NL2015888B1 - Pyrolysis carbon black powder. - Google Patents
Pyrolysis carbon black powder. Download PDFInfo
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- NL2015888B1 NL2015888B1 NL2015888A NL2015888A NL2015888B1 NL 2015888 B1 NL2015888 B1 NL 2015888B1 NL 2015888 A NL2015888 A NL 2015888A NL 2015888 A NL2015888 A NL 2015888A NL 2015888 B1 NL2015888 B1 NL 2015888B1
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- rubber
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- 238000000197 pyrolysis Methods 0.000 title claims abstract description 52
- 239000000843 powder Substances 0.000 title claims abstract description 48
- 239000006229 carbon black Substances 0.000 title abstract description 76
- 238000010058 rubber compounding Methods 0.000 claims abstract description 52
- 239000000203 mixture Substances 0.000 claims abstract description 45
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- 229920001971 elastomer Polymers 0.000 claims description 44
- 239000005060 rubber Substances 0.000 claims description 43
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 31
- 239000000377 silicon dioxide Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- 244000043261 Hevea brasiliensis Species 0.000 claims description 7
- 229920003052 natural elastomer Polymers 0.000 claims description 7
- 229920001194 natural rubber Polymers 0.000 claims description 7
- 229910052681 coesite Inorganic materials 0.000 claims description 6
- 229910052906 cristobalite Inorganic materials 0.000 claims description 6
- 229910052682 stishovite Inorganic materials 0.000 claims description 6
- 229910052905 tridymite Inorganic materials 0.000 claims description 6
- 238000005299 abrasion Methods 0.000 claims description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims description 4
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 229920003051 synthetic elastomer Polymers 0.000 claims description 3
- 239000006057 Non-nutritive feed additive Substances 0.000 claims description 2
- 239000005062 Polybutadiene Substances 0.000 claims description 2
- 235000021355 Stearic acid Nutrition 0.000 claims description 2
- 239000003963 antioxidant agent Substances 0.000 claims description 2
- 230000003078 antioxidant effect Effects 0.000 claims description 2
- 239000010692 aromatic oil Substances 0.000 claims description 2
- 239000000839 emulsion Substances 0.000 claims description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 2
- 229920002857 polybutadiene Polymers 0.000 claims description 2
- 239000008117 stearic acid Substances 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 22
- 229910052799 carbon Inorganic materials 0.000 claims 11
- 239000003674 animal food additive Substances 0.000 claims 1
- 239000011593 sulfur Substances 0.000 claims 1
- 229910052717 sulfur Inorganic materials 0.000 claims 1
- 235000019241 carbon black Nutrition 0.000 description 72
- 239000000945 filler Substances 0.000 description 16
- 150000001875 compounds Chemical class 0.000 description 13
- 230000000694 effects Effects 0.000 description 10
- 239000000463 material Substances 0.000 description 8
- 238000009472 formulation Methods 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 230000002787 reinforcement Effects 0.000 description 3
- 239000006235 reinforcing carbon black Substances 0.000 description 3
- 241000239290 Araneae Species 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000006240 Fast Extruding Furnace Substances 0.000 description 2
- 239000006238 High Abrasion Furnace Substances 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 239000006236 Super Abrasion Furnace Substances 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 235000010216 calcium carbonate Nutrition 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- 235000012241 calcium silicate Nutrition 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- -1 for example Chemical compound 0.000 description 1
- 229920006247 high-performance elastomer Polymers 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention relates to a pyrolysis carbon black powder and a rubber formulation comprising such a pyrolysis carbon black powder. In addition the present invention also relates to a rubber formulation comprising a mixture of different types of carbon black powders. Furthermore, the present invention relates to use of such a rubber formulation in the manufacture of tyres. The present invention relates to a tyre comprising the present rubber formulation as well.
Description
Title: Pyrolysis carbon black powder
The present invention relates to pyrolysis carbon black powder and a rubber formulation comprising such a pyrolysis carbon black powder. In addition the present invention also relates to a rubber formulation comprising a mixture of different types of carbon black powders. Furthermore, the present invention relates to use of such a rubber formulation in the manufacture of tyres. The present invention relates to a tyre comprising the present rubber formulation.
Rubber compositions typically contain particulate filler reinforcement to promote enhancement of physical properties of the rubber composition. Conventional filler reinforcement used for rubber compositions is typically at least one of rubber reinforcing carbon black and silica such as, for example, precipitated silica, including combinations of rubber reinforcing carbon black and the silica.
Rubber being one of the most outstanding materials is widely used in many engineering applications such as automotive, civil and electrical. It has been well established that rubber without filler materials have very low physical strength and of no practical use. Fillers are compounding ingredients added to a rubber compound for the purpose of either reinforcing or cheapening the compound. Despite that, fillers can also be used to modify the physical properties of both unvulcanized and vulcanized rubbers. Typical filler materials include carbon black, calcium silicate, calcium carbonate, silicon dioxide (silica) and clay. Fillers can be classified as black or white (non-black) fillers. Black fillers are more widely used in the rubber industry than white fillers. It is used in tyres, hoses and cable industries. Meanwhile, white fillers are used in the footwear, general rubber goods and automotive industries. In tyres both black fillers, such as carbon black, and white (non-black) fillers, such as silica, are used.
Carbon black is the most popular filler added into the rubber compound due to its ability to enhance the strength properties of rubber vulcanizate as compared to gum vulcanizate; where no filler added. Generally, there are various types of carbon black grades used in the rubber industry such as N-220 ISAF (Intermediate Super Abrasion Furnace), N-330 HAF (High Abrasion Furnace), N-550 FEF (Fast Extruding Furnace) and N-660 GPF (General Purpose Furnace) series. However, the choice of carbon black grades for any given rubber formulation must take into account the desired physical properties of the end products, processing methods and costs.
European patent application EP 2 457 945 relates to two rubber compositions, namely a silica-rich rubber compound and a carbon black-rich rubber compound without silica coupler and without sulphur curatives. The silica-rich rubber compound contains all of the silica reinforcement for the final rubber composition.
The carbon black-rich rubber compound contains all of the rubber reinforcing carbon black for the final rubber composition, wherein the two individual rubber compounds would not be silica coupler-containing reactive rubber compounds. Each of the rubber compounds are prepared by mixing the respective rubber compounds in an internal rubber mixer or on an open cylindrical mill after which the two rubber compounds are mixed together in desirable ratios.
International application WO2013095145 in the name of the present applicant relates a method for recycling a scrap rubber, in particular tyres, which method comprises the following steps: i) pyrolyzing a scrap rubber to obtain a char material; ii) milling the char material obtained in step i) to obtain a carbon black powder wherein the pyrolysis in step i) comprises at least a two-stage pyrolysis process: a) a first pyrolysis stage to obtain an intermediate char material and b) a second pyrolysis stage to obtain a char material, wherein at least one of the stages a) or b) is carried out in a rotary kiln. International application WO2013095145 also relates to the use of a scrap rubber derived carbon black powder as a filler or reinforcing agent in a rubber composition, an ink, a paint, a bitumen, a thermoplastic composition or a thermoplastic elastomer. A tyre is a ring-shaped covering that fits around a wheel's rim to protect it and enable better vehicle performance. Most tires, such as those for automobiles and bicycles, provide traction between the vehicle and the road while providing a flexible cushion that absorbs shock. The materials of modern pneumatic tires are synthetic rubber, natural rubber, fabric and wire, along with carbon black and other chemical compounds. They consist of a tread and a body. The tread provides traction while the body provides containment for a quantity of compressed air.
The performance characteristics of tyres are important, such as rolling resistance, i.e. the resistance to rolling caused by deformation of the tire in contact with the road surface, abrasion and wet traction, i.e. the tire's traction, or grip, under wet conditions.
An aspect of the present invention is to provide a pyrolysis carbon black powder having specific properties.
Another aspect of the present invention is to provide a rubber formulation comprising a pyrolysis carbon black powder, said rubber formulation showing a high level of mechanical properties.
Another aspect of the present invention is to provide a rubber formulation comprising a mixture of standard of carbon black powder and a pyrolysis carbon black powder, said rubber formulation being suitable as a component for the manufacture of tyres.
The present invention relates thus to a pyrolysis carbon black powder having a BET (ASTM D6556) in a range of 72-92 m2/g, a STSA (ASTM D6556) in a range of 57-75 m2/g, a OAN (ASTM D2414) in a range of 82-102 cm3/100g, a total inorganic content (DIN 51719) in a range of 9-38%, and a Si02 content in ash (DIN EN 15309) in a range of 0-30%.
The term “pyrolysis” means here that the carbon black powder has been manufactured according to a pyrolysis process. Carbon black powder produced by the incomplete combustion of heavy petroleum products does not fall within the definition of the present term “pyrolysis carbon black powder”.
According to a preferred embodiment the present pyrolysis carbon black powder has a BET (ASTM D6556) in a range of 82-92 m2/g, a STSA (ASTM D6556) in a range of 65-75 m2/g, a OAN (ASTM D2414) in a range of 92-102 cm3/100g, a total inorganic content (DIN 51719) in a range of 9-19%, and a Si02 content in ash (DIN EN 15309) in a range of 0-10%.
According to another preferred embodiment the present pyrolysis carbon black powder has a BET (ASTM D6556) in a range of 72-82 m2/g, a STSA (ASTM D6556) in a range of 57-67 m2/g, a OAN (ASTM D2414) in a range of 82-92 cm3/100g, a total inorganic content (DIN 51719) in a range of 28-38%, and a Si02 content in ash (DIN EN 15309) in a range of 10-30%.
In addition, the present invention relates to a rubber formulation comprising a mixture of any of the present pyrolysis carbon black powder as mentioned before and at least a carbon black, classified according to ASTM D1765-13, chosen from the group of N110, N115, N121, N134, N220, N234, N299, N326, N330, N339, N343, N347, N375, N539, N550, N650, N660 and N762.
In a preferred embodiment the present invention relates to a rubber formulation comprising any of the present pyrolysis carbon black powders as mentioned above.
The present inventors found that by applying any of the present pyrolysis carbon black powders or a mixture of any of the present pyrolysis carbon black powder as mentioned before and at least a carbon black chosen from the group mentioned before in a rubber formulation results in high performance rubber formulation.
The term pyrolysis carbon black powder as mentioned before refers to a specific type of carbon black especially manufactured according to the two-stage pyrolysis process as disclosed in International application WO2013095145 in the name of the present applicant. The Technical Data Sheet of two different grades of pyrolysis carbon black powder according to the present invention can be found in Table 1 below.
The rubber formulation according to the present invention preferably comprises a rubber chosen from the group of natural rubber (NR), synthetic polyisoprene rubber (IR), solution type styrene butadiene rubber (S-SBR), emulsion type styrene butadiene rubber (E-SBR) and polybutadiene rubber (BR), or a combination thereof.
According to a preferred embodiment the present rubber formulation comprises a mixture of any one of the present pyrolysis carbon black powders and at least a carbon black from the group mentioned before wherein the amount of any one of the present pyrolysis carbon black powders is in the range of 10-90 wt. % and the amount of said at least a carbon black is in the range of 90-10 wt. %, based on the total weight of said mixture.
According to another embodiment the present rubber formulation comprises a mixture of any one of the present pyrolysis carbon black powders and at least a carbon black from the group mentioned before wherein the amount of any one of the present pyrolysis carbon black powders is in the range of 20-80 wt. % and the amount of said at least a carbon black is in the range of 80-20 wt. %, based on the total weight of said mixture.
According to another embodiment the present rubber formulation comprises a mixture of any one of the present pyrolysis carbon black powders and at least a carbon black from the group mentioned before wherein the amount of any one of the present pyrolysis carbon black powders is in the range of 40-60 wt. % and the amount of the at least a carbon black is in the range of 60-40 wt. %, based on the total weight of said mixture.
The present rubber formulation further comprises one or more usual additives, such as zinc oxide, stearic acid, antioxidant, sulphur, accelerator, antiozonant, processing aid naphthenic and aromatic oil. These additives are commonly used in rubber formulations. A preferred rubber formulation according to the present invention comprises a mixture of different types of carbon black powders, the mixture comprising 20-80 wt. % of any one of the present pyrolysis carbon black powders and 80-20 of N330 wt. %, based on the total weight of said mixture of carbon blacks, wherein the rubber preferably comprises natural rubber (NR).
The amount of the mixture of different types of carbon black powders, that is a mixture of any one of the present pyrolysis carbon black powders and at least a carbon black, classified according to ASTM D1765-13, chosen from the group of N110, N115, N121, N134, N220, N234, N299, N326, N330, N339, N343, N347, N375, N539, N550, N650, N660 and N762, in the final rubber formulation is in a range of 5-50 wt. %, based on the total weight of said rubber formulation.
The Hardness Shore A, measured according to ISO 7619-1, of the rubber formulation is at least 55, preferably at least 57, more preferably at least 60.
The abrasion loss, measured according to ISO 4649:2010, of the rubber formulation is less than 150 mm3, preferably less than 130 mm3, more preferably less than 120 mm3.
Furthermore, the present invention relates to the use of a rubber formulation according to the present invention in the manufacture of tyres.
In addition, the present invention relates to a tyre comprising the present rubber formulation as discussed above.
The invention will be described by way of examples and these examples are used as exemplary embodiments of the present invention.
Figure 1 shows a comparison between a pyrolysis carbon black powder according to the present invention vs. a standard carbon black N330, classified according to ASTM D1765-13.
Figure 2 shows a comparison between an 80:20 wt. % mixture of a pyrolysis carbon black powder according to the present invention and a standard carbon black N330, classified according to ASTM D1765-13 vs. a standard carbon black N347, classified according to ASTM D1765-13.
Figure 1 and Figure 2 are so-called spider graphs which mean that some values have been inverted. Spider graphs provide the reader a direct impression of the results. In other words, for all values means a high value is a good result. Thus a point “outside” the inner circle, which inner circle refers to a reference value, can be identified as “good” orbetter”.
For Figure 1 the inverted values relate to Tan delta at 0 °C (ISO 4664-1), Tan delta at 60 °C (ISO 4664-1), Payne effect A(G'1-G'20), Payne effect A(G'1-G'90) and hysteresis.
For Figure 2 the inverted values relate to abrasion loss (ISO 4649 Method A), compression set (24h @ 70°C, ISO 815), Tan delta at 0 °C (ISO 4664-1), Tan delta at 60 °C (ISO 4664-1), Payne effect A(G'1-G'20) and Payne effect A(G'1-G'90).
Table 1: Properties of two grades of pyrolysis carbon black powder according to the present invention.
Example 1 A rubber recipe was prepared on basis of carbon black powder BBC t30, i.e. a pyrolysis carbon black powder according to the present invention. Another rubber recipe was prepared on basis standard carbon black N330, classified according to ASTM D1765-13. These recipes tested in ASTM D3192 standard rubber recipe.
The performance results of the present rubber formulation, i.e. a formulation comprising carbon black powder BBC t30, were compared to the performance results of standard carbon black N330, classified according to ASTM D1765-13.
The results have been shown in figure 1.
Figure 1 clearly shows that BBC t30 outperforms standard carbon black N330, especially for properties such as Tear nick-crescent (ISO 34-1 Method C), rebound resilience (ISO 4662), Tan delta at 0 °C (ISO 4664-1), Tan delta at 60 °C (ISO 4664-1), Payne effect A(G'1-G'20), Payne effect A(G'1-G'90) and hysteresis. Please note that there is no international standard for determining Payne effect. The method used (ERT403) is an internal method developed by Elastomer
Research Testing (ERT) laboratory, Deventer, Netherlands.
Example 2 A carbon black mixture was prepared on basis of a mixture of 20 wt.% carbon black powder BBC t30, i.e. a pyrolysis carbon black powder according to the present invention, and 80 wt.% N330, a standard carbon black N330, classified according to ASTM D1765-13. On basis of this mixture a rubber composition according to the present invention was prepared.
Another rubber composition was prepared on basis of a standard carbon black N347, classified according to ASTM D1765-13.
Both recipes were tested in ASTM D3192 standard rubber recipe.
The performance results of the present rubber formulation, i.e. a formulation comprising a mixture of carbon black powder BBC t30 and N330, were compared to the performance results of standard carbon black N347, classified according to ASTM D1765-13.
The results have been shown in figure 2.
Figure 2 clearly shows that present rubber formulation, i.e. a formulation comprising a mixture of carbon black powder BBC t30 and N330, outperforms standard carbon black N347, especially for properties such as abrasion loss (ISO 4649 Method A), compression set (24h @ 70°C, ISO 815), Rebound resilience (ISO 4662), DeMattia flex fatigue (ASTM D-430 Method B), Tear nick-crescent (ISO 34-1 Method C), Tan delta at 0 °C (ISO 4664-1), Tan delta at 60 °C (ISO 4664-1), Payne effect A(G'1-G'20) and Payne effect A(G'1-G'90). Please note that there is no international standard for determining Payne effect.
Claims (16)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NL2015888A NL2015888B1 (en) | 2015-12-01 | 2015-12-01 | Pyrolysis carbon black powder. |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NL2015888A NL2015888B1 (en) | 2015-12-01 | 2015-12-01 | Pyrolysis carbon black powder. |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| NL2015888B1 true NL2015888B1 (en) | 2017-06-14 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NL2015888A NL2015888B1 (en) | 2015-12-01 | 2015-12-01 | Pyrolysis carbon black powder. |
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| NL (1) | NL2015888B1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110878148A (en) * | 2019-11-19 | 2020-03-13 | 珠海格力绿色再生资源有限公司 | Method for modifying pyrolysis carbon black |
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2015
- 2015-12-01 NL NL2015888A patent/NL2015888B1/en active
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110878148A (en) * | 2019-11-19 | 2020-03-13 | 珠海格力绿色再生资源有限公司 | Method for modifying pyrolysis carbon black |
| CN110878148B (en) * | 2019-11-19 | 2021-06-15 | 珠海格力绿色再生资源有限公司 | Method for modifying pyrolysis carbon black |
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