The invention relates to additive material materials as a part of a rubber-based material for the purpose of restricting fluid permeability. In other terms, the invention relates to articles suitable for use as at least a part of a pressurizable container or pipeline, the article comprising rubber-based material and an additive material. The invention relates to use of such articles such that a pressure difference exits between sides of the article. In particular, the article may be a pneumatic tyre for a motor vehicle. The invention relates to methods for manufacturing pneumatic tires.
Articles formed of rubber-based material are commonly used in containers or pipelines, the articles thus forming at least a part of such a container or a pipeline. Examples of such articles include pipes, tubes, hoses, sealing rings, pneumatic tyres (tubeless and/or inner tyres), containers, such inflatable containers, vessels, and parts of any one of these.
A purpose of the rubber-based material in such articles is to restrict fluid permeability of the container or the pipeline. Herein the term “fluid” refers to liquid or gaseous fluid. In pneumatic tyres, the fluid is a gas.
Because of purpose of the material, a low fluid permeability is required. Fluid permeability can be affected by mixing some additive material or additive materials with a rubber-based matrix material to form a rubber-based material comprising the additive material. However, depending on the type of the additive, even if permeability can be lowered, some other properties (e.g. ductility) may be lost. Therefore, some additives may deteriorate other properties of the rubber-based material, whereby they are, in practice, not usable, or usable only to a small extent.
A problem in such articles is to find a rubber-based material that has a decreased fluid permeability at the same time the other properties are not compromised.
The inventors have found that lignin that has been treated by hydrothermal carbonization (hereinafter HTC-lignin) is capable of decreasing fluid permeability of many rubber-based materials. In particular, the inventors have found that lignin that has been treated by hydrothermal carbonization (i.e. HTC-lignin) is capable of decreasing air permeability of many rubber-based materials. HTC-lignin can be mixed with a rubber-based matrix material to form rubber-based material that is configured to restrict fluid permeability and that comprises HTC-lignin. An example of the article is a pneumatic tyre for a motor vehicle. The pneumatic tyre may be an inner tyre or a tubeless tyre. Moreover, the rubber-based material comprising the HTC-lignin forms, or is arranged close to, an inner surface of the pneumatic tyre. Thus, the fluid does not penetrate the tyre. In use, the sides of the article/tyre are exposed to fluid environments having different pressures. The invention is more specifically disclosed in the appended independent claims 1 and 17. Dependent claims define preferable embodiments. The description including numbered examples includes also other embodiments and examples not falling within the scope of claims but are considered useful for understanding the invention. Claims cover also further solutions not explicitly disclosed in the description.
Articles formed of rubber-based material are commonly used in chambers, containers, or pipelines, the articles thus forming at least a part of such a container, chamber, or a pipeline. Examples of such articles (100, 200, 300, 400, 900) include tubeless pneumatic tyres 100 for a motor vehicle, shown in
Common to all these articles 100, 200, 300, 400, 900 is that the article 100, 200, 300, 400, 900 comprises a first side 111, 211, 311, 411, 911 and a second side 112, 212, 312, 412, 912. The first side is, in use, configured to be exposed to a first environment ENV1 and the second side is, in use, configured to be exposed to a second environment ENV2. Moreover, in use, the first side is, in use, configured to be exposed to a higher pressure than the second side. In particular, the surface formed by the first side 111, 211, 311, 411, 911, or a coating (136, 137, 237, 937, 337) of the first side, is, in use, configured to be exposed to the first environment ENV1. The coating, if any, is relatively thin, as discussed below. The first side thus refers to an inner side of the pneumatic tyre.
Because of this pressure difference, low fluid permeability is required from such articles. The term “fluid” refers to liquid or gaseous fluid, or a mixture of a gas (vapor) and a liquid, or a substance in a supercritical stage. However, as well known, the state of the material depends on temperature and pressure. Thus, the term “fluid” refers to such material that is in the liquid and/or gaseous state or in the supercritical state at temperature 0° C. and pressure 1 bar. In particular, the term “fluid” relates to gaseous material at this temperature and pressure.
As indicated above, the inventors have found that lignin that has been treated by hydrothermal carbonization (hereinafter HTC-lignin) is capable of decreasing fluid permeability of many rubber-based materials. Reference is made to the section “Experimental” below. Because the results show this effect for a wide variety of rubber materials and a wide variety of HTC-content, the inventors consider that this effect is universal for a large variety of rubber materials.
As readable from above, the inventors have found that lignin that has been treated by hydrothermal carbonization (hereinafter HTC-lignin) is capable of decreasing fluid permeability of many rubber-based materials without compromising with other properties of the rubber-based material. In particular, the inventors have found that HTC-lignin is capable of decreasing air permeability of many rubber-based materials. In general, this may be due to structure of HTC-lignin, the structure being a polymer. Most likely the HTC-lignin forms, in the rubber matrix, a polymer network that resists fluid permeation. In contrast, traditional fillers do not form such a polymer network. Furthermore, HTC-lignin comprises relatively high amounts of functional groups. It seems that these functional groups may participate in chemical reactions and form chemical bonds with halogens of the rubber matrix so as to improve air tightness. At least halogenated butyl rubber comprises such halogen atoms, and as detailed below, their air tightness has been observed to be extremely good.
Therefore, the article 100, 200, 300, 400, 900 comprises first rubber-based material that is configured to restrict fluid permeability. In addition, the first rubber-based material comprises lignin that has been treated by hydrothermal carbonization (i.e. HTC-lignin). In particular, at least a part of the article comprises the first rubber-based material such that the first rubber-based material or a coating thereof forms at least a part of the first side 111, 211, 311, 411, 911. The article may comprise also a second rubber-based material. However, when considered feasible, the first rubber based material will be simply referred to as the rubber based material. The second rubber-based material, if present, need not comprise, but may comprise, HTC-lignin.
In general, the coating of the first rubber-based, if even present, is thin. A thickness of the coating may be e.g. at most 5 mm, at most 1 mm, or at most 500 μm. In some cases, the coating may be thicker. Examples will follow.
Because of the HTC-lignin, the fluid permeability of the article 100, 200, 300, 400, 900 is reduced. Moreover, the rubber-based material comprising the HTC-lignin has been applied at least close to that side of the article 100, 200, 300, 400, 900 that is exposed to a high pressure in use, i.e., close to the first side 111, 211, 311, 411, 911. Therefore, penetration of the fluid to the article and through the article is effectively prevented. Since the article may comprise the coating in between the first environment ENV1 and the first rubber-based material, the fluid may penetrate the coating. However, because the coating is thin, this does not affect the properties of the article.
Referring to
A tubeless pneumatic tyre 100 for a vehicle comprises multiple components shown by the references 121 to 135. The tyre 100 comprises a variety of materials, such as metal, textile and multiple types of rubber-based components. In general, a pneumatic tyre 100 may comprise one or more layers of reinforcing textile or textiles, such as polyester and/or nylon for a ply 128, as well as nylon belts 124, 125. The pneumatic tyre TYR1 may comprise one or more metal components for reinforcement purposes, such as resilient steel belts 126, 127 and bead cable 129. The reinforcing material (128, 124, 125) is arranged such that at least some of the rubber-based material that comprises lignin that has been treated by hydrothermal carbonization is arranged between the inner side of the pneumatic tyre and the reinforcing material. As the reinforcing material e.g. a fibrous material, a textile, or a metal may be used.
The exterior of the tyre is called a tyre carcass, referring to a thick profile surrounding the tyre. Tread area components of the tyre carcass provide an interface between the tyre 100 and the road (e.g. 900). In general, hard tread area components may provide less wear and reduce the rolling resistance of the tyre. Soft tread area components may provide better traction. The rubber-based components of the tread area may comprise components such as tread 121, tread base 122, undertread 123 and shoulder 135. The tread has a tread pattern affecting noise, handling, traction and/or wear of the tyre 100. The tread 121 may comprise additional structural elements, such as metal studs.
In addition to tread area components, the pneumatic tyre 100 comprises a sidewall 132. The sidewall is typically configured to withstand flexing and provide protection for the ply 128. A bead area of the tyre 100 may comprise, for example, a clinch 133, an apex 130 and bead base 134. Clinch 133 enables a proper seating of the bead base 134 to a rim flange, thereby enabling a tight sealing of the tyre with the wheelrim.
The pneumatic tyre 100 of
In
As depicted in
The innerliner 131 may comprise butyl rubber that comprises HTC-lignin. As will be detailed below, HTC-lignin has been observed to decrease air permeability of butyl rubber, the term “butyl rubber” including also halobutyl rubbers, significantly. Moreover, butyl rubbers also naturally have relatively low air permeability, which makes them suitable candidates for various applications (also other than tyres) requiring air tightness.
As indicated above, the material of the innerliner 131 can be called the first rubber-based material. The tread 121 may be optimized for other purposes than the innerliner 131. Such other purposes include traction (characterized by a coefficient of friction), avoiding noise (characterized by a noise production), avoiding wear (characterized by a wear resistance), enabling rolling (characterized by a rolling resistance), and strengthening (characterized e.g. by a modulus). Typically, such properties are best achieved with a different material composition than that of the innerliner 131. Thus, in an embodiment, the tread 121 comprises second rubber-based material, wherein the second rubber-based material is different from the first rubber-based material of the innerliner 131. However, the second rubber-based material may also comprise HTC-lignin but be different in some other way (e.g. amount of HTC-lignin, and/or type of the rubber-based matrix material). The second rubber-based material need not comprise HTC-lignin. The second material may be a rubber-based material comprising suitable filler, such as carbon black, silica, and/or HTC-lignin.
Referring now to
The self-sealant material 136 is typically uncured in order for the self-sealant to be able to penetrate and fix punctures of the tyre. As the function of self-sealant is to prevent gas leakage, the self-sealant material 136 may comprise the rubber-based material comprising HTC-lignin. In a tyre comprising both the innerliner 131 and self-sealant material 136, preferably at least one of them comprises rubber-based material comprising HTC-lignin. When both comprise rubber-based material comprising HTC lignin, they need not comprise the same material. In particular, the innerliner 131 may be cured, and the self-sealant 136 may be uncured. Clearly, the tread 121 may be comprise different material than the self-sealant 136 and different material than the innerliner 131. Thus, the material of the self-sealant may be referred to as a third material that is rubber-based.
Referring to
A pneumatic tire may be provided with noise cancelling foam (not shown). Noise cancelling foam, if used, is typically applied on some parts of the inner side of the pneumatic tire. A thickness of the noise cancelling foam is typically of the order of some centimetres, such as 2 cm to 4 cm. However, most often at least some parts of the inner surface are free from noise cancelling foam. Also in this case, the rubber-based material or a coating of the rubber-based material forms at least a part of the first side of the pneumatic tyre. In the alternative, the noise cancelling foam may be seen as a coating. If the foam would fully cover the inner side of the tyre, it would form the coating, and a thickness of the coating could be large (e.g. up to some centimetres).
Even if not shown in
A method for manufacturing a pneumatic tyre for a vehicle comprises manufacturing a preform of a pneumatic tyre, which is then cured. Curing the preform of a pneumatic tyre bonds the components together by means of curing. The preform of the pneumatic tyre is manufactured by arranging metal components and textile components to a carcass of a tire. The carcass of the tire is manufactured by arranging materials, i.e. at least a rubber-based component, onto a building drum to form a tubular preform and by expanding the tubular preform. When the tubular preform is expanded, the carcass of the pneumatic tyre is obtained. Reference is made, with respect to manufacturing a pneumatic tyre and its composition, to the publication “The Pneumatic Tyre” (publication by the U.S. Department of Transportation, National Highway Traffic Safety Administration, February 2006) in particular to Chapter 1, Section 5 (“An Overview of Tire Technology—Tire manufacturing”) and Chapter 2, Section 1 (“Mechanical Properties of Rubber—Elasticity and visco-elasticity”). Said sections describe common compositions and components of a pneumatic tyre as well as steps for assembling and curing a pneumatic tyre.
When manufacturing a pneumatic tyre for a vehicle configured to restrict gas permeability, the method comprises receiving rubber-based material that has been formed by mixing lignin that has been treated by hydrothermal carbonization and rubber-based matrix material for restricting gas permeability of the rubber-based material.
The rubber-based component, which is arranged onto the building drum, may comprise the rubber-based material that is for restricting gas permeability. Thus, the method may comprise arranging the rubber-based material onto the building drum before said expanding the tubular preform to form a carcass of the pneumatic tyre. For example, an innerliner may be so arranged. In the alternative, the innerliner may be applied onto the tire after the curing. In the alternative or in addition, the rubber-based material may be arranged onto an inner surface of the carcass. For example, a self-sealant may be so arranged. The self-sealant may be applied after the preform has been cured. The rubber-based material may be arranged onto an inner surface of the carcass during the curing.
If the preform of the tire comprises an innerliner, a surface of the innerliner may be provided with inside tire paint in order to ease the removal of the tyre preform from a mould, in which the preform is cured. The tire inside paint may serve as the coating of the rubber-based material.
The preform of the tire may be cured at a temperature of 150° C. to 200° C.
An embodiment comprises receiving or forming an innerliner comprising the rubber-based material. Then the innerliner may be arranged onto the building drum before said expanding the tubular preform to form a carcass of the pneumatic tyre. In the alternative, the innerliner may be arranged onto an inner surface of the carcass. The innerliner may be received in a finished and cured form, e.g. it may be bought. The material for the innerliner may be formed e.g. my mixing the HTC-lignin with the matrix material. The uncured material for the innerliner may be bought. Uncured innerliner material may be arranged on the building drum before said expanding or after the expanding but before curing the preform. The rubber-based material, e.g. an innerliner, may be arranged onto the building drum before said expanding such that the rubber-based material forms a radially innermost layer of the materials arranged on the building drum. Other material layers, e.g. plies of the carcass, may be arranged on the innerliner.
An embodiment comprises applying the rubber-based material onto the inner surface of the carcass after said curing for using the rubber-based material as a self-sealant. If another part of the tyre comprises the rubber-based material, a self-sealant that is not rubber-based and/or does not comprise HTC-lignin may be used.
What has been said about the rubber-based material in the context of the tire, in particular the rubber part of the material, applies in the context of the method, particularly to the rubber-based matrix material.
The rubber-based material may be received in a finished form (cured or uncured), e.g. it may be bought. The rubber-based material may be formed e.g. by mixing the HTC-lignin with the matrix material. Thus, an embodiment comprises providing the lignin that has been treated by hydrothermal carbonization and providing the rubber-based matrix material. Thereafter, the rubber-based material (e.g. an innerliner and/or a self-sealant) is formed by mixing the lignin that has been treated by hydrothermal carbonization with the rubber-based matrix material for restricting gas permeability of the rubber-based material.
In an embodiment, a specific surface area of the lignin that has been treated by hydrothermal carbonization and that is mixed with the rubber-matrix material is in the range of 7 m2/g to 150 m2/g, when measured according to ASTM D-6556-10. In an embodiment, an oil absorption number of the lignin that has been treated by hydrothermal carbonization and that is mixed with the rubber-matrix material is the range of 50 ml/100 g to 130 ml/100 g, when measured according to ASTM D2414-09. As an alternative to mixing, a finished rubber-based material may be received. These preferable properties of the HTC-lignin apply also in such a case.
Referring now to
In use, a first side 211 (i.e. an inner side) of the inner tyre 200 is exposed to a first environment ENV1 as depicted in
Even if not shown in
Even if not shown in
Even if this invention relates to a pneumatic tyre for a motor vehicle (and a method for manufacturing the same), it is noted that the same principles apply also in other applications.
The capability of the HTC-lignin to decrease fluid permeability applies also more generally, as will be detailed below in the context of
Referring more specifically to
Referring to
A tube 300 may be used for conveying e.g. water, air, liquid petroleum gas, or nitrogen. The outer side of the tube is typically exposed to regular atmosphere (i.e. air at the pressure of 1 atm), while other uses are also possible. A pressure difference between the first and second environments depends on the intended use. E.g. in water tubes, a pressure difference may be e.g. at least 1 bar. This applies also when pressurized air is being conveyed in the tube 300. E.g. in liquid petroleum gas tubes, a pressure difference of at least 15 mbar may be sufficient.
The article, such as the tube 300, may comprise reinforcing material 328 (
Referring to
In
A method for manufacturing the article that is not a pneumatic tyre for a motor vehicle comprises providing rubber-based material comprising lignin that has been treated by hydrothermal carbonization and rubber-based matrix material. Thereafter, the article is formed using the rubber-based material such that the article comprises the first side, the second side, and, optionally, the coating. For a more specific definition of these terms, reference is made to the article as such. As detailed in the context of the article as such, the rubber-based material or a coating of the rubber-based material forms at least a part of the first side.
The rubber-based material may have been cured, i.e. the article may be formed from cured rubber-based material e.g. by cutting and/or gluing. The rubber-based material may be provided in a form of an uncured mixture of the HTC-lignin and the matrix material. The rubber-based material may be provided by mixing HTC-lignin and the matrix material. In the latter two cases, the method comprises curing the rubber-based material.
If the method comprises curing the rubber-based material, the rubber-based material at a temperature of 150 to 200° C.
What has been said about the composition of the rubber-based material, in particular the rubber part thereof, applies to the rubber-based matrix material.
As indicated above, the rubber-based material may be manufactured. Thus, an embodiment comprises providing lignin that has been treated by hydrothermal carbonization and rubber-based matrix material. Thereafter, the embodiment comprises mixing the lignin that has been treated by hydrothermal carbonization with the rubber-based matrix material to form a rubber-based material for restricting fluid permeability of the rubber-based material. As detailed above, thereafter the rubber-based material is cured.
In an embodiment, a specific surface area of the lignin that has been treated by hydrothermal carbonization and that is mixed with the rubber-matrix material is in the range of 7 m2/g to 150 m2/g, when measured according to ASTM D-6556-10. In an embodiment, an oil absorption number of the lignin that has been treated by hydrothermal carbonization and that is mixed with the rubber-matrix material is the range of 50 ml/100 g to 130 ml/100 g, when measured according to ASTM D2414-09. As an alternative to mixing, rubber-based material may be received in the cured or uncured form. These preferable properties of the HTC-lignin apply also in such a case.
An embodiment comprises providing the rubber-based material with a coating such that the coating forms at least a part of the first side of the article. What has been said about the thickness of the coating in the context of the article, applies.
As indicated above, the HTC-lignin improves fluid tightness of the articles including pneumatic tyres. This property may be important for a person seeking such articles or tyres. Therefore, it is beneficial to provide the person with information indicative of the article (100, 200, 300, 400, 900) having reduced fluid permeability or reduced gas permeability. Referring to
The information carrier 510 needs not carry information that is indicative of the article 100 having low fluid permeability. Referring to
As a third alternative, the database 520 may comprise information indicative of the article having a low fluid permeability. Thus, the information carrier 510 is not needed. Thus, the information on reduced fluid permeability of the article can be found from the database e.g. by using a color and shape of the article.
The information carrier 510 may be e.g. a marking (e.g. text, a barcode or a 2D barcode, such as QR-code), an RFID circuit, or an electric circuit. The database 520 (if any) may be comprised by the article, or the database may be located in a different place.
Thus, in an embodiment, the pneumatic tyre (100, 200) or the other article (300, 400, 900) comprises
An embodiment of an arrangement 500 comprises the article (100, 200, 300, 400, 900), and the arrangement 500 comprises
In the context of tyres, the first information and/or the second information, in combination, may be indicative of the pneumatic tyre (100, 200) having low gas permeability.
As for the term “lignin that has been treated by hydrothermal carbonization” (i.e. HTC-lignin), this involves two aspects: lignin and hydrothermal carbonization.
Concerning the former (i.e. lignin), lignin is renewable and environmentally sustainable raw material that is comprised by many plants, including trees, which further to lignin comprise cellulose and hemicellulose. Black liquor is an example of a material that comprises lignin but is substantially free from cellulose and hemicellulose. Black liquor is a major by-product of pulp and paper industry. Paper is manufactured from softwood and hardwood, which contain significant amounts of lignin; and the process of papermaking separates cellulose and hemicellulose from the wood, while the lignin dissolves in the chemicals thereby forming spent liquor. A typical example of lignin containing material is spent liquor from biomass fractionation, such as pulp mill black liquor.
The term “black liquor” refers to spent liquor of a Kraft pulp process, i.e. a sulphate process. Spent liquor of a sulphite process also comprises lignin, but that liquor is commonly called “brown liquor”. However, the sulphite process does not dissolve lignin to the same extent as the sulphate process. Lignin can be extracted from the liquor e.g. by precipitation. Hereinabove the term “lignin” in the term HTC-lignin refers to lignin that has been extracted from biomass-based material. More preferably, the term “lignin” in the term HTC-lignin refers to lignin that has been extracted, e.g. precipitated, from a spent liquor of a Kraft process or a sulphite pulp process. Lignin needs not be pure lignin. However, typically extraction of lignin includes washing steps of precipitated lignin. Lignin in native form has very high molecular weight. The molecular structure of lignin comprises phenylpropane (C9) units, which are connected to each other, typically via carbon-carbon (C—C) and/or ether (C—O—C) linkages.
Lignin in general contains relatively high amounts of functional groups. Lignin contains functional groups, which may participate in chemical reactions and form chemical bonds. Functional groups typically present in lignin comprise, for example, carbonyl groups, aliphatic hydroxyl groups and phenolic hydroxyl groups. Functional groups of lignin are detectable even after a chemical pulping process, in black liquor. The further processing of lignin containing material, particularly of lignin originating from wood, therefore is environmental and cost-effective way of providing lignin derivatives with functional properties. As indicated above, at least some of the functional group of lignin remain in the HTC-lignin.
Concerning the latter (i.e. hydrothermal carbonization), a hydrothermal carbonization treatment (i.e. a HTC treatment) of lignin refers to a thermochemical conversion process of lignin in an aqueous suspension. Hydrothermal carbonization treatment of lignin produces lignin derivatives having high carbon content and functional groups. In particular, the hydrothermal carbonization treatment (i.e. a HTC treatment) of lignin refers to a thermochemical conversion process of the lignin as defined above in an aqueous suspension at elevated pressure and temperature, typically in a reactor suitable for the purpose. In the treatment, a pressure in the reactor may be in the range of 10 to 40 bar, preferably equal to or higher than 15 bar. A temperature in the reactor may be from 150° C. to 300° C., such as in the range of 150° C. to 250° C. The temperature equals the temperature of the aqueous lignin suspension inside the reactor during the hydrothermal carbonization treatment (i.e. HTC treatment). The hydrothermal carbonization may further comprise at least partial refining of the carbonized lignin. Typically, the carbonized lignin may be at least partially charred. Hydrothermal carbonization treatment of lignin has the effect of increasing the carbon content of lignin containing material. HTC lignin has a high carbon content, typically 40 wt. % or more, such as in the range of 40 to 65 wt. %, or even higher.
As discussed above, it has now been found that lignin that has been treated by hydrothermal carbonization (i.e. HTC-lignin) improves fluid tightness (i.e. reduces fluid permeability) of a rubber-based matrix material. To this end, the HTC-lignin may be mixed with rubber-based matrix material to form a mixture, the mixture being hereinabove and hereinbelow referred to as the “rubber-based material”, which thus comprises at least HTC-lignin. As it comprises HTC—lignin, the rubber-based material is configured to restrict fluid permeability. In particular, the rubber-based material is applied in such a part of the article 100, 200, 300, 400, 900 that in the article 100, 200, 300, 400, 900, the rubber-based material is configured to restrict fluid permeability. In addition to the HTC-lignin, some filler material may be added to the rubber-based matrix material. Such fillers include carbon black and silica.
After mixing, the rubber-based material may be subjected to curing (i.e. hardening). Thus, after curing, the rubber-based material may cured, at least to some extent. However, in certain applications, such as when used as self-sealant, the rubber-based material need not be cured. Moreover, the curing may be done only partially, whereby the rubber-based material may be only partially cured. However, in an embodiment, the rubber-based material of the article 100, 200, 300, 400, 900 has been cured. Curing may be a vulcanization process, wherein the uncured material is heated in a temperature typically less than 200° C., such as in the range of 150 to 200° C. During the curing reaction rubber-based components undergo cross-linking reactions. The formed cross-linked structure bonds the tyre components firmly together. The duration of the curing may vary depending on the side of the article. Passenger car tyres are typically cured from few minutes up to half an hour, while curing of heavy tyres may take several hours.
As indicated above, the hydrothermal carbonization treatment of lignin has the effect of fragmenting the lignin molecular structure. Moreover, it has been observed that the HTC-lignin has the effect of reducing air permeability of rubber. Examples showing this for a wide range of rubber material will be given below. The specific surface area of HTC-lignin may be in the range of 7 m2/g to 150 m2/g, when measured according to ASTM D-6556-10. More specifically, these values relate to the specific surface area of the material after the hydrothermal carbonization treatment of lignin and before the HTC-lignin is mixed with the rubber-based matrix material. Another property of the HTC-lignin that may affect binding with the matrix rubber material, and in this way also air tightness, is an oil absorption number. In an embodiment, an oil absorption number of HTC lignin is the range of 50 ml/100 g to 130 ml/100 g, when measured according to ASTM D2414-09. More specifically, these values relate to the specific surface area of the material after the hydrothermal carbonization treatment of lignin and before the HTC-lignin is mixed with matrix rubber.
The rubber-based matrix material may be one of, or comprise at least one of: natural rubber, styrene-butadiene rubber, nitrile-butadiene tuber, nitrile rubber, chloroprene rubber, ethylene propylene diene rubber, and butyl rubber, such as halobutyl rubber. Thus, in an embodiment, the rubber-based material comprises, in addition to the HTC lignin, at least one of: natural rubber, styrene-butadiene rubber, nitrile-butadiene tuber, nitrile rubber, chloroprene rubber, ethylene propylene diene rubber, and butyl rubber, such as halobutyl rubber.
As detailed below, the HTC-lignin functions particularly well with Nitrile Butadiene Rubber (NBR), Chloroprene Rubber (CR), Ethylene Propylene Diene Monomer rubber (EPDM), Natural Rubber (NR), and Butyl Rubber (BR), in particular bromobutyl rubber (BIIR).
Thus, preferably, the rubber-based material comprises HTC-lignin and at least one of Nitrile Butadiene Rubber (NBR), Chloroprene Rubber (CR), Ethylene Propylene Diene Monomer rubber (EPDM), Natural Rubber (NR), and Butyl Rubber (BR).
When the HTC-lignin is applied to an innerliner of a pneumatic tyre, the innerliner preferably comprises butyl rubber (optionally at least partly halogenated). The innerliner may further comprise natural rubber.
Butyl rubber may be halogenated or non-halogenated. Herein the term “halobutyl rubber” refers to halogenated butyl rubber. When partially halogenated, the butyl rubber comprises both a halogenated butyl rubber compound and a non-halogenated butyl rubber compound. Examples of halobutyl rubber include chlorobutyl rubber and bromobutyl rubber.
Preferably, an inneliner of a pneumatic tyre comprises at least partly halogenated butyl rubber, such as bromobutyl rubber, and HTC-lignin.
The rubber matrix material for other applications may be selected according to needs.
After the initial observation that HTC-lignin decreases air permeability in certain rubber materials, a series of tests were conducted. To this end, the effect of replacing a part or all of a conventional filler material (Carbon black N550) with HTC-lignin on air permeability of four rubber materials (A, B, C, D) suitable for various rubber articles, was tested. The materials were A: Nitrile Butadiene Rubber (NBR), B: Chloroprene Rubber (CR), C: Ethylene Propylene Diene Monomer rubber (EPDM), and D: Natural Rubber (NR); reference is made to Tables 1a, 1b, 2a, and 2b These materials are typically not used as rubber material for an innerliner of a pneumatic tyre. In contrast, these samples represent general technical rubber goods. However, butyl rubber, in particular halobutyl rubber, such as bromobutyl rubber, which is shown in Tables 3 and 4, can be used as material for general technical rubber goods. Thus, even if BIIR is shown as an example of tyre material, the same material can be used for other purposes as well.
As a reference for the materials A, B, C, and D, only carbon black N550 was used as filler. The samples contained 60 phr filler. These references are shown below in Tables 1a and 1b Aa, Ba, Ca, and Da, respectively. To test the effect of HTC-lignin either ⅔ (i.e. 40 phr) or all of the filler material was replaced with HTC lignin. The former are shown below by the references Ab, Bb, Cb, and Db, respectively. The latter are shown below by references Ac, Bc, Cc, and Dc, respectively.
The terms in tables 1a and 1b are as follows:
The rubber compositions A, B, C, D (all versions a, b, and c) were mixed using a Brabender mixer. The formed rubber compositions were thereafter vulcanized. Vulcanization temperature was 160° C. for compositions A, B, C (all versions a, b, and c) and 150° C. for composition D (all versions a, b, and c).
After manufacturing the samples of Tables 1a and 1b, their air permeability was tested according to the standard ASTM D 3985-2017. The instrument Mocon OX-TRAN 2/61 was used for the purpose. Test temperature was 23° C. The results are shown in Tables 2a and 2b.
Tables 2a and 2b show the air permeability in units of cc·mm/(m2·day). Herein the unit cc refers to cubic centimetre at measurement conditions, i.e. temperature 23° C. and pressure 1 atm, which at the time of measurement was 760 mmHg. Furthermore, the tables show the decrement (in percentages) of the air permeability of the sample, as compared to the reference sample without any HTC-lignin. Thus, the “A” samples are compared to the sample “Aa”, the “B” samples to “Ba”, etc.
As shown by the results, replacing some or all of the carbon black of the rubber decreases air permeability in all these cases. Replacing all of the carbon black of the rubber implies that rubber-based material that is configured to restrict gas permeability does not comprise carbon black. However, it has been found that small amounts of carbon black do not significantly affect the gas permeability of the rubber material. Thus, in an embodiment, the rubber-based material that is configured to restrict gas permeability comprises less than 10 wt % carbon black, preferably less than 5 wt % carbon black, and more preferably less than 1 wt % carbon black. The rubber-based material that is configured to restrict gas permeability can be comprised by (i) the innerliner, (ii) a self-sealant of the tire, or (iii) both the innerliner and the self-sealant of the tire.
Replacing 2/3 of the carbon black with HTC-lignin implies a HTC-lignin content of 22 w % (see Tables 1a and 1b). Replacing all of the carbon black with HTC-lignin implies a HTC-lignin content of 34 w % (see Tables 1a and 1b). Thus, it seems that in order to improve the air tightness, the HTC-lignin content may be e.g. up to 40 w %, such as up to 35 w %, or up to 34 wt %. As for the effect at a lower end, the authors are confident that improved air tightness (reduced permeability) are observable at a HTC-lignin content of at least 8 w %, such as at least 10 w %. Thus, it sees that a suitable range for the content of HTC-lignin with these rubbers is from 8 w % to 40 w %, such as from 10 w % to 35 w %. It may be that already a lower HTC-lignin content, such as at least 3 w %, improves air tightness. As indicated in Tables 1a, 1b, 2a, and 2b, when the content of HTC-lignin is at least 22 wt %, the gas permeability is reduced. Thus, in an embodiment, the rubber-based material that is configured to restrict gas permeability comprises at least 22 wt % HTC-lignin. As indicated in Tables 1a, 1b, 2a, and 2b, at least the range 22 wt % to 34 wt % improves gas tightness.
Thus, in an embodiment, the rubber-based material that is configured to restrict gas permeability comprises 22 wt % to 34 wt % HTC-lignin. However, it seems that the content of HTC-lignin may be up to 40 wt %. Thus, in an embodiment, the rubber-based material that is configured to restrict gas permeability comprises 22 wt % to 40 wt % HTC-lignin.
In an embodiment, in an embodiment, the rubber-based material that is configured to restrict gas permeability comprises at least 22 wt %, such as 22 wt % to 40 wt %, such as 22 wt % to 34 wt %, HTC-lignin and comprises at most 5 wt % carbon black. If needed, another filler, such as silica, can be used to increase the overall filler content.
Furthermore, as indicated in Tables 1a, 1b, 2a, and 2b, in an embodiment, the rubber-based material that is configured to restrict gas permeability comprises at least one of magnesium oxide (MgO) and zinc oxide (ZnO).
As shown in Tables 2a and 2b, by replacing carbon black with HTC-lignin, the air permeability decreased up to 43% (sample Bc compared to Ba; chloroprene rubber). Very good results were obtained also for nitrile butadiene rubber (material A), wherein the air permeability decreased by 38%. As also readable from table 1a, the air permeability of nitrile butadiene rubber (material A) and chloroprene rubber (material B) even without the HTC-lignin is below 200 cc·mm/(m2·day). A piece of material having an absolute air permeability below 200 cc/(m2·day) is reasonably commonly considered as a level required for materials referred to as “air tight”. In these experiments, a thickness of the sample was 2 mm (2±0.2 mm). As also readable from tables 1a and 1b, the air permeability precisely these materials could be lowered a lot by using HTC-lignin. Thus, particularly these materials seem attractive for applications requiring air tightness of the material.
As indicated above, the materials A-D represent materials of general technical rubber goods. To test the effect of HTC-lignin in conventional tyre innerliner rubber, similar test were carried out for bromobutyl rubber (BIIR), hereinafter denoted by material E. A filler used in the BIIR was Carbon black N660. In the experiments, a part or all of the carbon black was replaced by HTC-lignin. The samples contained 60 phr filler. A reference sample is shown below in Table 3 as Ea, and it contains only carbon black as filler. To test the effect of HTC-lignin, 5 phr, 40 phr, or all of the filler material was replaced with HTC lignin. These are shown in Table 3 as Es, Eb, and Ec, respectively.
The acronyms in table 3 are as follows:
As readable from Tables 3 and 1, the effect of a small amount of HTC-lignin for only BIIR is shown. Unfortunately, for reasons of shortage of HTC-lignin, extensive tests could not be performed.
The rubber compositions E (all versions a, b, and c) were mixed using a Brabender mixer. The formed rubber composition were thereafter vulcanized. Vulcanization temperature was 180° C.
After manufacturing the samples of Table 3, their air permeability was tested according to the standard ASTM D 3985-2017. The instrument Mocon OX-TRAN 2/61 was used for the purpose. Test temperature was 23° C. The results are shown in Table 4.
As shown by the results, replacing some or all of the carbon black of the rubber decreases air permeability of also bromobutyl rubber. Replacing 5 phr of the carbon black with HTC-lignin implies a HTC-lignin content of 3 w % (see Table 3) Replacing all of the carbon black with HTC-lignin implies a HTC-lignin content of 34 w % (see Table 3). Thus, it seems that in order to improve the air tightness, the HTC-lignin content may be e.g. up to 40 w %, such as up to w %, or up to 34 wt %. As for the effect at a lower end, for bromobutyl rubber it seems that beneficial effects are seen already for a very low content of HTC-lignin, such as 3 w %. Thus, it seems that a suitable range for the content of HTC-lignin with butyl rubber (in particular halobutyl rubber, such as bromobutyl rubber) is from 3 w % to 40 w %, such as from 8 w % to 35 w %.
As indicated in Tables 3 and 5, when the content of HTC-lignin is at least 22 wt %, the air tightness of Bromobutyl rubber is significantly improved. Thus, in an embodiment, the rubber-based material that is configured to restrict gas permeability comprises at least 22 wt % HTC-lignin and butyl rubber, e.g. halobutyl rubber, e.g. bromobutyl rubber. As indicated in Tables 3 and 5, at least the range 22 wt % to 34 wt % of HTC-lignin improves gas tightness. Thus, in an embodiment, the rubber-based material that is configured to restrict gas permeability comprises 22 wt % to 34 wt % HTC-lignin and comprises butyl rubber, e.g. halobutyl rubber, e.g. bromobutyl rubber. However, it seems that the content of HTC-lignin may be up to 40 wt %. Thus, in an embodiment, the rubber-based material that is configured to restrict gas permeability comprises 22 wt % to 40 wt % HTC-lignin and comprises butyl rubber, e.g. halobutyl rubber, e.g. bromobutyl rubber. The rubber-based material that is configured to restrict gas permeability can be comprised by (i) the innerliner, (ii) a self-sealant of the tire, or (iii) both the innerliner and the self-sealant of the tire.
In an embodiment, the rubber-based material that is configured to restrict gas permeability comprises at least 22 wt %, such as 22 wt % to 40 wt %, such as 22 wt % to 34 wt %, HTC-lignin and comprises at most 5 wt % carbon black. In an embodiment, the rubber-based material that is configured to restrict gas permeability comprises at least 22 wt %, such as 22 wt % to 40 wt %, such as 22 wt % to 34 wt %, HTC-lignin and comprises at most 5 wt % carbon black, and comprises butyl rubber, such as halobutyl rubber, such as bromobutyl rubber. If needed, another filler, such as silica, can be used to increase the overall filler content.
Furthermore, as indicated in Tables 3 and 5, in an embodiment, the rubber-based material that is configured to restrict gas permeability comprises at least one of magnesium oxide (MgO) and zinc oxide (ZnO), preferably both magnesium oxide (MgO) and zinc oxide (ZnO). In an embodiment, the rubber-based material that is configured to restrict gas permeability comprises comprises butyl rubber (e.g. halobutyl rubber, e.g. bromobutyl rubber) and at least one of magnesium oxide (MgO) and zinc oxide (ZnO). In an embodiment, the rubber-based material that is configured to restrict gas permeability comprises butyl rubber (e.g. halobutyl rubber, e.g. bromobutyl rubber), magnesium oxide (MgO), and zinc oxide (ZnO).
As shown in Table 4, by replacing carbon black with HTC-lignin, the air permeability decreased up to 72%. Moreover, the air permeability of BIIR is low even without using HTC-lignin, which is a reason, by BIIR is commonly used for tyre innerliner material.
While preparing the samples, the inventors also noted that characteristic values of the mixing process do not significantly change. Table 5 shows four characteristic mixing values for the bromobutyl rubber shown in Table 3.
The values of Table 5 are measured according to the standard ASTM D5289, they indicate vulcanization rate and ratio.
The values given in Table 5 are:
As seen from table 5, the forces needed to cure the mixture, as indicated by the value Fmax, remain at the same level even if some of the carbon black is replaced by HTC-lignin. This implies that the rubber vulcanizes to substantially the same level irrespective of the amount of HTC-lignin. This indicates that some elastic properties of the cured rubber do not change by replacing the filler material with HTC-lignin. However, a longer time for vulcanization may be required, as indicated by the time T 90. A longer T 90 time may be due to the functional groups of the lignin which stabilized radicals and that way slow down vulcanization reactions.
Particularly in applications, where rubber-material is used for improving air tightness, such as in tyres, application of HTC-lignin may involve significant savings. For example, if a purpose of an innerliner is to achieve a certain level of air tightness, the same level can be obtained by using HTC-lignin as a filler material, and, at the same time, decreasing the thickness of the innerliner. In this way, less innerliner material is needed in the tyres. Moreover, replacing carbon black with HTC-lignin does not increases costs, because of the market price of HTC-lignin. Finally, HTC-lignin is a renewable material, and replacing some fossil filler material with HTC-lignin is beneficial for environmental reasons, too.
The following examples illustrate a method for manufacturing a pneumatic tire.
101. A method for manufacturing a pneumatic tyre for a motor vehicle, the method comprising
102. The method of example 101 comprising
103. The method of example 101 or 102, comprising
104. The method of any of the examples 101 to 103, comprising
105. The method of any of the example 101 to 104, wherein
106. The method of example 105, wherein
107. The method of any of the examples 101 to 105, wherein
108. The method of example 107, wherein
109. The method of any of the examples 101 to 108, comprising
110. The method of any of the examples 101 to 109, comprising
111. The method of any of the examples 101 to 110, wherein
112. The method of any of the examples 101 to 111, wherein
113. The method of any of the examples 101 to 112, comprising
The following examples illustrate manufacturing an article other than a pneumatic tire.
201. A method for manufacturing an article that is not pneumatic tyre for a motor vehicle and that is suitable for use as at least a part of a pressurizable container or pipeline, the method comprising
202. The method of example 201 comprising
203. The method of the example 201 or 202, wherein
204. The method of any of the examples 201 to 203, wherein
205. The method of example 204, wherein
206. The method of any of the examples 201 to 204, wherein
207. The method of example 206, wherein
208. The method of any of the examples 201 to 207, comprising
209. The method of any of the examples 201 to 208, wherein
210. The method of any of the examples 201 to 209, wherein
211. The method of any of the examples 201 to 210, comprising
212. The method of any of the examples 201 to 211, comprising
The following examples illustrate uses of HTC-lignin for reducing fluid permeability in an article other than a pneumatic tyre for a motor vehicle:
1. An article that is not pneumatic tyre for a motor vehicle and that is suitable for use as at least a part of a pressurizable container or pipeline, the article comprising
2. The article of example 1, wherein
3. The article of example 1 or 2,
4. The article of any of the examples 1 to 3, wherein
5. The article of any of the examples 1 to 4, wherein
6. The article of any of the examples 1 to 5, wherein
7. The article of any of the examples 1 to 6, wherein
8. The article of any of the examples 1 to 7, comprising
9. The article of any of the examples 1 to 8, comprising
10. The article of any of the examples 1 to 9, wherein
11. The article of any of the examples 1 to 10, comprising
12. An arrangement, comprising
13. Use of the article of any of the examples 1 to 11, wherein
14. The use of example 13, wherein
15. The use of the example 13 or 14, wherein
16. The use of any of the examples 13 to 15, wherein
17. Use of lignin that has been treated by hydrothermal carbonization as a part of a rubber-based material for the purpose of restricting fluid permeability, such as for the purpose of restricting gas permeability, of an article that is not pneumatic tyre for a motor vehicle.
Number | Date | Country | Kind |
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21397503.0 | Mar 2021 | EP | regional |
Filing Document | Filing Date | Country | Kind |
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PCT/FI2022/050135 | 3/2/2022 | WO |