The paper presents the results of research on the possibility of using as plasticizers of rubber ... more The paper presents the results of research on the possibility of using as plasticizers of rubber compounds the heavy fractions of pyrolytic oil obtained in the industrial process of pyrolysis of car tyres. The content of carcinogenic polycyclic aromatic hydrocarbons (PAHs) in the obtained pyrolytic plasticizers was determined. Compounds and vulcanizates of styrene-butadiene rubber (SBR) containing the above plasticizers as well as commercial petroleum derivatives plasticizers were prepared for comparative purposes. The basic properties of compounds and vulcanizates containing pyrolytic plas-ticizers were investigated. The research found that one fraction of pyrolysis oil meet the requirements of the permitted content of PAHs. SBR blends and vulcanizates it gives similar properties as in the case of commercial plasticizers. Keywords: tyre pyrolysis, pyrolytic oil, plasticizer, rubber compound, vulcanizate, rubber.
Due to its high total sulphur content and other unfavourable properties, pyrolytic oil obtained a... more Due to its high total sulphur content and other unfavourable properties, pyrolytic oil obtained as a result of tyres pyrolysis is not suitable for use as motor or heating fuel. Therefore, pyrolytic oil was hydrorefined. Hydrorefined oil was used as a component of light heating oil. A composition was prepared from 30 wt % hydrorefinate with 70 wt % Ekoterm Plus (a commercial oil). Unfortunately, the flash point temperature of the hydrorefinate was too low, and did not allow fuel compliant with the Polish standard PN-C-96024:2011 for L1 light heating oil to be obtained. Therefore, the fraction with boiling point below 180 • C was removed from the hydrorefinate. The residue, with a flash point of 74 • C and a sulphur content of 0.143 wt %, was mixed with Ekoterm Plus and fuels with a hydrorefinate fraction content of 30 and 50 wt % were prepared. The composition containing 30 wt % met the requirements for L1 oil in the whole range of tested parameters. Total sulphur content was 0.092 wt %, specific weight was 856 kg/m 3 and closed cup flash point was 64 • C. However, the composition containing 50 wt % hydrorefinate did not meet the requirements regarding sulphur content and specific weight. Sulphur content, specific gravity, and flash point are the parameters limiting the possibility of using hydrorefined pyrolytic oil for composing light heating oils compliant with the mentioned standard. Keywords: tyre pyrolysis; rubber; pyrolytic oil; hydrorefining; hydrodesulphurization; light fuel oil
The paper presents the results of studies on the repeatability of properties of compounds and vul... more The paper presents the results of studies on the repeatability of properties of compounds and vulcanizates of styrene-butadiene rubber containing independent samples of pyrolytic carbon black. For comparison, analogous compounds and vulcanizates containing technical carbon black N550, N772 and kaolin were examined. It was found that pyrolytic carbon black gives the compounds high Mooney viscosity. The obtained viscosity values for the three carbon black tests are repeatable, within the range of ±5%. Compounds with pyrolytic carbon black samples have optimum vulcanization time (t90) values similar to those of compounds containing technical carbon black. The dispersion of the t90 values is greater and is ±14%. It was found that the more sulphur and zinc compounds containing pyrolytic carbon black, the higher the rate of vulcanization. Individual samples of pyrolytic carbon black give SBR vulcanizates a high and reproducible hardness equal to that of carbon black vulcanizate N550 and much higher than that of carbon black vulcanizate N772 or kaolin. Tensile strength at break (TSb) values of vulcanizates with pyrolytic carbon black samples are also repeatable, but much lower than those obtained for carbon black vulcanizate N550 and N772. Similarly, the abrasion resistance of vulcanizates with pyrolytic carbon black samples reaches similar values, but is significantly lower than that of vulcanizates with carbon black N550, N772, but higher than that of vulcanizates with kaolin. Pyrolytic carbon black has unfavourable features which weaken the possible amplifying effect resulting from the relatively high iodine value (approx. 50 g/kg). These can be: the presence of a significant amount of mineral parts, insufficient fineness of carbon black particles, altered surface structure of primary carbon black particles or the presence of heavy pyrolytic oils and oligomeric rubber substances resulting from pyrolysis process. Key words: recycling, pyrolytic carbon black, filler, rubber compounds, vulcanizate, rubber, styrenebutadiene rubber.
The paper presents the properties of recycled toner used in laser printers and the properties o... more The paper presents the properties of recycled toner used in laser printers and the properties of rubber compounds and vulcanizates of SBR, NBR and EPDM rubbers containing toner as a filler. To compare the properties of rubber compounds and vulcanizates, analogous rubber mixes containing technical grade carbon blacks: N330, N550 and N772 were made. Obtained results were evaluated because of the possibility of recycling toner as a filler in rubber products. It has been found possible to use toner as a filler in NBR vulcanizates because it provides satisfactory mechanical properties, improvement of processing properties and resistance to thermal ageing. Keywords: toner, recycling, carbon black, filler, rubber compounds, vulcanizate, rubber, SBR, NBR, EPDM
The paper presents parameters of pyrolytic carbon black, obtained in an industrial installation o... more The paper presents parameters of pyrolytic carbon black, obtained in an industrial installation operating in batch mode, important from the point of view of application as a filler for rubber and plastic composites. Thanks to the investigation of pyrolytic carbon black samples from three independent processes carried out in the same way, the dispersion of properties was evaluated. Average values of parameters were compared with properties of technical carbon black N330, N550, N772 and N990. Individual samples of pyrolytic carbon black do not show significant dispersion of properties in structural parameters, i.e. iodine adsorption (average 50 g/kg) and DBF number (average 73 cm3/100 g). The dispersion of the obtained values does not exceed the acceptable values for technical carbon black. The average value of iodine adsorption 50 g/kg for pyrolytic carbon black is close to that of N550 carbon black (43 g/kg), while the average value of DBF absorption 73 g/kg is close to that of N772 carbon black (65 g/kg). Pyrolytic carbon black is polluted with a significant amount of mineral compounds. The dispersion of the value of these contaminants is relatively significant and amounts to 15.5–21.8% wt.%. Technical carbon black contains up to 0.5% wt.% of mineral impurities, therefore in this respect pyrolytic carbon black cannot be compared to technical carbon black. Pyrolytic carbon black is a carbon-mineral material. SEM analysis have shown that the fragmentation of crude pyrolytic carbon black is insufficient and particles which are secondary carbon black agglomerates are not disintegrated during the determination of the screening value on the 0.045 mm sieve. The morphology of pyrolytic carbon black as determined by SEM proves that this carbon black has the structure of technical carbon black. It is basically a recovered technical carbon black (more precisely, a mixture of technical carbon black) contaminated with mineral compounds and a small number of organic compounds: oils and undecomposed rubber. Keywords: pyrolytic carbon black, technical carbon black, pyrolysis, thermolysis, rubber waste, recycling.
Many years of coal mining resulted in the depletion of currently exploited deposits of raw materi... more Many years of coal mining resulted in the depletion of currently exploited deposits of raw materials. Therefore, the mines are forced to reach for ever lower surging coal seams. Consequently it becomes necessary to deepen existing shafts. To protect teams operating in the shaft, artificial bottom (safety platforms) are used. Old solutions based on rigid steel construction with the top, several meters height, damping layer such as slag, can absorb the energy of drop an object with a mass of 5 Mg to a depth of 700 m. Currently, the requirements of mines assume collapse of weight 20 Mg at a depth of 1000 m! Compact safety platforms (about 3 m in height), consisting of carrier rings and networks of wire ropes (rope platforms) used in Poland by Sadex Ltd are able to take the energy of drop for the mass of 5 Mg and depth of 900 m. These platforms, together with the use of elastomeric layers, according to the FEM, are able to absorb the energy of drop according the new requirements.
In this paper, the magnetorheological elastomers (MREs) based on natural rubber were studied. Sev... more In this paper, the magnetorheological elastomers (MREs) based on natural rubber were studied. Several MRE samples, with different weight percentages of carbon iron particles, were fabricated without applying a magnetic field. Their microstructures were observed by using an environmental scanning electron microscope (SEM), and their rheological measurements were carried out using ARES rheometer. The MR effect was investigated by changing the volume of carbon iron particles.
Właściwości elastomerów magnetoreologicznych mogą być kontrolowane za pomocą pola magnetycznego. ... more Właściwości elastomerów magnetoreologicznych mogą być kontrolowane za pomocą pola magnetycznego. Materiały te mają duże możliwości zastosowania w transporcie ale również w innych gałęziach przemysłu. W pracy przedstawiono otrzymywanie elastomerów mr bez obecnego pola magnetycznego. Następnie przeprowadzono badania na magnetometrze z wibrującą próbką. Dokonano analizy wyników i przedstawiono wnioski.
In the pilot plant for pyrolysis of whole tyres for passenger cars and vans we received a liquid ... more In the pilot plant for pyrolysis of whole tyres for passenger cars and vans we received a liquid product, hydrocarbon fraction known as pyrolytic oil, two solid products, i.e. pyrolytic carbon, scrap metal cord and gaseous mixture of hydrocarbons. The main goal of the research was to determine susceptibility of the obtained pyrolytic oils to hydrorefining. The analysis showed that hydrorefining process, carried out in the presence of commercial catalysts, allows for much improvement of its characteristics. However, it is necessary to apply relatively hard process conditions: temperature of at least 360 oC and hydrogen pressure of about 5 MPa. Then the product is desulphurised down to the sulphur content of less than 0.2% by weight and the unsaturated hydrocarbons are partially hydrogenated, which is characterised by the decrease of bromine number to less than 20 g Br2/100 g. As a result of high content of aromatic hydrocarbons, in respect of relatively high sulphur content, high density and low cetane index (lower than 35), even after hydrorefining process, pyrolytic oil can only be used as a component of fuel oils.
Tłumienie dźwięków oraz drgań materiałowych ma znaczący wpływ na jakość pracy maszyn i urządzeń m... more Tłumienie dźwięków oraz drgań materiałowych ma znaczący wpływ na jakość pracy maszyn i urządzeń mechanicznych oraz komfort pracy ich operatorów. W artykule przedstawiono metodę tłumienia drgań materiałowych, polegająca na zastosowaniu kompozytów elastomerowych wylewanych w miejscu ich zastosowania. Opracowana metoda została wykorzystana do wytłumienia drgań materiałowych konstrukcji wsporczej hybrydowego robota frezującego o pięciu stopniach swobody. W artykule przedstawiono konstrukcję hybrydowego robota frezującego konstruowanego w Katedrze Robotyki i Mechatroniki AGH oraz wstępne badania dotyczące zastosowania kompozytów elastomerowych do tłumienia drgań materiałowych na przykładzie elementów konstrukcji wsporczej robota.
Many factors influence the mechanical properties, morphology of polar/nonpolar rubber blends. Thi... more Many factors influence the mechanical properties, morphology of polar/nonpolar rubber blends. This work describes the influence of smalmolecule modifier – maleic acid dodecyl ester on mechanical properties of NR/NBR blends with 25, 50, 75% NBR content of 100phr of rubbers, which were vulcanised by a sulphur system and filled by carbon black N220. Because the two phase structure of vulcanisates with 50phr NBR content the mechanical properties of these vulcanisates are worse than resulting from additivity law. As result of adding 3phr of the maleic acid dodecyl ester and 0,2 phr of a peroxide the increase of mechanical properties of NRNBR vulcanisates was observed also morphology of vulcanisates changed to fine dispersion. During the vulcanisation process the graft reaction of maleic acid ester on macromolecules can take place which results in increase of the adhesion between rubber phases – better morphology observed, which arise from dipole interactions, hydrogen bonds, and ionic clusters formation (with zinc ions).
Composites of SBS with 2-10 %wt. of an organophilic montmorillonite (Cloisite 15A) compatibilizat... more Composites of SBS with 2-10 %wt. of an organophilic montmorillonite (Cloisite 15A) compatibilizated with silanes: 3-chloropropyltrimethoxy silane, 3-aminopropyltrimethoxy silane, octadecyltrimethoxy silane were prepared using a laboratory extruder Brabender. The obtained composites were characterized by SEM, DSC and tensile test. The properties of SBS/montmorillonite composites were compared with reference samples: pristine SBS and SBS/silica 10 %wt. (Ultrasil VN3) composites compatibilized with the 3-chloropropyltrimethoxy silane. Based on SEM observations it was found that the intercalated SBS/montmorillonite composites were obtained. Tensile properties of composites were dependent on filler content and applied compatibilizing agent. The best mechanical properties had the composite containing 5 %wt. of montmorillonite and 3-aminopropyltrimethoxy silane. In comparison with pristine SBS tensile strength was 65 % and elongation at break 12 % greater. DSC measurements showed that a small quantity of the organophilic montmorillonite added to SBS caused considerable increase of Tg of polystyrene phase (about 8 ºC) without change of Tg of polybutadiene phase what is a very advantageous effect.
Studies on the possibility of the application of the solid-state postpolycondensation (SSP) proce... more Studies on the possibility of the application of the solid-state postpolycondensation (SSP) process to increase the average molecular weight of bisphenol A-based polycarbonate (PBC) were carried out. The thermally stable PBC with a very high molecular weight reaching about 50,000 g/mol was obtained by the applied SSP technique. Some factors influencing the effectiveness of the SSP process were initially examined: the mode of preparation (crystallization) of the PBC prepolymer, condensation temperature and time, and the vacuum applied in the reaction vessel. It was found that the superior yield of the high molecular weight PBC was obtained by the employing as high as possible values of the parameters taken into consideration.
Wulkanizaty kauczuków nienasyconych ze względu na dużą zawartość wiązań podwójnych węgiel-węgiel ... more Wulkanizaty kauczuków nienasyconych ze względu na dużą zawartość wiązań podwójnych węgiel-węgiel łatwo ulegają starzeniu atmosferycznemu, szczególnie pod wpływem ozonu. Przykładem mogą być szeroko rozpowszechnione lecz mało odporne na działanie czynników atmosferycznych wyroby z kauczuków butadienowo-styrenowych (SBR). W niniejszej pracy omówiono znane i stosowane metody poprawy odporności na starzenie atmosferyczne wulkanizatów kauczuków nienasyconych. Mają one jednak wiele wad, na które zwrócono uwagę. W części doświadczalnej pracy podjęto próbę wykorzystania granulatu kauczuku etylenowo-propylenowo-dienowego (EPDM) jako dodatku chroniącego wulkanizaty SBR przed niszczącym działaniem czynników atmosferycznych. Uzyskane wyniki świadczą o możliwości wykorzystania odpadów EPDM jako dodatku poprawijącego odporność na warunki atmosferyczne wyrobów gumowych z SBR lub innych kauczuków dienowych. Dodatek granulatu EPDM zwiększa odporność na starzenie cieplno-tlenowe wulkanizatów SBR oraz znacznie poprawia ich odporność na starzenie ozonowe wydłużając 10-krotnie okres pojawiania się wyraźnych spękań próbek wulkanizatów.
The process for synthesis of high-molecular-weight poly(bisphenol A carbonate) (PBC) by the solid... more The process for synthesis of high-molecular-weight poly(bisphenol A carbonate) (PBC) by the solid state postpolycondensation (SSP) process using 5 - 20 wt.-% of thermally unstable poly(propylene carbonate) (PPC) was investigated and compared with the analogous process without addition of the thermally unstable polymer. An application of poly(propylene carbonate) for the SSP process was found to enable the process to be carried out with poly(bisphenol A carbonate) not being precrystallized prior to postpolycondensation. It does mean that the inconvenient stage of crystallization of the prepolymer could be omitted. PBC of v 48 000 g/mol was obtained by the standard procedure of SSP process starting with a prepolymer crystallized in acetone (for 192 hrs at a condensation temperature of 230-255 oC and pressure of 0.07 mm Hg). Instead, in the presence of 20 wt.-% PPC (without inconvenient etape of crystallization of the prepolymer), PBC of v 42 000 g/mol with inconspicous contents of PPC was obtained. The results have been discussed in terms of appearing of propylene carbonate in the postpolycondensation system due to the thermall decomposition of poly(propylene carbonate) under conditions applied. Propylene carbonate probably acts as a swelling agent which makes the prepolymer chain mobility and increased crystallization as well as the removing of condensation low-molecular-weight by-products more facile.
Ethylene-propylene copolymer was functionalized with 2-isopropenyl-2-oxazoline by radical cross-l... more Ethylene-propylene copolymer was functionalized with 2-isopropenyl-2-oxazoline by radical cross-linking with (PhCMe2O)2 and used to prepare bi-elastomeric blends with natural rubber. Layered montmorillonite was used as a filler. The modification resulted in an increase of tensile strength of the natural rubber vulcanizates
The influence of engine oil absorption on the dynamic properties of NR, NBR and their mixtures co... more The influence of engine oil absorption on the dynamic properties of NR, NBR and their mixtures containing 50 or 75 phr of NBR modified various amounts of carbon black as filler has been investigated. It was determined that a slight absorption of oil by the NBR vulcanizates leads to an increase in the space phase angles but a decrease in the value of the module G*. A high degree of absorption of oil observed in the case of NR vulcanizates results however in a significant decrease in the δ angle as well as the G*module. The dynamic properties of the NR/NBR mixture vulcanizates did not constitute a combination, but differ in a crucial manner from the properties of the individual vulcanizates. The influence of oil adsorption on the properties the tested vulcanizates depends on both the filler (carbon black) as well as the NBR content in the system. However, in the case of the 25/75 NR/NBR vulcanizates with 50 phr of the filling carbon black, a change in the values of space phase angle and group module was not observed. Keywords: natural rubber, butadiene-acrylonitrile rubber, rubber mixtures, oil adsorption, sooth, dynamic properties.
Ethylene/propylene elastomer (EPM), hydrogenated butadiene/acrylonitrile rubber (HNBR) and their ... more Ethylene/propylene elastomer (EPM), hydrogenated butadiene/acrylonitrile rubber (HNBR) and their mixts. Were modified by addn. of 2-isopropenyl-2-oxazoline (IPO), filled with SiO2 and vulcanized with (PhCMe2O)2 at 160°C. The vulcanizates were studied for mech. properties (tensile strength, elongation at break, tearing strength) and swelling ability. The addn. of IPO (up to 7%) resulted in an increase in the elasticity modulus. An increase in the tensile and tearing strength was clearly obsd. only in the vulcanizates of the EPM/HNBR blends.
The paper presents the results of research on the possibility of using as plasticizers of rubber ... more The paper presents the results of research on the possibility of using as plasticizers of rubber compounds the heavy fractions of pyrolytic oil obtained in the industrial process of pyrolysis of car tyres. The content of carcinogenic polycyclic aromatic hydrocarbons (PAHs) in the obtained pyrolytic plasticizers was determined. Compounds and vulcanizates of styrene-butadiene rubber (SBR) containing the above plasticizers as well as commercial petroleum derivatives plasticizers were prepared for comparative purposes. The basic properties of compounds and vulcanizates containing pyrolytic plas-ticizers were investigated. The research found that one fraction of pyrolysis oil meet the requirements of the permitted content of PAHs. SBR blends and vulcanizates it gives similar properties as in the case of commercial plasticizers. Keywords: tyre pyrolysis, pyrolytic oil, plasticizer, rubber compound, vulcanizate, rubber.
Due to its high total sulphur content and other unfavourable properties, pyrolytic oil obtained a... more Due to its high total sulphur content and other unfavourable properties, pyrolytic oil obtained as a result of tyres pyrolysis is not suitable for use as motor or heating fuel. Therefore, pyrolytic oil was hydrorefined. Hydrorefined oil was used as a component of light heating oil. A composition was prepared from 30 wt % hydrorefinate with 70 wt % Ekoterm Plus (a commercial oil). Unfortunately, the flash point temperature of the hydrorefinate was too low, and did not allow fuel compliant with the Polish standard PN-C-96024:2011 for L1 light heating oil to be obtained. Therefore, the fraction with boiling point below 180 • C was removed from the hydrorefinate. The residue, with a flash point of 74 • C and a sulphur content of 0.143 wt %, was mixed with Ekoterm Plus and fuels with a hydrorefinate fraction content of 30 and 50 wt % were prepared. The composition containing 30 wt % met the requirements for L1 oil in the whole range of tested parameters. Total sulphur content was 0.092 wt %, specific weight was 856 kg/m 3 and closed cup flash point was 64 • C. However, the composition containing 50 wt % hydrorefinate did not meet the requirements regarding sulphur content and specific weight. Sulphur content, specific gravity, and flash point are the parameters limiting the possibility of using hydrorefined pyrolytic oil for composing light heating oils compliant with the mentioned standard. Keywords: tyre pyrolysis; rubber; pyrolytic oil; hydrorefining; hydrodesulphurization; light fuel oil
The paper presents the results of studies on the repeatability of properties of compounds and vul... more The paper presents the results of studies on the repeatability of properties of compounds and vulcanizates of styrene-butadiene rubber containing independent samples of pyrolytic carbon black. For comparison, analogous compounds and vulcanizates containing technical carbon black N550, N772 and kaolin were examined. It was found that pyrolytic carbon black gives the compounds high Mooney viscosity. The obtained viscosity values for the three carbon black tests are repeatable, within the range of ±5%. Compounds with pyrolytic carbon black samples have optimum vulcanization time (t90) values similar to those of compounds containing technical carbon black. The dispersion of the t90 values is greater and is ±14%. It was found that the more sulphur and zinc compounds containing pyrolytic carbon black, the higher the rate of vulcanization. Individual samples of pyrolytic carbon black give SBR vulcanizates a high and reproducible hardness equal to that of carbon black vulcanizate N550 and much higher than that of carbon black vulcanizate N772 or kaolin. Tensile strength at break (TSb) values of vulcanizates with pyrolytic carbon black samples are also repeatable, but much lower than those obtained for carbon black vulcanizate N550 and N772. Similarly, the abrasion resistance of vulcanizates with pyrolytic carbon black samples reaches similar values, but is significantly lower than that of vulcanizates with carbon black N550, N772, but higher than that of vulcanizates with kaolin. Pyrolytic carbon black has unfavourable features which weaken the possible amplifying effect resulting from the relatively high iodine value (approx. 50 g/kg). These can be: the presence of a significant amount of mineral parts, insufficient fineness of carbon black particles, altered surface structure of primary carbon black particles or the presence of heavy pyrolytic oils and oligomeric rubber substances resulting from pyrolysis process. Key words: recycling, pyrolytic carbon black, filler, rubber compounds, vulcanizate, rubber, styrenebutadiene rubber.
The paper presents the properties of recycled toner used in laser printers and the properties o... more The paper presents the properties of recycled toner used in laser printers and the properties of rubber compounds and vulcanizates of SBR, NBR and EPDM rubbers containing toner as a filler. To compare the properties of rubber compounds and vulcanizates, analogous rubber mixes containing technical grade carbon blacks: N330, N550 and N772 were made. Obtained results were evaluated because of the possibility of recycling toner as a filler in rubber products. It has been found possible to use toner as a filler in NBR vulcanizates because it provides satisfactory mechanical properties, improvement of processing properties and resistance to thermal ageing. Keywords: toner, recycling, carbon black, filler, rubber compounds, vulcanizate, rubber, SBR, NBR, EPDM
The paper presents parameters of pyrolytic carbon black, obtained in an industrial installation o... more The paper presents parameters of pyrolytic carbon black, obtained in an industrial installation operating in batch mode, important from the point of view of application as a filler for rubber and plastic composites. Thanks to the investigation of pyrolytic carbon black samples from three independent processes carried out in the same way, the dispersion of properties was evaluated. Average values of parameters were compared with properties of technical carbon black N330, N550, N772 and N990. Individual samples of pyrolytic carbon black do not show significant dispersion of properties in structural parameters, i.e. iodine adsorption (average 50 g/kg) and DBF number (average 73 cm3/100 g). The dispersion of the obtained values does not exceed the acceptable values for technical carbon black. The average value of iodine adsorption 50 g/kg for pyrolytic carbon black is close to that of N550 carbon black (43 g/kg), while the average value of DBF absorption 73 g/kg is close to that of N772 carbon black (65 g/kg). Pyrolytic carbon black is polluted with a significant amount of mineral compounds. The dispersion of the value of these contaminants is relatively significant and amounts to 15.5–21.8% wt.%. Technical carbon black contains up to 0.5% wt.% of mineral impurities, therefore in this respect pyrolytic carbon black cannot be compared to technical carbon black. Pyrolytic carbon black is a carbon-mineral material. SEM analysis have shown that the fragmentation of crude pyrolytic carbon black is insufficient and particles which are secondary carbon black agglomerates are not disintegrated during the determination of the screening value on the 0.045 mm sieve. The morphology of pyrolytic carbon black as determined by SEM proves that this carbon black has the structure of technical carbon black. It is basically a recovered technical carbon black (more precisely, a mixture of technical carbon black) contaminated with mineral compounds and a small number of organic compounds: oils and undecomposed rubber. Keywords: pyrolytic carbon black, technical carbon black, pyrolysis, thermolysis, rubber waste, recycling.
Many years of coal mining resulted in the depletion of currently exploited deposits of raw materi... more Many years of coal mining resulted in the depletion of currently exploited deposits of raw materials. Therefore, the mines are forced to reach for ever lower surging coal seams. Consequently it becomes necessary to deepen existing shafts. To protect teams operating in the shaft, artificial bottom (safety platforms) are used. Old solutions based on rigid steel construction with the top, several meters height, damping layer such as slag, can absorb the energy of drop an object with a mass of 5 Mg to a depth of 700 m. Currently, the requirements of mines assume collapse of weight 20 Mg at a depth of 1000 m! Compact safety platforms (about 3 m in height), consisting of carrier rings and networks of wire ropes (rope platforms) used in Poland by Sadex Ltd are able to take the energy of drop for the mass of 5 Mg and depth of 900 m. These platforms, together with the use of elastomeric layers, according to the FEM, are able to absorb the energy of drop according the new requirements.
In this paper, the magnetorheological elastomers (MREs) based on natural rubber were studied. Sev... more In this paper, the magnetorheological elastomers (MREs) based on natural rubber were studied. Several MRE samples, with different weight percentages of carbon iron particles, were fabricated without applying a magnetic field. Their microstructures were observed by using an environmental scanning electron microscope (SEM), and their rheological measurements were carried out using ARES rheometer. The MR effect was investigated by changing the volume of carbon iron particles.
Właściwości elastomerów magnetoreologicznych mogą być kontrolowane za pomocą pola magnetycznego. ... more Właściwości elastomerów magnetoreologicznych mogą być kontrolowane za pomocą pola magnetycznego. Materiały te mają duże możliwości zastosowania w transporcie ale również w innych gałęziach przemysłu. W pracy przedstawiono otrzymywanie elastomerów mr bez obecnego pola magnetycznego. Następnie przeprowadzono badania na magnetometrze z wibrującą próbką. Dokonano analizy wyników i przedstawiono wnioski.
In the pilot plant for pyrolysis of whole tyres for passenger cars and vans we received a liquid ... more In the pilot plant for pyrolysis of whole tyres for passenger cars and vans we received a liquid product, hydrocarbon fraction known as pyrolytic oil, two solid products, i.e. pyrolytic carbon, scrap metal cord and gaseous mixture of hydrocarbons. The main goal of the research was to determine susceptibility of the obtained pyrolytic oils to hydrorefining. The analysis showed that hydrorefining process, carried out in the presence of commercial catalysts, allows for much improvement of its characteristics. However, it is necessary to apply relatively hard process conditions: temperature of at least 360 oC and hydrogen pressure of about 5 MPa. Then the product is desulphurised down to the sulphur content of less than 0.2% by weight and the unsaturated hydrocarbons are partially hydrogenated, which is characterised by the decrease of bromine number to less than 20 g Br2/100 g. As a result of high content of aromatic hydrocarbons, in respect of relatively high sulphur content, high density and low cetane index (lower than 35), even after hydrorefining process, pyrolytic oil can only be used as a component of fuel oils.
Tłumienie dźwięków oraz drgań materiałowych ma znaczący wpływ na jakość pracy maszyn i urządzeń m... more Tłumienie dźwięków oraz drgań materiałowych ma znaczący wpływ na jakość pracy maszyn i urządzeń mechanicznych oraz komfort pracy ich operatorów. W artykule przedstawiono metodę tłumienia drgań materiałowych, polegająca na zastosowaniu kompozytów elastomerowych wylewanych w miejscu ich zastosowania. Opracowana metoda została wykorzystana do wytłumienia drgań materiałowych konstrukcji wsporczej hybrydowego robota frezującego o pięciu stopniach swobody. W artykule przedstawiono konstrukcję hybrydowego robota frezującego konstruowanego w Katedrze Robotyki i Mechatroniki AGH oraz wstępne badania dotyczące zastosowania kompozytów elastomerowych do tłumienia drgań materiałowych na przykładzie elementów konstrukcji wsporczej robota.
Many factors influence the mechanical properties, morphology of polar/nonpolar rubber blends. Thi... more Many factors influence the mechanical properties, morphology of polar/nonpolar rubber blends. This work describes the influence of smalmolecule modifier – maleic acid dodecyl ester on mechanical properties of NR/NBR blends with 25, 50, 75% NBR content of 100phr of rubbers, which were vulcanised by a sulphur system and filled by carbon black N220. Because the two phase structure of vulcanisates with 50phr NBR content the mechanical properties of these vulcanisates are worse than resulting from additivity law. As result of adding 3phr of the maleic acid dodecyl ester and 0,2 phr of a peroxide the increase of mechanical properties of NRNBR vulcanisates was observed also morphology of vulcanisates changed to fine dispersion. During the vulcanisation process the graft reaction of maleic acid ester on macromolecules can take place which results in increase of the adhesion between rubber phases – better morphology observed, which arise from dipole interactions, hydrogen bonds, and ionic clusters formation (with zinc ions).
Composites of SBS with 2-10 %wt. of an organophilic montmorillonite (Cloisite 15A) compatibilizat... more Composites of SBS with 2-10 %wt. of an organophilic montmorillonite (Cloisite 15A) compatibilizated with silanes: 3-chloropropyltrimethoxy silane, 3-aminopropyltrimethoxy silane, octadecyltrimethoxy silane were prepared using a laboratory extruder Brabender. The obtained composites were characterized by SEM, DSC and tensile test. The properties of SBS/montmorillonite composites were compared with reference samples: pristine SBS and SBS/silica 10 %wt. (Ultrasil VN3) composites compatibilized with the 3-chloropropyltrimethoxy silane. Based on SEM observations it was found that the intercalated SBS/montmorillonite composites were obtained. Tensile properties of composites were dependent on filler content and applied compatibilizing agent. The best mechanical properties had the composite containing 5 %wt. of montmorillonite and 3-aminopropyltrimethoxy silane. In comparison with pristine SBS tensile strength was 65 % and elongation at break 12 % greater. DSC measurements showed that a small quantity of the organophilic montmorillonite added to SBS caused considerable increase of Tg of polystyrene phase (about 8 ºC) without change of Tg of polybutadiene phase what is a very advantageous effect.
Studies on the possibility of the application of the solid-state postpolycondensation (SSP) proce... more Studies on the possibility of the application of the solid-state postpolycondensation (SSP) process to increase the average molecular weight of bisphenol A-based polycarbonate (PBC) were carried out. The thermally stable PBC with a very high molecular weight reaching about 50,000 g/mol was obtained by the applied SSP technique. Some factors influencing the effectiveness of the SSP process were initially examined: the mode of preparation (crystallization) of the PBC prepolymer, condensation temperature and time, and the vacuum applied in the reaction vessel. It was found that the superior yield of the high molecular weight PBC was obtained by the employing as high as possible values of the parameters taken into consideration.
Wulkanizaty kauczuków nienasyconych ze względu na dużą zawartość wiązań podwójnych węgiel-węgiel ... more Wulkanizaty kauczuków nienasyconych ze względu na dużą zawartość wiązań podwójnych węgiel-węgiel łatwo ulegają starzeniu atmosferycznemu, szczególnie pod wpływem ozonu. Przykładem mogą być szeroko rozpowszechnione lecz mało odporne na działanie czynników atmosferycznych wyroby z kauczuków butadienowo-styrenowych (SBR). W niniejszej pracy omówiono znane i stosowane metody poprawy odporności na starzenie atmosferyczne wulkanizatów kauczuków nienasyconych. Mają one jednak wiele wad, na które zwrócono uwagę. W części doświadczalnej pracy podjęto próbę wykorzystania granulatu kauczuku etylenowo-propylenowo-dienowego (EPDM) jako dodatku chroniącego wulkanizaty SBR przed niszczącym działaniem czynników atmosferycznych. Uzyskane wyniki świadczą o możliwości wykorzystania odpadów EPDM jako dodatku poprawijącego odporność na warunki atmosferyczne wyrobów gumowych z SBR lub innych kauczuków dienowych. Dodatek granulatu EPDM zwiększa odporność na starzenie cieplno-tlenowe wulkanizatów SBR oraz znacznie poprawia ich odporność na starzenie ozonowe wydłużając 10-krotnie okres pojawiania się wyraźnych spękań próbek wulkanizatów.
The process for synthesis of high-molecular-weight poly(bisphenol A carbonate) (PBC) by the solid... more The process for synthesis of high-molecular-weight poly(bisphenol A carbonate) (PBC) by the solid state postpolycondensation (SSP) process using 5 - 20 wt.-% of thermally unstable poly(propylene carbonate) (PPC) was investigated and compared with the analogous process without addition of the thermally unstable polymer. An application of poly(propylene carbonate) for the SSP process was found to enable the process to be carried out with poly(bisphenol A carbonate) not being precrystallized prior to postpolycondensation. It does mean that the inconvenient stage of crystallization of the prepolymer could be omitted. PBC of v 48 000 g/mol was obtained by the standard procedure of SSP process starting with a prepolymer crystallized in acetone (for 192 hrs at a condensation temperature of 230-255 oC and pressure of 0.07 mm Hg). Instead, in the presence of 20 wt.-% PPC (without inconvenient etape of crystallization of the prepolymer), PBC of v 42 000 g/mol with inconspicous contents of PPC was obtained. The results have been discussed in terms of appearing of propylene carbonate in the postpolycondensation system due to the thermall decomposition of poly(propylene carbonate) under conditions applied. Propylene carbonate probably acts as a swelling agent which makes the prepolymer chain mobility and increased crystallization as well as the removing of condensation low-molecular-weight by-products more facile.
Ethylene-propylene copolymer was functionalized with 2-isopropenyl-2-oxazoline by radical cross-l... more Ethylene-propylene copolymer was functionalized with 2-isopropenyl-2-oxazoline by radical cross-linking with (PhCMe2O)2 and used to prepare bi-elastomeric blends with natural rubber. Layered montmorillonite was used as a filler. The modification resulted in an increase of tensile strength of the natural rubber vulcanizates
The influence of engine oil absorption on the dynamic properties of NR, NBR and their mixtures co... more The influence of engine oil absorption on the dynamic properties of NR, NBR and their mixtures containing 50 or 75 phr of NBR modified various amounts of carbon black as filler has been investigated. It was determined that a slight absorption of oil by the NBR vulcanizates leads to an increase in the space phase angles but a decrease in the value of the module G*. A high degree of absorption of oil observed in the case of NR vulcanizates results however in a significant decrease in the δ angle as well as the G*module. The dynamic properties of the NR/NBR mixture vulcanizates did not constitute a combination, but differ in a crucial manner from the properties of the individual vulcanizates. The influence of oil adsorption on the properties the tested vulcanizates depends on both the filler (carbon black) as well as the NBR content in the system. However, in the case of the 25/75 NR/NBR vulcanizates with 50 phr of the filling carbon black, a change in the values of space phase angle and group module was not observed. Keywords: natural rubber, butadiene-acrylonitrile rubber, rubber mixtures, oil adsorption, sooth, dynamic properties.
Ethylene/propylene elastomer (EPM), hydrogenated butadiene/acrylonitrile rubber (HNBR) and their ... more Ethylene/propylene elastomer (EPM), hydrogenated butadiene/acrylonitrile rubber (HNBR) and their mixts. Were modified by addn. of 2-isopropenyl-2-oxazoline (IPO), filled with SiO2 and vulcanized with (PhCMe2O)2 at 160°C. The vulcanizates were studied for mech. properties (tensile strength, elongation at break, tearing strength) and swelling ability. The addn. of IPO (up to 7%) resulted in an increase in the elasticity modulus. An increase in the tensile and tearing strength was clearly obsd. only in the vulcanizates of the EPM/HNBR blends.
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Papers by Cezary Dębek
Keywords: tyre pyrolysis, pyrolytic oil, plasticizer, rubber compound, vulcanizate, rubber.
Keywords: tyre pyrolysis; rubber; pyrolytic oil; hydrorefining; hydrodesulphurization; light fuel oil
It was found that pyrolytic carbon black gives the compounds high Mooney viscosity. The obtained viscosity values for the three carbon black tests are repeatable, within the range of ±5%. Compounds with pyrolytic carbon black samples have optimum vulcanization time (t90) values similar to those of compounds containing technical carbon black. The dispersion of the t90 values is greater and is ±14%. It was found that the more sulphur and zinc compounds containing pyrolytic carbon black, the higher the rate of vulcanization.
Individual samples of pyrolytic carbon black give SBR vulcanizates a high and reproducible hardness equal to that of carbon black vulcanizate N550 and much higher than that of carbon black vulcanizate N772 or kaolin. Tensile strength at break (TSb) values of vulcanizates with pyrolytic carbon black samples are also repeatable, but much lower than those obtained for carbon black vulcanizate N550 and N772. Similarly, the abrasion resistance of vulcanizates with pyrolytic carbon black samples reaches similar values, but is significantly lower than that of vulcanizates with carbon black N550, N772, but higher than that of vulcanizates with kaolin.
Pyrolytic carbon black has unfavourable features which weaken the possible amplifying effect resulting from the relatively high iodine value (approx. 50 g/kg). These can be: the presence of a significant amount of mineral parts, insufficient fineness of carbon black particles, altered surface structure of primary carbon black particles or the presence of heavy pyrolytic oils and oligomeric rubber substances resulting from pyrolysis process.
Key words: recycling, pyrolytic carbon black, filler, rubber compounds, vulcanizate, rubber, styrenebutadiene
rubber.
It has been found possible to use toner as a filler in NBR vulcanizates because it provides satisfactory mechanical properties, improvement of processing properties and resistance to thermal ageing.
Keywords: toner, recycling, carbon black, filler, rubber compounds, vulcanizate, rubber, SBR, NBR, EPDM
Pyrolytic carbon black is polluted with a significant amount of mineral compounds. The dispersion of the value of these contaminants is relatively significant and amounts to 15.5–21.8% wt.%. Technical carbon black contains up to 0.5% wt.% of mineral impurities, therefore in this respect pyrolytic carbon black cannot be compared to technical carbon black. Pyrolytic carbon black is a carbon-mineral material.
SEM analysis have shown that the fragmentation of crude pyrolytic carbon black is insufficient and particles which are secondary carbon black agglomerates are not disintegrated during the determination of the screening value on the 0.045 mm sieve.
The morphology of pyrolytic carbon black as determined by SEM proves that this carbon black has the structure of technical carbon black. It is basically a recovered technical carbon black (more precisely, a mixture of technical carbon black) contaminated with mineral compounds and a small number of organic compounds: oils and undecomposed rubber.
Keywords: pyrolytic carbon black, technical carbon black, pyrolysis, thermolysis, rubber waste,
recycling.
Old solutions based on rigid steel construction with the top, several meters height, damping layer such as slag, can absorb the energy of drop an object with a mass of 5 Mg to a depth of 700 m. Currently, the requirements of mines assume collapse of weight 20 Mg at a depth of 1000 m! Compact safety platforms (about 3 m in height), consisting of carrier rings and networks of wire ropes (rope platforms) used in Poland by Sadex Ltd are able to take the energy of drop for the mass of 5 Mg and depth of 900 m. These platforms, together with the use of elastomeric layers, according to the FEM, are able to absorb the energy of drop according the new requirements.
NR/NBR blends with 25, 50, 75% NBR content of 100phr of rubbers, which were vulcanised by a sulphur system and filled by carbon black N220. Because the two phase structure of vulcanisates with 50phr NBR content the mechanical properties of these vulcanisates are worse than resulting from additivity law. As result of adding 3phr of the maleic acid dodecyl ester and 0,2 phr of a peroxide the increase of mechanical properties of NRNBR vulcanisates was observed also morphology of vulcanisates changed to fine dispersion. During the vulcanisation process the graft reaction of maleic acid ester on macromolecules can take place which results in increase of the adhesion between rubber phases – better morphology observed, which arise from dipole interactions, hydrogen bonds, and ionic clusters formation (with zinc ions).
The obtained composites were characterized by SEM, DSC and tensile test. The properties of SBS/montmorillonite composites were compared with reference samples: pristine SBS and SBS/silica 10 %wt. (Ultrasil VN3) composites compatibilized with the 3-chloropropyltrimethoxy silane.
Based on SEM observations it was found that the intercalated SBS/montmorillonite composites were obtained. Tensile properties of composites were dependent on filler content and applied compatibilizing agent. The best mechanical properties had the composite containing 5 %wt. of montmorillonite and 3-aminopropyltrimethoxy silane. In comparison with pristine SBS tensile strength was 65 % and elongation at break 12 % greater. DSC measurements showed that a small quantity of the organophilic montmorillonite added to SBS caused considerable increase of Tg of polystyrene phase (about 8 ºC) without change of Tg of polybutadiene phase what is a very advantageous effect.
as high as possible values of the parameters taken into consideration.
W niniejszej pracy omówiono znane i stosowane metody poprawy odporności na starzenie atmosferyczne wulkanizatów kauczuków nienasyconych. Mają one jednak wiele wad, na które zwrócono uwagę.
W części doświadczalnej pracy podjęto próbę wykorzystania granulatu kauczuku etylenowo-propylenowo-dienowego (EPDM) jako dodatku chroniącego wulkanizaty SBR przed niszczącym działaniem czynników atmosferycznych.
Uzyskane wyniki świadczą o możliwości wykorzystania odpadów EPDM jako dodatku poprawijącego odporność na warunki atmosferyczne wyrobów gumowych z SBR lub innych kauczuków dienowych. Dodatek granulatu EPDM zwiększa odporność na starzenie cieplno-tlenowe wulkanizatów SBR oraz znacznie poprawia ich odporność na starzenie ozonowe wydłużając 10-krotnie okres pojawiania się wyraźnych spękań próbek wulkanizatów.
The results have been discussed in terms of appearing of propylene carbonate in the postpolycondensation system due to the thermall decomposition of poly(propylene carbonate) under conditions applied. Propylene carbonate probably acts as a swelling agent which makes the prepolymer chain mobility and increased crystallization as well as the removing of condensation low-molecular-weight by-products more facile.
Keywords: natural rubber, butadiene-acrylonitrile rubber, rubber mixtures, oil adsorption, sooth, dynamic properties.
Keywords: tyre pyrolysis, pyrolytic oil, plasticizer, rubber compound, vulcanizate, rubber.
Keywords: tyre pyrolysis; rubber; pyrolytic oil; hydrorefining; hydrodesulphurization; light fuel oil
It was found that pyrolytic carbon black gives the compounds high Mooney viscosity. The obtained viscosity values for the three carbon black tests are repeatable, within the range of ±5%. Compounds with pyrolytic carbon black samples have optimum vulcanization time (t90) values similar to those of compounds containing technical carbon black. The dispersion of the t90 values is greater and is ±14%. It was found that the more sulphur and zinc compounds containing pyrolytic carbon black, the higher the rate of vulcanization.
Individual samples of pyrolytic carbon black give SBR vulcanizates a high and reproducible hardness equal to that of carbon black vulcanizate N550 and much higher than that of carbon black vulcanizate N772 or kaolin. Tensile strength at break (TSb) values of vulcanizates with pyrolytic carbon black samples are also repeatable, but much lower than those obtained for carbon black vulcanizate N550 and N772. Similarly, the abrasion resistance of vulcanizates with pyrolytic carbon black samples reaches similar values, but is significantly lower than that of vulcanizates with carbon black N550, N772, but higher than that of vulcanizates with kaolin.
Pyrolytic carbon black has unfavourable features which weaken the possible amplifying effect resulting from the relatively high iodine value (approx. 50 g/kg). These can be: the presence of a significant amount of mineral parts, insufficient fineness of carbon black particles, altered surface structure of primary carbon black particles or the presence of heavy pyrolytic oils and oligomeric rubber substances resulting from pyrolysis process.
Key words: recycling, pyrolytic carbon black, filler, rubber compounds, vulcanizate, rubber, styrenebutadiene
rubber.
It has been found possible to use toner as a filler in NBR vulcanizates because it provides satisfactory mechanical properties, improvement of processing properties and resistance to thermal ageing.
Keywords: toner, recycling, carbon black, filler, rubber compounds, vulcanizate, rubber, SBR, NBR, EPDM
Pyrolytic carbon black is polluted with a significant amount of mineral compounds. The dispersion of the value of these contaminants is relatively significant and amounts to 15.5–21.8% wt.%. Technical carbon black contains up to 0.5% wt.% of mineral impurities, therefore in this respect pyrolytic carbon black cannot be compared to technical carbon black. Pyrolytic carbon black is a carbon-mineral material.
SEM analysis have shown that the fragmentation of crude pyrolytic carbon black is insufficient and particles which are secondary carbon black agglomerates are not disintegrated during the determination of the screening value on the 0.045 mm sieve.
The morphology of pyrolytic carbon black as determined by SEM proves that this carbon black has the structure of technical carbon black. It is basically a recovered technical carbon black (more precisely, a mixture of technical carbon black) contaminated with mineral compounds and a small number of organic compounds: oils and undecomposed rubber.
Keywords: pyrolytic carbon black, technical carbon black, pyrolysis, thermolysis, rubber waste,
recycling.
Old solutions based on rigid steel construction with the top, several meters height, damping layer such as slag, can absorb the energy of drop an object with a mass of 5 Mg to a depth of 700 m. Currently, the requirements of mines assume collapse of weight 20 Mg at a depth of 1000 m! Compact safety platforms (about 3 m in height), consisting of carrier rings and networks of wire ropes (rope platforms) used in Poland by Sadex Ltd are able to take the energy of drop for the mass of 5 Mg and depth of 900 m. These platforms, together with the use of elastomeric layers, according to the FEM, are able to absorb the energy of drop according the new requirements.
NR/NBR blends with 25, 50, 75% NBR content of 100phr of rubbers, which were vulcanised by a sulphur system and filled by carbon black N220. Because the two phase structure of vulcanisates with 50phr NBR content the mechanical properties of these vulcanisates are worse than resulting from additivity law. As result of adding 3phr of the maleic acid dodecyl ester and 0,2 phr of a peroxide the increase of mechanical properties of NRNBR vulcanisates was observed also morphology of vulcanisates changed to fine dispersion. During the vulcanisation process the graft reaction of maleic acid ester on macromolecules can take place which results in increase of the adhesion between rubber phases – better morphology observed, which arise from dipole interactions, hydrogen bonds, and ionic clusters formation (with zinc ions).
The obtained composites were characterized by SEM, DSC and tensile test. The properties of SBS/montmorillonite composites were compared with reference samples: pristine SBS and SBS/silica 10 %wt. (Ultrasil VN3) composites compatibilized with the 3-chloropropyltrimethoxy silane.
Based on SEM observations it was found that the intercalated SBS/montmorillonite composites were obtained. Tensile properties of composites were dependent on filler content and applied compatibilizing agent. The best mechanical properties had the composite containing 5 %wt. of montmorillonite and 3-aminopropyltrimethoxy silane. In comparison with pristine SBS tensile strength was 65 % and elongation at break 12 % greater. DSC measurements showed that a small quantity of the organophilic montmorillonite added to SBS caused considerable increase of Tg of polystyrene phase (about 8 ºC) without change of Tg of polybutadiene phase what is a very advantageous effect.
as high as possible values of the parameters taken into consideration.
W niniejszej pracy omówiono znane i stosowane metody poprawy odporności na starzenie atmosferyczne wulkanizatów kauczuków nienasyconych. Mają one jednak wiele wad, na które zwrócono uwagę.
W części doświadczalnej pracy podjęto próbę wykorzystania granulatu kauczuku etylenowo-propylenowo-dienowego (EPDM) jako dodatku chroniącego wulkanizaty SBR przed niszczącym działaniem czynników atmosferycznych.
Uzyskane wyniki świadczą o możliwości wykorzystania odpadów EPDM jako dodatku poprawijącego odporność na warunki atmosferyczne wyrobów gumowych z SBR lub innych kauczuków dienowych. Dodatek granulatu EPDM zwiększa odporność na starzenie cieplno-tlenowe wulkanizatów SBR oraz znacznie poprawia ich odporność na starzenie ozonowe wydłużając 10-krotnie okres pojawiania się wyraźnych spękań próbek wulkanizatów.
The results have been discussed in terms of appearing of propylene carbonate in the postpolycondensation system due to the thermall decomposition of poly(propylene carbonate) under conditions applied. Propylene carbonate probably acts as a swelling agent which makes the prepolymer chain mobility and increased crystallization as well as the removing of condensation low-molecular-weight by-products more facile.
Keywords: natural rubber, butadiene-acrylonitrile rubber, rubber mixtures, oil adsorption, sooth, dynamic properties.