aminoethers as Potential Photoinitiators for Controlled Radical Polymerization. Fort Belvoir, VA: Defense Technical Information Center, November 1999. http://dx.doi.org/10.21236/ada370961.

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Matyjaszewski, Krzysztof. The Importance of Exchange Reactions in Controlled/Living Radical Polymerization in the Presence of Alkoxyamines and Transition Metals. Fort Belvoir, VA: Defense Technical Information Center, June 1996. http://dx.doi.org/10.21236/ada309796.

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