The examination of network formation theories ad rubber elasticity on model poly(urethane-isocyanurate) systems

U radu su prvi put za proveru teorija nastajanja i gumolike elastičnosti polimernih mreža primenjeni modelni poliuretanski sistemi čiji su čvorovi veoma stabilni izocijanurat(heksahidro-1,3,5-triazin- 2,4,6-trion) prstenovi. Rad obuhvata: (1) Sintetezu nekoliko serija homogenih poli(uretan-izocijanuratnih) mreža, na bazi 2.4-TDI i poli(oksipropilen)diola, dvoetapnim postupkom u masi, tj. ciklotrimerizacijom teleheličnih diizocijanata uz katalizator Polycat 41. (2) Sintezu manje savršenih mreža sa nekom definisanom koncentracijom visećih lanaca koja je postignuta uvodenjem monoola dietilenglikol- monometiletra u toku pripreme prepolimera. (3) Odredivanje povoljnih reakcionih uslove svih etapa sinteze uz primenu i modifikaciju postojećih analitičkih postupaka za karakterizaciju svojstava reakcionih komponenti i praćenja reakcija umrežavanja. (4) Procenu mogućih bočnih reakcija u toku nastajanja mreža jer one mogu značajno uticati na raspodelu različitih fragmenata u mrežama praćenjem koncentracija reakcionih proizvoda kod modelnih reakcija u rastvoru uz isti diol i isti katalizator i odgovarajuće mono-funkcionalne izocijanatne komponente. (5) Karakterizaciju svojstava i strukturnih parametara modelnih mreža i to primenom postupaka ekstrakcije i bubrenja, diferencijalne skanirajuće kalorimetrije, fotoelastičnih merenja, dinamičko-mehaničke spektroskopije i merenja napon-istezanje. Izborom nominalne Mn diola od 400 do 4000 postigne gustina umreženja 0.1x10-4mol/cm3 do 10x10-4mol/cm3 sa rasponom temperatura staklastog prelaza od -60°C do +30°C. Za procenu strukturnih parametara mreža primenjena je teorija granajućih procesa sa kaskadnom zamenom za slučaj nastajanja mreža ciklotrimerizacijom i dvoetapni postupak. U zavisnosti od konverzije NCO grupa u mrežama izračunate su masa po monomernoj jedinici, maseni udeo, broj po monomernoj jedinici, koncentracija po jedinici zapremine, Mn, Mw, Mz i Mw/Mn kako za elastično aktivne, osnovne i viseće lance tako i zamolekule sola. Ključni ekspehmentalni podaci koji su korišćeni za proveru teorija nastajanja bio sadržaj gela dobijen višestrukim ekstrakcijama, a za teorije gumolike elastičnosti ravnotežni modul dobijen iz fotoelastičnih merenja. Provera teorija gumolike elastičnosti se zasnivala se u nalaženje vrednosti pred- faktora 3 (tzv. faktora pamćenja) u jednačini koja daje vezu ravnotežnog modula elastičnosti i koncentracije elastično aktivnih lanaca mreže koji ukazuje na način fluktuacije cvorova mreže. Fotoelastična merenja su omogućila da se preko njih parameter pred-faktor 3 proceni pri malim deformacijama. Potvrden je koncept stvarnih mreža sa delimično potisnutim fluktuacijama čvorova uz aditivni doprinos zapletenosti lanaca modulu elastičnosti prema Langley-Graesley konceptu zarobljenih prepletaja.In this thesis polymer network formation theories and rubber elasticity of polymer networks on model polyurethane systems having as a junction very stable isocyanurate(hexahidro-1,3,5-tгiazin-2,4,6- trion) rings are for the first time investigated. The work contains: (1) Synthesis of homogenious series of several poly(urethane-isocyanurate) networks based on poly(oxypropylene)diol and 2.4-TDI by two stages procedures in bulk i.e. cyclotrimerization of telechelic diisoicyanates with Polycat 41 as catalyst. (2) Synthesis of less perfect networks with some concentration of dangling chains obtained by introduction of monofunctional component diethyleneglycolmonomethylether during prepolymer formation. (3) Determination of optimal reaction conditions for both stages of the synthesis. (4) Estimation of possible side reaction during network formation because of theirs important influence on nework fragment distribution. (5) Caracterization of networks structure and properties by swelling and multiply extraction, differential scanning calorimetry, photoelastical measurements, dynamic-mechanical spectroscopy and stress-strain measurements. By using the different Mn of diols (400 - 4000) the network density from 0.1x10-4mol/cm3 to 10x10-4mol/cm3 and glass transition temperatures from -60°C to +30°C was achieved. For network structure determinations the theory of branching processes with cascade substitution was used. Mass per monomer unit, mass fraction, number per monomer unit, concentration per unit volume, Mn, Mw, Mz and Mw/Mn for elastically active network chains, backbone chains, dangling chains and sol molecules In the dependence on NCO groups conversion are calculated. Crucial experimental data for examination of network formation theories was the gel content and for rubber elasticity theories the equilibrium modulus received from photoelastical measurement. The estimation of rubber elasticity theories was based on the analysis of the front factor 3 in the equation which gives the relation between the equilibrium modulus and concentration of elastically active network chains. It is estimated the additive contribution of chain entanglements to the equilibrium modulus, especially in the case of high networks density according to Langley-Graesley theory of trapped entanglements

The examination of network formation theories ad rubber elasticity on model poly(urethane-isocyanurate) systems

U radu su prvi put za proveru teorija nastajanja i gumolike elastičnosti polimernih mreža primenjeni modelni poliuretanski sistemi čiji su čvorovi veoma stabilni izocijanurat(heksahidro-1,3,5-triazin- 2,4,6-trion) prstenovi. Rad obuhvata: (1) Sintetezu nekoliko serija homogenih poli(uretan-izocijanuratnih) mreža, na bazi 2.4-TDI i poli(oksipropilen)diola, dvoetapnim postupkom u masi, tj. ciklotrimerizacijom teleheličnih diizocijanata uz katalizator Polycat 41. (2) Sintezu manje savršenih mreža sa nekom definisanom koncentracijom visećih lanaca koja je postignuta uvodenjem monoola dietilenglikol- monometiletra u toku pripreme prepolimera. (3) Odredivanje povoljnih reakcionih uslove svih etapa sinteze uz primenu i modifikaciju postojećih analitičkih postupaka za karakterizaciju svojstava reakcionih komponenti i praćenja reakcija umrežavanja. (4) Procenu mogućih bočnih reakcija u toku nastajanja mreža jer one mogu značajno uticati na raspodelu različitih fragmenata u mrežama praćenjem koncentracija reakcionih proizvoda kod modelnih reakcija u rastvoru uz isti diol i isti katalizator i odgovarajuće mono-funkcionalne izocijanatne komponente. (5) Karakterizaciju svojstava i strukturnih parametara modelnih mreža i to primenom postupaka ekstrakcije i bubrenja, diferencijalne skanirajuće kalorimetrije, fotoelastičnih merenja, dinamičko-mehaničke spektroskopije i merenja napon-istezanje. Izborom nominalne Mn diola od 400 do 4000 postigne gustina umreženja 0.1x10-4mol/cm3 do 10x10-4mol/cm3 sa rasponom temperatura staklastog prelaza od -60°C do +30°C. Za procenu strukturnih parametara mreža primenjena je teorija granajućih procesa sa kaskadnom zamenom za slučaj nastajanja mreža ciklotrimerizacijom i dvoetapni postupak. U zavisnosti od konverzije NCO grupa u mrežama izračunate su masa po monomernoj jedinici, maseni udeo, broj po monomernoj jedinici, koncentracija po jedinici zapremine, Mn, Mw, Mz i Mw/Mn kako za elastično aktivne, osnovne i viseće lance tako i zamolekule sola. Ključni ekspehmentalni podaci koji su korišćeni za proveru teorija nastajanja bio sadržaj gela dobijen višestrukim ekstrakcijama, a za teorije gumolike elastičnosti ravnotežni modul dobijen iz fotoelastičnih merenja. Provera teorija gumolike elastičnosti se zasnivala se u nalaženje vrednosti pred- faktora 3 (tzv. faktora pamćenja) u jednačini koja daje vezu ravnotežnog modula elastičnosti i koncentracije elastično aktivnih lanaca mreže koji ukazuje na način fluktuacije cvorova mreže. Fotoelastična merenja su omogućila da se preko njih parameter pred-faktor 3 proceni pri malim deformacijama. Potvrden je koncept stvarnih mreža sa delimično potisnutim fluktuacijama čvorova uz aditivni doprinos zapletenosti lanaca modulu elastičnosti prema Langley-Graesley konceptu zarobljenih prepletaja.In this thesis polymer network formation theories and rubber elasticity of polymer networks on model polyurethane systems having as a junction very stable isocyanurate(hexahidro-1,3,5-tгiazin-2,4,6- trion) rings are for the first time investigated. The work contains: (1) Synthesis of homogenious series of several poly(urethane-isocyanurate) networks based on poly(oxypropylene)diol and 2.4-TDI by two stages procedures in bulk i.e. cyclotrimerization of telechelic diisoicyanates with Polycat 41 as catalyst. (2) Synthesis of less perfect networks with some concentration of dangling chains obtained by introduction of monofunctional component diethyleneglycolmonomethylether during prepolymer formation. (3) Determination of optimal reaction conditions for both stages of the synthesis. (4) Estimation of possible side reaction during network formation because of theirs important influence on nework fragment distribution. (5) Caracterization of networks structure and properties by swelling and multiply extraction, differential scanning calorimetry, photoelastical measurements, dynamic-mechanical spectroscopy and stress-strain measurements. By using the different Mn of diols (400 - 4000) the network density from 0.1x10-4mol/cm3 to 10x10-4mol/cm3 and glass transition temperatures from -60°C to +30°C was achieved. For network structure determinations the theory of branching processes with cascade substitution was used. Mass per monomer unit, mass fraction, number per monomer unit, concentration per unit volume, Mn, Mw, Mz and Mw/Mn for elastically active network chains, backbone chains, dangling chains and sol molecules In the dependence on NCO groups conversion are calculated. Crucial experimental data for examination of network formation theories was the gel content and for rubber elasticity theories the equilibrium modulus received from photoelastical measurement. The estimation of rubber elasticity theories was based on the analysis of the front factor 3 in the equation which gives the relation between the equilibrium modulus and concentration of elastically active network chains. It is estimated the additive contribution of chain entanglements to the equilibrium modulus, especially in the case of high networks density according to Langley-Graesley theory of trapped entanglements

Thermal ageing and γ-radiation resistance of polyisoprene /chlorosulphonated polyethylene rubber blends

The effect of carbon black (average particle size 26nm) and wood flour (particle size from 300 to 400 μm) on thermal ageing and γ-radiation resistance of polyisoprene /chlorosulphonated polyethylene rubber blend (NR/CSM) was studied. The tensile strength of the aged samples was determined, after conditioning at 70°C during 72h. The radiation exposure of samples was performed at two doses: 212 and 400 kGy.Physical chemistry 2008 : 9th international conference on fundamental and applied aspects of physical chemistry; Belgrade (Serbia); 24-28 September 200

The influence of carbon black on curing kinetics and thermal aging of acrylonitrile–butadiene rubber

Elastomers based on a copolymer of butadiene and acrylonitrile (NBR) have excellent oil resistance but are very sensitive for degradation at very high temperatures. The aim of this applicative contribution was to determine the effect of high abrasion furnace carbon black with primary particle size 46 nm on aging properties of elastomeric materials based on NBR as network precursor. The curing kinetics was determined using the rheometer with an oscillating disk, in which the network formation process is registered by the torque variation during time. The vulcanizates were obtained in a hydraulic press at 150 °C. The mechanical properties of elastomeric composites were determined before and after thermal aging in an air circulating oven. The reinforcing effect of the filler particles was assessed according to mechanical properties before and after aging

Properties of elastomeric materials based on polychloroprene/chlorosulfonated polyethylene rubber blends

In this work the elastomeres based on polychloroprene/chlorosulphonated polyethylene rubber blends (CR/CSM) intended for rubber-metal bonding has been studied. The rheographs and curing characteristics of blends reinforced by active precipitated silica and diatomaceous earth were obtained using a Monsanto rheometer. Crosslinking has been performed by sulphur at 160 °C up to optimum cure time. Temperature dependence of storage modulus (E’), tanδ and glass transition temperature were determinated by mechanical spectroscopy. Adhesion strength has been measured by two methods. It was concluded that a adhesion strength value can be increased by using nano fillers as reinforcing agensPhysical chemistry 2004 : 7th international conference on fundamental and applied aspects of physical chemistry; Belgrade (Serbia); 21-23 September 200

Fermentation of lignocellulosic renewable resources and hydrogen production

Using cheap renewable raw materials such as lignocellulosic feedstock for hydrogen production by fermentation has great significance and potential to give a major contribution to future clean energy. Using hydrogen as a promising alternative energy source for fossil fuels is increasing. Hydrogen is clean, renewable high energy fuel that does not contribute the greenhouse gas effect. The main challenges in developing hydrogen production are the low hydrogen yields due to poor efficiency on a direct microbial assimilation of cellulosic materials. From this reason, in the world today occurs considerable research efforts to improve the pretreatment and hydrolysis of lignocellulosic materials. The development of effective cellulase enzymes, optimization and improvement of the fermentation process as well as engineering approaches to application processes are the basis of the increased popularity of the lignocellulosic feedstock. Research on the genomic combined with genetic engineering offers a wide range of opportunities to improve the performance of using cellulosic raw materials in the production of hydrogen. This paper provides an overview of key technologies in the world today that research and development biohydrogen from lignocellulosic feedstocks

Curing characteristics of chlorosulphonated polyethylene and natural rubber blends

The dependence of the Mooney scorch time and cure index on the blend ratio of chlorosulphonated polyethylene/natural rubber (CSM/SMR 20 CV) and chlorosulphonated polyethylene/chlorinated natural rubber (CSM/Pergut S 40) blends were determined in the temperature range from 120 C to 160 C using a Monsanto Mooney viscometer. Semi-efficient vulcanization systems were used for the study. The morphology of the fracture surface of the crosslinked systems was determined by Scanning Electron Microscopy (SEM). The results showed that the scorch time decreased with increasing SMR 20 CV and Pergut S 40 contents. This observation is attributed to the increasing solubility of sulfur, as the content of SMR 20 CV and Pergut S 40 in the composition increased. For temperatures greater than 140 C, the dependence of the scorch time on blend ratios diminishes, as enough thermal energy is available to overcome the activation energy of vulcanization. The differing curing characteristics of the two blends is explained by the compatibility factor of the respective blend. Morphological analysis of the blends shows a very satisfactory agreement

Thermostability and surface morphology of nano- and micro-filled NBR/CSM and CR/CSM rubber blends

Acrylonitrile-butadiene rubber (NBR), polychloroprene rubber (CR). chlorosulphonated polyethylene rubber (CSM) and their blends were cross-linked with sulphur, ethylene-thiourea. magnesium oxide or their combination. The effect of nano- and micro- particle sized of 35 pphr SiO2 on the thermostability and surface morphology of all the crosslinked systems,vas investigated. Identification of the structure of nano- and micro- particle sized SiO2 filled NBR/CSM and CR/CSM crosslinked systems was carried out by Fourier transform infrared spectroscopy (FTIR) with an attenuated total reflectance (ATR) extension. The thermal stability of the nano- and micro- particle sized SiO2 filled NBR/CSM and CR/CSM crosslinked systems were carried out by thermogravimetric analysis (TGA). The glass transition temperature (T-g) of the samples was determined by differential Scanning calorimetry (DSC). The morphology of the fracture surface of the crosslinked systems was carried out by scanning electron microscope (SEM). The results show when filled with nano-particle sized of SiO2 NBR/CSM and CR/CSM polymer matrix have a strong peak from SiO-C at 1079 cm(-1). This suggests the an interaction between the SiO2, which should lead to an increased thermal stability, higher values of T-g, better dispersion the nano-SiO2 and more polish, without cracks than micro-filled NBR/CSM and CR/CSM crosslinked systems

The High-Energy Irradiation Ageing of Reinforced Elastomers Based on Rubber Blends

Elastomers are very often used in severe environments, for instance, in nuclear power plants, where they may be degraded by high-energy radiation and heat. The ageing behaviour of materials used in different equipments is very important. Elastomers based on chlorosulfonated polyethylene (CSM) are used for cable jacketing materials and have excellent radiation resistance needed in nuclear power stations. In the current work, the influence of gamma-irradiation dose (100, 200 and 400 kGy) on the ageing of reinforced blends based on CSM, styrene butadiene rubber (SBR) and natural rubber (NR) has been evaluated. The content of silica in CSM/SBR and CSM/NR rubber blends was varied. The curing behavior of compounds was estimated using the oscillating disk reometer. The irradiation of nano composites has been performed in air in the Co 60 radiation sterilization unit with the dose rate of 10 kGy h(-1). The thermal properties were studied by thermogravimetric test. The mechanical properties (hardness, modulus at 100% elongation, tensile strength and elongation at break) were determined before and after irradiation. A decrease in the elastic modulus and in the strain at break has been observed with increasing irradiation. At higher doses, the network chain scissions become the main degradation process, the cross-linked topology becomes irregular, and material contains more and more weak zones, which deteriorate the ultimate properties.4th International Conference on Radiation and Applications in Various Fields of Research (RAD), Proceedings, May 23-27, 2016, Nis, Serbi

The effect of gamma radiation on the ageing of sulfur cured nr/csm and nbr/csm rubber blends reinforced by carbon black

In this work the effect of the γ-radiation dose on ageing of carbon black reinforced elastomeric materials was studied. The compounds based on natural rubber/chlorosulfonated rubber blend (NR/CSM) and butadiene acrylonitrile rubber/chlorosulfonated rubber blend (NBR/CSM) (50:50, w/w) with different loadings (0, 20, 40, 50, 60, 80 and 100 phr) of the filler with the average particle size of 40 nm were cured by sulfur. The obtained elastomeric composites were subjected to radiation doses (100, 200, 300 and 400 kGy) in the presence of oxygen. The changes of material mechanical properties were estimated after radiation accelerated ageing. By using Fourier transform infrared measurements (ATR-FTIR) it was assessed that after exposure to doses of 100 kGy alcohols, ethers, lactones, anhydrides, esters and carboxylic acids are formed in materials. The formation of shorter polyene sequences and aromatic rings in aged samples are assumed on the basis of the obtained spectra