Patent Application
20140339478
The present invention pertains to the field of electrically conductive polymer-based materials. In particular, the invention pertains to the use of carbon black for incorporation into a polymer to produce a compound having a defined volume resistivity, methods for producing such compounds and use of such compounds as antistatic or conductive materials.
Most polymer-based materials are inherently electrically insulating materials. However, imparting electrical conductivity can add significant value or utility. For example, imparting electrical conductivity to polymers enables electrostatic painting in automotive bumpers and can reduce creation and storage of static electricity. Electrically conductive polymer materials can also be used for protecting sensitive electronic components. Among the possible applications of electrically conductive or antistatic materials are:
However, other uses will be apparent to the skilled artisan in the field of conductive polymers.
In general, different performance regions of electrical conductivity of polymer-based materials can be distinguished: (1) Antistatic applications usually involve materials that exhibit surface resistivity of 1012 to 106 Ohm.cm. (2) Applications where electrical current or charges have to be transported, e.g., as heating elements, need resistivities below 106 Ohm.cm. Also electrostatic dissipation (ESD) applications usually involve imparting sufficient conductivity to polymer-based materials.
A typical way of conferring electrically conductive properties to inherently electrically insulating polymers involves the incorporation of carbon black as described, e.g., in EP 0109824. Usually, the addition of conductive additives like carbon black to highly resistive polymers like polyolefin results in an evolution of the resistivity as shown in
The evolution of the resistivity, called percolation curve, is characterized by mainly 3 parameters:
From
As a consequence, compounds having defined electrical resistivity levels between the plateau before the percolation threshold on the one hand, i.e., at the level of the virgin polymer, and the ultimate resistivity level on the other hand cannot be manufactured with acceptable reproducibility and stability. This applies even more as the standard deviation in compounding exceeds usually 0.5% (w/w). Also, a safety margin must usually be built into the recipe in order to cover variations to be brought to the resistivity during processing.
The prior art addresses this problem by adding further resistivity adjusting additives, with limited success in some specific polymers, however. Moreover, additional compounds may detrimentally affect mechanical and/or optical properties of the resulting materials.
EP 0109824 discloses an electrically conductive plastic complex material which comprises a mixture of the synthetic base resin material, an electrically conductive carbon black and at least one inorganic filler selected from graphite, calcium carbonate, talcum, alumina and titanium. EP 0109824 does not relate to carbon black obtainable through pyrolysis.
US2010249353 relates to the field of waste recycling, and particularly, to methods for reclaiming carbonaceous materials from scrap rubber tires and pyrolytic carbon black produced from such methods. US2010249353 does not disclose conductivity characteristics with respect to the carbon black obtained.
Dufeu, 2296 Journal of Applied Polymer Science 46 (1992), No.12, relates to PVC filled with vacuum pyrolysis scrap tires-derived carbon blacks and investigates rheological, mechanical, and electrical properties thereof. Dufeu does not disclose conductivity characteristics of PVC loaded with pyrolysis carbon black beyond the percolation threshold.
Boukadir, Journal of Analytical and Applied Pyrolysis, 3 (1981) p. 3, relates to the preparation of a filler for thermoplastics by pyrolysis of rubber powder recovered from tyres. Boukadir does not address conductivity characteristics with respect to pyrolysis carbon black.
Pantea, Journal of Analytical and Applied Pyrolysis 67 (2003) 55-76, discusses the heat-treatment of carbon blacks obtained by pyrolysis of used tires and investigates their effect on the surface chemistry and porosity of materials. Pantea does not investigate conductivity characteristics with respect to pyrolysis carbon black, either.
There remains a need for reproducible and cost-effective ways to produce polymer-based compounds of defined or predetermined volume resistivity, particularly in the range between 1012 and 104 Ohm.cm, in a convenient manner.
This problem is solved by the methods and compounds defined in the independent claims. Preferred embodiments are specified in the dependent claims.
Due to the use of carbon black according to the invention the slope of the decrease of the resistivity with increasing carbon black content can be reduced. For example, the 14 orders of magnitude of the resistivity can be covered by a variation of the carbon black content by 40%. This means that typically a range of about 3% of carbon black can be available per order of magnitude of resistivity.
Accordingly, the present invention is directed to the use of carbon black for incorporation into a polymer to produce a compound having a defined or predetermined volume resistivity, wherein the carbon black is obtainable by pyrolysis of carbon black filled crosslinked and/or uncrosslinked polymers. Hence, a compound having a defined volume resistivity can be produced by incorporating carbon black obtainable by pyrolysis of carbon black filled crosslinked and/or uncrosslinked polymers into a polymer in an amount above the percolation threshold. In particular, the carbon black can be incorporated into the polymer such that an alteration of the carbon black content by ±0.5% (w/w) within the percolation zone does not alter the volume resistivity of the resulting compound by more than a factor of 10. Percolation zone in this context means the zone between the percolation threshold and the ultimate resistivity level. It typically encompasses at least the zone between two orders of magnitude of volume resistivity below the volume resistivity level of the virgin (unloaded) polymer and one order of magnitude of volume resistivity above the ultimate resistivity level of the carbon black loaded polymer having minimum volume resistivity.
Polymer in the context of the present invention means any type of large molecule (macromolecule) composed of repeating structural units. A polymer that contains only a single type of repeat unit is known as homopolymer, while a polymer containing a mixture of repeat units is known as copolymer. For example, the polymer in which the carbon black is to be incorporated can be a synthetic polymer, particularly an organic polymer, such as a polyolefin, e.g., a low-density polyethylene. Examples of synthetic polymers are Low Density Polyethylene (LDPE), High Density Polyethylene (HDPE), Polypropylene (PP), Polyvinyl Chloride (PVC), Polystyrene (PS), Nylon, nylon 6, nylon 6,6, Teflon (Polytetrafluoroethylene), and Thermoplastic polyurethanes (TPU). Exemplary polymers in which the carbon black can be incorporated are non-rubber compounds, particularly compounds such as Acrylnitrile-butadiene-styrene terpolymer (ABS), Ethylen-metacrylic acid copolymers, Polyacetaldehyde, Polyacrolein, Polyacrylamide, Poly(acrylamide oxime), Poly(acrylic anhydride), Polyacrylonitrile, Poly(b-alanine)(3-Nylon), Ethylene-Propylene elastomers, Melamine-formaldehyde resins (MF), Phenol-formaldehyde resins (PF), Polyallene, Polybenzimadazole, Polybutylene terphtalate (PBT), Poly-n-butyraldehyde, Polychloroprene, Poly(decamethyleneoxamide), Polydecamethylenesebacamide (10-10 Polyamide), Polydeamethyleneurea, Polydichloroacetaldehyde, Polydiethynylbenzene, Poly(3.3′-dimethoxy-4-4′-biphenylene carbodiimide), Poly(2-3-dimethylbutadiene), Poly(2,5-dimethylpiperazine terephthalamide), Polydimethylsilylmethylene, Poly(ethylene terephthalate (PET), Poly(ethylene tetrasulfide), Poly-a-L-glutamic acid, Poly(glyceryl phthalate), Poly(glycolic ester), Poly(hexamethyleneadipamide) (6-6 Nylon), Polyethylene (PE), Poly(ethylene-co-proplylene adipate), Poly(ethylene glycol) (PEG), Poly(ethylene methylene bis(4-phenylcarbamate), Poly(ethylene N, N′-piperazinedicarboxylate), Poly(ethylene terephtalamide), Poly(hexamethylene m-benzenedisulfonamide), Poly(hexamethylenedi-n-butylmalonamide), Poly(N,N′-hexamethylen, 2,5-diketopiperazine), Polyhexamtylenesebacamide (6-10 Nylon), Poly(hexamethylen thioether), Polyhexamethyleneurea, Polyisobutylene (PIB), Poly(methyl acrylate), Polymethyleneadipamide (1-6 Nylon), Polynonamethylenepyromellitimide, Poly(3,5-octamethylene-4-amino-1,2,4-triazole), Poly(4-oxaheptamethyleneurea), Poly(l,4-phenylene sebacate), Poly(phenylene sulphide) (PPS), Poly(phenyl vinylene carbonate), Polystyrene (PS), Polytetrafluoroethylene (PTFE), Polypropanesultam, Polypropylene (PP), Poply(propylene glycol) (PPG), Poly(vinyl butyral) (PVB), Poly(vinyl bytyrate), Poly(vinyl carbazole), Poly(vinyl chloride-co-vinyl acetate), Polythiazyl, Poly(vinyl acetate) (PVAc), Poly(vinyl alcohol) (PVA), Poly(vinyl t-butyl ether), Poly(vinyl formal) (PVF), Poly(vinyl pyridine), Poly(vinyl pyrrolidone), Poly(vinyl isobutyl ether), Styrene-acrylonitrile copolymer (SAN), Potassium polymetaphosphate, Poly(p-xylene thiodipropionate), Urea-formaldehyde resins (UF). However, it will be understood that the carbon black can also be incorporated in rubber compounds such as Natural Rubber (NR), Synthetic Polyisoprene (IR), Styrene Butadiene Rubbers (SBR), Polybutadiene Rubbers (BR), Butyl and Halobutyl Rubbers (IIR, BIIR, CIIR), Ethylene Propylene Rubbers (EPM, EPDM), Crosslinked Polyethylene (XLPE), Neoprenes (CR), Nitrile Rubbers (NBR), HYPALON and Chlorinated Polyethylene (CSM, CPE), Silicone Rubbers (MQ), Fluorocarbon Rubbers (FKM), Specialty Heat & Oil Resistant Rubbers (ACM, ECO, FVMQ), Other Specialty Rubbers (AU, EU, T), Thermoplastic Rubbers (SBS, TPE, MPR, TPU).
Also comprised by the term polymer in the context of the present invention is a mixture of two or more polymers.
The term crosslinked polymer means that the polymer molecules have been submitted to a crosslinking between molecules by for example sulphur or peroxide or any other technique like electron beam radiation creating bridges between the macro-molecules.
A filled polymer generally means a polymer in which one or several fillers have been incorporated. Possible examples of fillers are carbon black, white fillers such as kaolin and talc, and others. Depending on the polymer and its intended application the amount of carbon black as filler varies typically between 5-80% (w/w) or between 10-50% (w/w), particularly in the case of tires. In the present invention, useful carbon black filled polymers to be pyrolysed may contain between 1-80% (w/w) carbon black, particularly between 10-70% (w/w) carbon black, of the total weight of the filled polymer.
Pyrolysis in the context of the present invention means any kind of thermal degradation in the absence of oxygen. Pyrolysis, or depolymerisation, particularly of crosslinked and/or uncrosslinked polymers filled with carbon black, is usually carried out at temperatures between 350 and 900° C., especially 400 to 550° C. Pyrolysis may be performed in the presence of one or more catalysts or additional mechanisms such as microwave irradiation in order to accelerate or facilitate the decomposition, which could result in a decrease in the amount of time and/or temperature needed for decomposition.
Absence of oxygen means that the pyrolysis is performed in an environment which is essentially oxygen-free, e.g., in a liquid and/or gaseous oxygen-free medium, or in vacuum.
In a preferred embodiment the carbon black is obtainable by pyrolysis of cured or uncured rubber compounds containing carbon black, particularly of used tires. Cured rubber compounds are crosslinked (mainly sulphur or peroxide) rubber based compounds. Typical examples of cured rubber compounds are tires, hoses, or seals. Uncured rubber compounds are the above mentioned compounds prior to cross-linking.
In general, the pyrolysis process can be a continuous or a batch process whereby the temperature can be in the range between 350° C. and 600° C., particularly between 450° C. and 550° C. The pressure is typically kept in the range between 101 KPa and 120 KPa.
The carbon black as described herein is obtainable by a process comprising
The optional treatment of the pyrolysate with inert gas(es) in step b) is useful to purge the oven and/or to avoid condensation of residual molecules from the pyrolysis process or gaseous reagents used to aftertreat the pyrolysis carbon black to obtain specific reinforcing or curing characteristics. Inert gases can be nitrogen, argon, and the like.
The mechanical treatment in step c) to separate metals can be carried out by magnetic separation or eddy current separation and the textiles or other solid contaminants can be separated by sieving or air stream.
Optionally, the pyrolysate can be treated with liquids in step d) to modify its surface chemistry and/or to leach inorganic compounds deposited on its surface. This treatment can be carried out by processing the carbon black as a slurry in vessels. Further steps to wash and dry the material may be used.
In step e) the carbon black can be grinded into finest particles of <45 μm, especially <10 μm diameter, for example by jet mill and/or shock wave treatment. The grinding step may comprise a step to produce a delivery form of carbon black. This step is useful in most cases in order to assure a carbon particle size suitable for a good wetting by the polymer and also not to interfere with the finishing processing and to guarantee a smooth surface.
Optionally, the process may further comprise a pelletization step to form pellets of the carbon black particles. Pelletization may be achieved by (1) production of small beads by a so-called wet process, mixing the carbon powder with water with or without pelleting additives (i.e. molasses) and followed by a drying step; or (2) production of beads by a dry process based on an electrostatic agglomeration produced in a rotating drum due to friction between the carbon particles. Alternatively, the carbon black particles can be compacted to form a densified powder for transport and handling reasons. Further explanation is given in “Kühner, G; Voll, M; Chapter 1, Manufacture of Carbon Black, Carbon Black Second Edition, Ed. J. B. Donnet, R.C. Bansal, Meng-Jiao Wang, Marcel Dekker”, which is incorporated herein by reference in its entirety.
One characteristic property of carbon black obtainable by pyrolysis of filled crosslinked and/or uncrosslinked polymers, particularly by the above described process, is an ash content of about 1% or more (w/w), for example of between 1-30% (w/w), particularly of between 5-25% (w/w) or 12-20% (w/w) of the total weight of the carbon black.
The ash content of a carbon black is the amount of non-carbon components present after combustion. It is determined according to ASTM D 1506. Primary contributants to ash are usually SiO2, ZnS, and ZnO and, depending on the starting material, also CaO or other white fillers or additives.
The carbon black can further be characterized by a volume resistivity of between 0.02-1.0 Ohm.cm, particularly of between 0.08-0.2 Ohm.cm, more particularly of about 0.1 Ohm.cm. The volume resistivity of the carbon black is measured according to ASTM D 6086 9a. This test method covers a procedure to measure a carbon black structure property known as “void volume”. Compressed void volumes are obtained by measuring the compressed volume of a weighed sample as a function of applied pressure in a cylindrical chamber by a movable piston with a displacement transducer on the piston mechanism. A profile of void volume as a function of applied pressure provides a means to assess carbon black structure at varying levels of density and aggregate reduction. Concurrently, and following the procedure of ASTM D 6086 9a, the volume resistivity of the sample can be measured as described in “Grivei, Eusebiu; Probst, Nicolas; Conductivity and carbon network in polymer composites, Kautschuk, Gummi, Kunststoffe-9-2003”, which is incorporated herein by reference in its entirety.
In another aspect, the invention is directed to a method for producing a compound having a defined volume resistivity, comprising incorporating carbon black as defined above into a polymer. In a particular embodiment the carbon black is incorporated in an amount of between 5-80% (w/w), particularly 10-60% (w/w), more particularly 15-50% (w/w), of the total weight of the resulting compound.
Particularly useful concentrations may depend on the type of polymer and possible other components of the compound. For a given polymer the skilled person is able to identify particularly useful carbon black values by performing routine tests with different carbon black concentrations, such as described in, e.g., “Probst, Nicolas; Chapter 8, Conductive carbon blacks, Carbon Black Second Edition, Ed. J. B. Donnet, R. C. Bansal, Meng-Jiao Wang, Marcel Dekker”, which is incorporated herein by reference in its entirety.
The incorporation of the carbon black into the polymer can be achieved by mixing carbon black and polymer in an internal mixer or mixing extruder, mixing in a dry blender followed by an extruder or any other mixing equipment used for mixing polymers, or blending the carbon black with the polymer during the polymerization step.
It is thus possible to produce a compound of defined volume resistivity without the addition of any further resistivity adjusting additives. However, in certain cases it can be beneficial to incorporate one or more additional additives, also resistivity modifying, i.e., resistivity increasing or decreasing additives. Suitable additives can be the different types of carbon black described in the prior art. Suitable additives can also be natural, synthetic, or expanded graphite; white fillers such as kaolin, CaCO3, talc, or clay; non miscible polymers; or polymer cristallites.
Also provided by the present invention is a compound of defined volume resistivity comprising a polymer and carbon black as defined above. In a particular embodiment the carbon black is present in an amount of between 5-80% (w/w), particularly 10-60% (w/w), more particularly 15-50% (w/w), of the total weight of the compound. The compound can have a volume resistivity of between 102-1016 Ohm.cm, particularly between 102-1012 Ohm.cm or between 104-1012 Ohm.cm.
The volume resistivity of the compound is measured according to ASTM D 991 for the range ≦106 Ohm.cm and to ASTM D 257 for the range >106 Ohm.cm. (general usage also in plastics). ASTM D991 is a standard test method for rubber property-volume resistivity of electrically conductive and antistatic products. In general, surface resistivity and volume resistivity are measured according to ASTM D257, IEC 60093. Surface resistivity is the resistance to leakage current along the surface of an insulating material. Volume resistivity is the resistance to leakage current through the body of an insulating material. The higher the surface/volume resistivity, the lower the leakage current and the less conductive the material is.
The test procedure according to ASTM D 991 and also ASTM D 257 involves that a standard size specimen is placed between two electrodes. For sixty seconds, a voltage is applied and the resistance is measured. Surface or volume resistivity is calculated, and apparent value is given (60 seconds electrification time). Specimen size: A 4-inch disk is preferable, but may be any practical form, such as flat plates, rods or tubes for insulation resistance. Data: Surface and Volume resistivity are calculated. Surface Resistivity is expressed in ohms (per square). Volume Resistivity is expressed in Ohm.cm.
From these methods one can generate the percolation curve and determine the percolation threshold as the value of carbon black concentration at which the resistivity of the compound begins to drop significantly. As an approximate value, the percolation threshold can be considered as the lowest value of carbon black concentration at which the addition of one further weight percent carbon black into the polymer would result in a drop of resistivity of the resulting compound by more than a factor of 3, particularly more than a factor of 5. It will be understood that the ultimate resistivity level in a similar manner can be considered, as an approximate value, as the highest value of carbon black concentration at which the removal of one weight percent carbon black from the polymer would result in an increase of resistivity of the resulting compound by more than a factor of 3, particularly more than a factor of 5.In another aspect, the invention is directed to the use of such compounds as an antistatic or conductive material.
In the following the invention is further explained with reference to the accompanying figures, which illustrate exemplary and non-limiting examples of the invention.
With reference to
All compounds were based on the same LDPE grade and have been mixed in a laboratory mixer type Brabender (50 ml volume chamber). The mixing cycle was (in minutes): 0′ Polymer; 2′ carbon black; 7′ Stop mixing. 2 mm plates were prepared by compression at 180° C. for 10 min.
N-472 stands for Carbon Black Grade N-472, which is obtained in a continuous process in the furnace by a thermal-oxidative decomposition of highly aromatic hydrocarbon oil. It belongs to low reinforcing grades of carbon black and it shows low values of dispersion and structural features. Carbon Black Grade N-472 can be obtained from all major carbon black producers (e.g., Cabot, Columbian).
All tested types of prior art carbon black have in common that once the percolation threshold is exceeded the resistivity of the compound dramatically drops over several orders of magnitude with a minimum increase of carbon black content. In the tested examples, the slope is characterized in that a 3% increase in the carbon black content results in a change of the resistivity of the compound from 1015 Ohm.cm to 101 Ohm.cm, respectively. In the case of Carbon Black Grade N-472, for example, a content of about 11% (w/w) carbon black results in a volume resistivity of the compound of about 1015 Ohm.cm, whereas a content of about 14% (w/w) carbon black grade N-472 leads to a volume resistivity of about 10 Ohm.cm. Apparently, a desired resistivity level in the range between, e.g., 1012 and 104 Ohm.cm, can hardly be adjusted with such carbon blacks.
It can be seen from
As a consequence, the range of allowed carbon black content in a compound having an intended defined volume resistivity is expanded. In other words, a slight alteration of the carbon black content within the percolation zone, e.g., by ±0.5% (w/w), does not overly alter the volume resistivity of the resulting compound, e.g., not more than a factor of 10. In certain embodiments, an alteration of the carbon black content by ±1.0% (w/w), particularly by ±1.5% (w/w), does not alter the volume resistivity of the resulting compound by more than a factor of 10 within the percolation zone. It is thus possible to achieve a desired resistivity level in the range between, e.g., 1012 and 104 Ohm.cm, simply by properly dosing the amount of carbon black.
In the following, non-limiting examples of the invention are described.
CCT R 632 and CCT R 610 (herein referred to as CBp) are carbon blacks produced by the pyrolysis of used tires. The pyrolysis is performed in a 10 m3 batch reactor. The reaction itself is endothermic and a small (10-80 mbar) overpressure is set throughout the whole process. During the process the crosslinked and/or uncrosslinked polymers, e.g., used tires are kept at a temperature between 420° C. and 600° C. in the reactor for 2-6 h. After the reaction time is over, the reactor is cooled to room temperature and the carbon char is collected.
The pyrolysis process results in two product streams, one gaseous, collecting the products from the depolymerisation of the polymers, and one solid phase, the metal from the wires and the carbonaceous part combining carbon black, ashes and carbonaceous residue. The process is carried out without any specific additive participating directly or indirectly in the process.
The gaseous phase is to a large extent condensed into the pyrolysis oil. The metal is separated from the carbonaceous material. The latter one is converted into particles with sizes of a maximum of 32 μm for CCT R 632 and 10 μm for CCT R 610, respectively, and pelletized for conditioning and transport.
CBp is, according to Reach (Regulation, Evaluation, Authorization and Restriction of Chemicals described in EC 1907/2006), classified as original carbon black from partial combustion processes, as long as the concentration of the original material, in this case carbon black, is at least 80%.
Analytical Properties
1.1 Morphology of the Pyrolysis Carbon Black
CBps have to be considered using the same criteria as other carbon blacks, some methods used however have to be adapted to this new material. Two reasons for the specific treatment of CBp are the feasibility of the test and the significance of the test results. Table I summarizes the most common parameters.
1.2 Particle Size
Carbon black particle size is determined by image analysis of a finely dispersed sample as described by ASTM D 3849. Particle size of classical carbon black is understood as being the size of the primary particle. Those particles are fused together in the aggregate and agglomerate to larger entities. Particle size can also be calculated with a quite good compliance from the value of the specific surface area. Typical classical carbon blacks range from 11 nm to 250 nm for thermal black, the coarsest material. These nanoparticles are believed to provide the largest contribution to the specific surface area.
CBps show a very complex particle size distribution. A large part of the particles remain more or less at their original size and give by TEM image analysis a broad distribution resulting from the variety of the various blacks present in a passenger car tire. A second group of particles results from the grinding of macroscopic solid parts into relatively large items.
Laser scattering can be used to determine the particle size distribution of those elements. The results could, however, be misleading, as the laser scattering gives the size of the entities visible to this technique and as such may represent an aggregate form or even an agglomerate. The interpretation of the results appears to be quite complex as laser scattering is not a commonly used method for the determination of particle size for classical carbon blacks in the nano-meter range.
Aggregate size distribution shows an average entity of 200 nm and ranges from 50 nm to 1000 nm, while the average of the blacks used in a tire averages around 140 nm. This observation is in line with the supposition that during pyrolysis, aggregates are fused together by the pyrolysis deposits.
In the literature CBps are usually reported with a Bi- or Tri-modal distribution. The first peek being most probably related to the original carbon black particles, in most cases slightly shifted to larger particles due to small surface deposits during pyrolysis. The two other peaks represent the particles generated during grinding. These larger micrometric particles have a very low if not negligible contribution to the specific surface area.
1.3 Specific Surface Area
For fillers specific surface area is a very important parameter determining the extension of the surface area available for polymer-filler interaction. Various techniques are available for the determination of the specific surface area. The commonly used iodine number is not suitable for use with pyrolysis carbon black. Iodine number observed reaches unrealistic values due to the interference of pyrolysis residues and ash.
Nitrogen surface area can be applied as inert N2 molecules are adsorbed. Nitrogen surface area is sensitive to the presence of micro- and nano-pores and is consequently also a measure of the reproducibility of the pyrolysis process. The rubber industry is commonly considering the round surface (surface area accessible to the large polymer molecules) as significant for predicting the performance in the compound. CTAB method can be replaced by STSA surface area (calculated from BET) as it gives quite similar information. Both techniques Nitrogen surface area and CTAB are applicable to CBp.
1.4 Surface Chemistry
Besides the extension of the polymer accessible surface area, the quality of the surface determines the reinforcement properties. Defects in carbon black graphitic surface texture and plane edges as well as fullerene like elements are considered responsible for the reinforcement phenomena.
Inverse Chromatography (IGC) has been used with furnace blacks to assess the surface energy and active sites at finite and infinite dilution.
Similar information was expected when IGC was performed on CBp.
Maafa and co-workers (D. Maafa, J. Balard, J.-B. Donnet ; KGK April 2011, p 24-28) showed that CBp does not have any significant surface activity. This fact is explained by the coverage of the original active sites by the pyrolysis inorganic parts and carbon deposit. This observation is in line with the expectation that all active sites will primarily react with the pyrolysis residues. Considering this fact, it can be concluded that the extension of the surface is not very relevant to the information one could expect for predicting the reinforcing potential of CBp. The surface of CBp can be considered as inert in comparison with furnace black of similar specific surface area and results in lower reinforcing activity, as will be demonstrated below.
The pH of CBp is quite neutral, reflecting to a large extent the mineral nature of the carbon surface.
Electrical measurements by compression on the powder show that the contacts with the carbon are relatively resistive in comparison with conventional furnace black. Conventional furnace black has a quite graphitic surface while CBp has ash and saturated carbon on the surface. As one can see from Table II below, the electrical resistivity of CBp lies in-between pure and oxidized furnace black. This subject was already discussed by Paneta and co-workers (H. Paneta, H. Darmstadt, S. Kaliaguine, S. Blacher, C. Roy, ACS Rubber Division spring meeting 2001). The authors documented their conclusions with tof-SIMS data showing the reduced graphitic nature of CBp.
1.5 Structure
Structure designates the interstitial and inter-particle volume of the carbon black and is in fact the result of the size and complexity of the arrangements of the carbon black particles within the aggregate and their agglomeration.
OAN, Oil Absorption Number, is the most common technique for the assessment of the structure of carbon black. The method given in ASTM D 2414 determines the structure of a carbon black by the determination of the saturation of the carbon black by the addition of oil. The saturation is achieved when the torque of the mixer incorporating the oil is suddenly increasing. This method is functioning very well with most furnace blacks, some blacks however show a very small increase in torque when the end point is reached and OAN is difficult to measure. The use of blends of those blacks with very high structure carbon blacks usually allows overcoming this problem. This is the case with most CBps. The direct measurement of the void volume is as such a method suggested for CBps for structure determination.
The void volume of the CBp is slightly below that of N-550. The original structure of the carbon black has been reduced during incorporation and most probably during the grinding step of the CBp. One can expect that the structure will not be broken down during further mixing steps.
COAN, Oil Absorption Number on the compressed carbon blacks is feasible with the method described in ASTM D 3493. This value, developed to assess the structure level of a carbon black after incorporation of the compound, is for the CBp comparable with the one obtained for N-550.
It can be expected that the information available from structure measurements is quite comparable with the one observed for furnace blacks. Others indicate that also here the original meaning of the carbon black parameter has to be considered with care.
2 Composition of Pyrolysis Carbon Black
The analysis of CBp as shown in Table III describes the mass composition of the material. Surface deposits resulting from the pyrolysis are deposited on the surface of the original particles. The performance of a filler in a polymer, its interaction with the polymer as well as its ability to interact with neighbour particles to form filler networks is mainly related to the surface quality of the material.
2.1 Carbonaceous Components in CBp
The main carbonaceous component of the CBp is the original carbon black. X-ray Photoelectron Spectroscopy (XPS) allows an analysis of the elemental composition of the surface. According to the analysis of several samples, carbon represents 94% of the surface followed by Zn, Si and S.
The elemental composition depends mainly on the composition of the raw material (e.g., used tire). The nature of the links between elements may vary with the pyrolysis process and operating conditions.
Darmstadt and co-workers (H. Darmstadt, C. Roy, S. Kaliaguine, Carbon, Vol. 33, N° 10, pp 1449-1455, 1995) have studied carbon blacks from vacuum pyrolysis by XPS. It has been shown that the major part of the carbon is graphitic, most probably resulting from the original carbon black. The remaining carbon is mainly involved in —C—O and C═O bindings.
It has further been shown that the largest part of the oxygen is in C═O and Si—O bonds and only 20% in C—O-bonds. It can be assumed that from the total 9% of oxygen 3 to 5% are linked with Si atoms, a few percent with Zn and the remaining with Ca and carbon.
2.2 Inorganic Components in CBp
Inorganic elements are mainly Si from the silica, Zn originally from the ZnO and transformed into ZnS during the vulcanization step and possibly during pyrolysis (Darmstadt and co-workers). Sometimes small quantities of Ca are observed, most probably from vulcanizing additives, aging retarders and antioxidants.
2.3 Contaminations in CBp
Inorganic components can be considered as contaminants in a carbon black, for CBp SiO2 and ZnO or ZnS will have to be considered as integral parts. Work done by Donnet and co-workers and Darmstadt and co-workers (A. Chaala, H. Darmstadt, C. Roy, Fuel Processing Technology 46, (1996) 1-5) have shown that the elimination of SiO2 and ZnO or ZnS are a very time- and energy consuming step. They additionally showed that the surface chemistry of the product was not modified. The term contamination includes sulphur and other trace elements present in the carbon black as well as organic molecules carried over from the tire and mainly generated during the pyrolysis process.
Darmstadt and co-workers (H. Darmstadt, C. Roy, S. Kaliaguine, KGK, 47, N° 12, 1994) have studied the sulphur compounds in CBp as a function of the operating conditions. Sulphur is present in small quantities in most commercial carbon blacks. Although very small amounts of free sulphur may exist, it is usually present in organic molecules. Rubber companies may have in some cases limitations around 1.5% on total sulphur, however the main reason for the reduction of sulphur in commercial carbon black is environmental. In CBp sulphur is mainly present in ZnS, and according to Roy and co-workers, no free Sulphur has been detected on CBp.
Other elements, as listed in the attached Table IV, are coming from the tire. The level of these trace contaminations are not expected to interfere with most of the carbon black applications. This has been confirmed by the development work of the present inventors.
Two origins can be mentioned as the main source of such contaminations:
The type and level of the trace elements varies with the tire composition. Some elements may also appear in certain CBps at relatively high level, due to the use of catalysts and specific pyrolysis techniques.
Polyaromatic molecules are today of quite important concern for health, safety and environmental reasons. Table V below illustrates typical values of polycyclic aromatic hydrocarbons (PAH) measured on CBp according to the US Environmental Protection Agency (EPA) and EC directives.
Commercial carbon blacks sometimes exhibit the presence of small quantities of organic residues. These residues result from the condensation of molecules onto the carbon black surface. The level of these residues depends on the operating conditions. Mainly short quenching is known to result in relatively high amounts of organic residues. CBp shows also some organic residues adsorbed on the surface. Analyses made on CBp blacks according to the EC directive and to EPA are given in Tables V and VI, respectively. The molecules listed in the EC directive appear to be present in very low quantities. Molecules listed in EPA are also present in very low levels for most of them except naphthalene and some of its substitutes.
Solid undispersible particles, commonly called sieve residue or grit are composed of carbonaceous particles, ash particles and metal.
The invention has been demonstrated with reference to exemplary embodiments. It will be understood by one skilled in the art that modifications to these embodiments can be made without departing from the scope of the invention as defined in the appended claims.
| Number | Date | Country | Kind |
|---|---|---|---|
| 11192994.9 | Dec 2011 | EP | regional |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/EP2012/075132 | 12/11/2012 | WO | 00 | 6/12/2014 |
| Number | Date | Country | |
|---|---|---|---|
| 61569298 | Dec 2011 | US |
