• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
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    • 专利摘要:
    ADJUSTABLE MATERIALS. Disclosed in the field of materials are one or more techniques for a method for functionalized graphitic material comprising the steps to: 1) provide a graphitic material; 2) providing a first molecule comprising a first group, a spacer, and a second group; 3) providing a second molecule comprising a third group, a spacer and a fourth group, wherein said third group is a group other than said first group; and 4) attaching the first and second molecules to the graphite material. Also described is an adjustable material composition comprising the functionalized carbon nanotubes or functionalized graphene prepared by the methods described herein.
    公开号:BR112014032285B1
    申请号:R112014032285-6
    申请日:2013-04-30
    公开日:2021-04-20
    发明作者:Jorma Virtanen
    申请人:Tesla Nanocoatings, Inc.；
    IPC主号:
    专利说明:

    [0001] This request claims priority with US Serial No. 61/850,561, entitled ADJUSTABLE MATERIALS, submitted on February 20, 2013 and Serial No. in Finland 201201980993, entitled ADJUSTABLE MATERIALS, submitted on June 21, 2012, incorporated herein by reference. BACKGROUND
    [0002] The compounds can be manufactured with thermosetting plastics such as epoxy, polyurethanes and silicones. Epoxies can be produced by reacting an epoxy resin and a hardener. Polyurethane polymers can be formed by reacting an isocyanate with a polyol. Silicones can comprise siloxanes polymerized with organic side groups.
    [0003] Carbon nanotubes (CNT) and graphene are used to reinforce thermosetting plastics such as epoxies, polyurethanes, silicones and other resins and polymers. CNTs, functionalized CNTs (or hybrid CNTs, denoted HNTs), graphene, and functionalized graphene may collectively be referred to as hybrid graphite materials (HGMs). These HGMs can be incorporated into any of the epoxy components, such as the epoxy resin and hardener. HGMs can also be incorporated into polyurethanes and silicones.
    [0004] Thermosetting plastics, carbon nanotubes, graphene and HNTs can increase modulus and strength, but elasticity may be preferred for certain plastic compounds. In order to increase elasticity, siloxane can be added. The siloxane backbone can be coiled and covered with alkyl or aryl groups in silicones. Thus, silicones can be very flexible and hydrophobic. Hydrophobicity can be increased by functionalization with groups such as fluorinated alkyl or aryl groups.
    [0005] Several functionalization methods for carbon nanotubes have been developed. They include nitric acid/sulfuric acid oxidation of CNTs, addition of aryl radicals to CNTs, a ball mill induces the addition of amines and sulfides to CNTs, activated butyllithium combines with alkyl halides, and from the assisted addition of ultrasonic vibration of various reagents, including amines and epoxies. Improving mechanochemical reactions, such as mechanical cutting or ultrasound, can induce chemical reactions in CNTs.
    [0006] An anti-corrosive coating may contain sacrificial metal particles such as zinc particles. The concentration of particles can exceed the percolation limit, which is about 30% for spherical particles. The high concentration of these particles can reduce coating integrity, especially if the particles are not chemically bonded with the polymer. Anti-corrosive coatings can use sacrificial metal particles that are electrically connected to a metal surface coated with a CNT or graphene mesh. Using CNT or graphene mesh may require fewer sacrificial metal particles within an anti-corrosive coating. Furthermore, the graphite material can be coated with a layer of metal. The metal layer can be made up of microparticles or nanoparticles. Metal particles can be coated with a thin layer of oxide unless the graphite material is coated in the absence of oxygen. With nanoparticles, the oxide layer can be a relatively large part of the particle. The oxide layer can also be a large portion of the metal coating around the CNT. In addition to being metallic, the particles can also be ceramic. ABSTRACT
    [0007] This summary is provided to introduce a variety of concepts in a simplified form that are further described below in the Detailed Description. This summary is not intended to identify key elements or essential features of the subject matter claimed, nor is it intended to be used to limit the scope of the subject matter claimed.
    [0008] In one form of implementation, a method of modifying a graphite material that includes the steps to: 1) provide a graphite material; 2) providing a first molecule comprising a first group, a spacer, and a second group; 3) providing a second molecule comprising a third group, a spacer and a fourth group, wherein said third group is a group other than said first group; and 4) attaching the first and second molecules to the graphite material.
    [0009] For the realization of the above and its related purposes, the following description and attached drawings define certain illustrative aspects and implementations. They are indicative of just a few of the many ways in which one or more aspects may be employed. Other aspects, advantages and new features of the present description will become apparent from the following detailed description when considered in conjunction with the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS
    [0010] The subject described herein may take physical form in certain parts and arrangement of parts, being described in detail in this specification and illustrated in the accompanying drawings which form part of the invention, and in which:
    [0011] FIGURE 1 is a plan view of the process described herein.
    [0012] FIGURE 2 schematically illustrates what is described herein.
    [0013] FIGURE 3 schematically illustrates what is described herein.
    [0014] FIGURE 4 schematically illustrates what is described herein.
    [0015] FIGURE 5 schematically illustrates what is described herein.
    [0016] FIGURE 6 schematically illustrates what is described herein.
    [0017] FIGURE 7 schematically illustrates what is described herein.
    [0018] FIGURE 8 schematically illustrates what is described herein.
    [0019] FIGURE 9 schematically illustrates what is described herein.
    [0020] FIGURE 10 schematically illustrates what is described herein. DETAILED DESCRIPTION
    [0021] The claimed subject matter will now be described with reference to the drawings, for which like reference numerals are generally used to refer to like elements. In the following description, for purposes of explanation, several specific details are presented in order to provide a thorough understanding of the claimed subject matter. It may be evident, however, that the claimed subject matter can be practiced without these specific details. In other cases, structures and devices are shown in block diagram form in order to facilitate the description of the claimed object.
    [0022] The word "exemplary" is used herein to mean that it serves as an example, case or illustration. Any aspect or design described herein as "exemplary" is not necessarily to be construed as advantageous over other features or designs. On the contrary, the use of the word exemplar is intended to present concepts in a concrete way. As used in this application, the term "or" is intended to mean an inclusive "or" rather than an exclusive. That is, unless otherwise specified, or clear from the context, "X employs A or B" is understood to mean any of the natural inclusive alternatives. That is, if X employs A; X employs B; or X employs both A and B, so "X employs A or B" satisfies either of the above instances. Furthermore, at least one of A and B and/or the like generally means A or B or A and B. Furthermore, the articles "a" and "an" as used in this application and in the appended claims may generally be interpreted to mean "one or more", unless otherwise specified or clear from the context to be singular form.
    [0023] Although the object has been described in language specific to the structural features and/or methodological acts, it should be understood that the matter defined in the appended claims is not necessarily limited to the specific characteristics or acts described above. Instead, the characteristics and specific acts described above are disclosed as an example of the ways of implementing the claims. Naturally, those skilled in the art will recognize that many modifications can be made to this configuration without departing from the scope or spirit of the claimed subject matter.
    [0024] Furthermore, although the subject matter has been shown and described, with respect to one or more implementations, equivalent changes and modifications will occur to others skilled in the art, based on a reading and understanding of this specification and the accompanying drawings. The disclosure includes all such modifications and changes and is only limited by the scope of the following claims. In particular with respect to the different functions performed by the components described above (eg elements, resources, etc.), the terms used to describe these components are intended to correspond, unless otherwise indicated, to any component that performs the specified function of the described component (e.g., which is functionally equivalent), though not structurally equivalent to the described structure, which performs the function in the exemplary implementations illustrated herein of the disclosure.
    [0025] Furthermore, while a particular feature of the disclosure may have been disclosed with respect to only one of several implementations, such feature may be combined with one or more other features of the other implementations as desired and advantageous for any particular or specific application. In addition, to the extent that the terms "comprises", "having", "has", "with", or its variants are used, either in the detailed description or in the claims, the terms are intended to be inclusive in a manner similar to the term "understanding".
    [0026] Both carbon nanotubes (also referred to as CNTs) and graphene are graphite materials. They are substances composed essentially of pure carbon. The edges of CNTs and graphene can have other elements, such as hydrogen and oxygen. Graphene can have atoms arranged in a regular hexangular pattern, similar to graphite, but a fixed bed of one atom. Graphene can be made up of carbon atoms, where each carbon atom is bonded with three other carbon atoms. The carbon atom can form four covalent bonds, where each carbon has both a single and a double bond. These covalent bonds can provide strength within the graphene material. It can be very light in weight, but it can provide strength as a material. Even with small amounts of graphite materials added to a composite, the composite's tensile strength can be increased. In addition to strength, graphite materials are also known for their electronic conductance.
    [0027] Generally, graphite materials can be smooth and regular in shape, but can easily slip into the nanocompound. Sliding may be prevented by functionalized graphite materials. Proper functionalization can allow the formation of covalent, coordination or formation or ionic bonds between the functionalized graphite material, various particles, polymers and the surface to be protected by the coating.
    [0028] Graphene can be manufactured in two different ways, either from smaller building blocks (bottom to top) or by exfoliating graphite (top to bottom). The bottom-up method allows for the fabrication of continuous graphene layers on a substrate. It is the ideal method for manufacturing transistors and electronic circuits. For the manufacture of large-scale materials, graphite exfoliation may be a more suitable approach. Exfoliation can be done by separating the graphene layers by intercalating hydrogen or other atoms or ions in graphite or by ultrasonic vibration. The edge of the graphene layer contains other carbon atoms, for example hydrogen or oxygen. The edge can be deliberately functionalized by any functional group.
    [0029] Carbon nanotubes are also a graphite material, but with a cylindrical structure. Each CNT is a molecule with a certain structure, which may or may not be exactly known. Carbon nanotubes can be durable and resist nanocracking due to thermal expansion and other contraction cycles when used in compositions or coatings. Carbon nanotubes can have a high tensile strength compared to many other materials. They can also increase the tensile strength of compounds even when they are added to compounds in small amounts. Furthermore, carbon nanotubes can have a longer persistence length. The persistence length is a measure of the mechanical property to quantify the stiffness of a polymer. Most polymers can have a persistence length of about 1 nm to 2 nm. However, multiwalled carbon nanotubes (NTCM) can have a persistence length of more than about 100 nm. Single-walled carbon nanotubes (SWNTs) and double-walled carbon nanotubes (DWNTs) may also have increased persistence length. Both the high tensile strength and the persistence length can allow graphite materials to provide a tensile strength of nanocompounds, especially if they can be chemically bonded with a polymer or particles that may form part of the composition described herein.
    [0030] Functionalized CNTs can be fundamentally different from CNTs that can be used as starting material. Functionalized CNTs can also be different from CNTs that have not been functionalized. Functionalized CNTs can be molecules that may have different chemical structures, chemical and physical properties than CNTs. For comparison, cellulose and functionalized celluloses, such as carboxymethyl cellulose (CMC), may have different properties. CMC can be chemically derived from cellulose, but it may not function like cellulose. CMC has totally different chemical and physical properties.
    [0031] FIGURE 1 shows a process for modifying graphite material, comprising the steps of: 1) providing a graphite material; 2) providing a first molecule comprising a first group, a spacer, and a second group; 3) providing a second molecule comprising a third group, a spacer and a fourth group, wherein said third group is a group other than said first group; and 4) attaching the first and second molecules to the graphite material. Within the process, the first group can comprise at least one hydroxyl, thiol, amino, epoxy, carboxyl and silyl group, and the second group can comprise at least one amino, epoxy, hydroxyl, carboxyl, silyl and thiol group. Also within the scope of the process described herein, the third group may comprise at least one thiol, carboxyl, trialkoxysilyl, phosphoryl ester, crown ether, cryptant, dioxime, and N-heterocycle group, and the fourth group may comprise at least one group of amino, epoxy, hydroxy, carboxy, silyl, and thiol. The first group may be different from the third group of graphite inside the material. The first molecule can be attached to the graphite material before the second molecule, or the second molecule can be attached to the graphite material before the first molecule. Furthermore, the first molecule comprising a first group, a spacer and a second group can be simultaneously linked to the second molecule comprising a third group, a spacer and a fourth group, as described in the above method. The first molecule can comprise at least one molecule of diamino compound, diepoxy compound and amino alcohol compound. The second molecule may comprise at least one molecule of an O-phosphorylethanolamine diester and aminopropyl trialkoxysilane.
    [0032] Within the method shown in FIGURE 1, the graphite material can be functionalized. The graphite material can be at least a graphene graphite material and carbon nanotubes. For FIGURE 1, a CNT 101 can be represented as the graphite material.
    [0033] The first group 102 (denominated Y) can be constituted by at least one hydroxyl, thiol, amino, epoxy, carboxyl and silyl group. Examples of the first silyl group 102 may include, but are not limited to, dimethylsilyl and diphenylsilyl.
    The third group 103 (denoted W) can be constituted by at least one thiol, carboxyl, trialkoxysilyl, phosphoryl ester, crown ether, cyclopetadienyl, cryptant, dioxime, and N-heterocycle group. Examples of the third group 103 may include, but are not limited to, diphosphoryl (trichloroethyl) ester, phosphoryl di(cyanoethyl)esters, 18-crown-6, 2,2,2-cryptant, 2,1,1-cryptant, dimethylglyoxime, and phenanthrolinil. For specific metals, cyclopentadienyl may bind iron, imidazolyl may bind iron, 18-crown-6 may bind magnesium, 2,2,2-cryptant may bind zinc , imidazolyl may bind zinc, 2,1,1-cryptant may bind magnesium, dimethylglyoxime may bind nickel, imidazolyl may bind copper, and phenanthrolinyl may bind copper. Various other linkers well known in the art can also be used.
    The second group 104 (designated as Z) and the fourth group 105 (designated as X) comprise at least one amino, epoxy, hydroxyl, carboxyl, silyl and thiol group. Examples of second group 104 and fourth group 105 for silyl may include, but are not limited to, dimethylsilyl and diethylsilyl.
    [0036] Within the first molecule, a spacer 106 can be attached between the first group 102 (denominated Y) and the second group 104 (denominated Z). The spacer 106 of the first molecule may vary. The spacer can be different for the first and second molecules. For example, the spacer can be a propylene spacer as shown in FIGURE 1. The spacer 106 can be less than about 1 nm. The length of spacer 106 can still allow for electron encapsulation when spacer 106 is less than about 1 nm. Furthermore, the first Y group 102, the third W group 103, or both the first Y group 102 and the third W group 103 can be connected to the spacer 106 such that the first Y group 102, the third W group 103, or both the first Y group 102 and the third W group 103 can be in contact with the CNT 101.
    [0037] The spacer 107 of the second molecule may vary. Within the second molecule, a spacer 107 can be attached between the third group 103 (denominated W) and the fourth group 105 (denominated X). For example, the spacer can be a propylene spacer as shown in FIGURE 1. The spacer 107 can be less than about 1 nm. The length of spacer 107 can also allow for electron encapsulation when spacer 107 is less than about 1 nm. Furthermore, the first Y group 102, the third W group 103, or both the first Y group 102 and the third W group 103 can be connected to the spacer 107 such that the first Y group 102, the third W group 103, or both the first Y group 102 and the third W group 103 can be in contact with the CNT 101.
    [0038] In addition, polymerization can take place in the first Y group 102. Polymerization can also take place in the third W group 103, unless the third W group 103 can be a specific metal binder. The polymerization can include a polyurethane, an epoxy resin or a silicone. A sacrificial metal particle can be bonded to the third W 103 group. The sacrificial metal particle can comprise at least one metal of zinc, magnesium, nickel, aluminum and cobalt. Within the methods described herein, the sacrificial metal particle can be in electrical contact with the graphite material. Within electrical contact, the spacer can be less than about 1 nm in length and electron encapsulation can occur.
    [0039] The method described in FIGURE 1 herein can allow at least two different types of molecules to be attached to a graphite material. Bonding can be provided by at least one method of mechanical grinding, ultrasonic vibration and high pressure microfluid injection. Rather than providing a mixture of graphite materials where only one type of molecule can be attached to a graphite material, the method described here can allow a single functionalized graphite material to be used. The amount and ratio of binding for both the first and second molecules can be tailored to a specific application.
    [0040] Functionalized graphite material can also be incorporated into a plastic composite. The plastic compound can be thermosetting. The plastic compound comprises at least one epoxy resin, polyacrylate, polyurethane and phenolformaldehyde. The plastic composite can be an adjustable material composition. The adjustable material may comprise: 1) a thermoset plastic; and 2) a graphite material prepared by the method comprising the steps to: a) provide a graphite material; b) providing a first molecule, comprising a first group, a spacer and a second group; c) providing a second molecule, comprising a third group, a spacer and a fourth group, wherein said third group is a group other than said first group; and d) attaching the first and second molecules to the graphite material. Within the process for providing the first molecule, the first group can comprise at least one hydroxyl, thiol, amino, epoxy, carboxyl and silyl group, and the second group can comprise at least one amino, epoxy, hydroxyl, carboxyl group, silyl and thiol. Also within the scope of the process described herein for providing the second molecule, the third group may comprise at least one thiol, carboxyl, trialkoxysilyl, phosphoryl ester, crown ether, cryptant, dioxime, and N-heterocycle group, and the fourth group may comprise at least one amino, epoxy, hydroxyl, carboxyl, silyl, and thiol group. The first group may be different from the third group of graphite inside the material. Adjustable material composition can be used in anti-corrosive coatings on electromagnetic interference shields, magnetic shielding, conductors, supercapacitors, pre-impregnated compounds, epoxies, polyacrylates and polyurethanes. The composition can also comprise a silicone.
    [0041] Within the composition described above, the thermosetting plastic can be at least a plastic of an epoxy, polyacrylate, polyurethane and phenolformaldehyde. The graphite material can be at least one carbon atom from carbon nanotubes and graphene. Furthermore, the graphite material can be functionalized. The graphite material can be functionalized with at least one diaminobenzene hardener, ethylene diamine oxide, polypropylene diamine oxide, cyclohexane diamine derivatives and tall oil amine. Graphite material can be functionalized in the absence of oxygen and water.
    [0042] The composition described above may further comprise at least one particle of macroparticles, microparticles and nanoparticles. The macroparticles can comprise at least one macroparticle of sand, glass, basalt, alumina, silica, titanium dioxide, ceramic and graphite fibers. The microparticles comprise at least one microparticle of titanium dioxide, silica, ceramic, graphite, iron phosphate, alumina, nickel, cobalt, zinc, aluminum and magnesium. The nanoparticles comprise at least one nanoparticle of titanium dioxide, copper oxide, iron phosphate, silver, silica and alumina.
    [0043] FIGURE 2 also provides an embodiment of the method described herein for a graphitic carbon modification process, comprising the steps to: 1) provide a graphite material; 2) providing a first molecule comprising a first amino group, a spacer and a trialkoxydosiloxane group; 3) providing a second molecule, comprising a second amino group, a spacer and a third amino group; and 4) attaching the first amino group and the second amino group to the graphite material. Alternatively, the method of Figure 2 described herein may be a graphitic carbon modification process, comprising the steps of: 1) providing a graphite material; 2) providing a first molecule comprising a second amino group, a spacer and a third amino group; 3) providing a second molecule, comprising a first amino group, a spacer and a trialkoxysiloxane group; and 4) attaching the first amino group and the second amino group to the graphite material. Furthermore, the molecule can comprise a first amino group, a spacer and a trialkoxysiloxane group can be added simultaneously with the molecule comprising a second amino group, a spacer and a third amino group, both described in the two methods described above. The first molecule can be attached to the graphite material before the second molecule, or the second molecule can be attached to the graphite material before the first molecule. Furthermore, the first molecule comprising a first group, a spacer and a second group can be simultaneously attached to the second molecule comprising a third group, a spacer and a fourth group, as described in the above method. Bonding can be provided by at least one method of mechanical grinding, ultrasonic vibration and high pressure microfluid injection.
    [0044] Within the method shown in FIGURE 2, the graphite material can be functionalized. The graphite material can be at least a graphene graphite material and carbon nanotubes. For FIGURE 2, a CNT 201 can be represented as the graphite material.
    [0045] The upper illustration in FIGURE 2 provides the introduction of both the amino group and the 202 group and the trialkoxysiloxane group 203 to the CNT 201. Within the method, both the amino group 202 and the trialkoxysiloxane group 203 can then be bonded to the CNT 201 with a spacer (206 and 207), as shown in the lower illustration in FIGURE 2. Specifically, the diamino compound can be bonded through the amine group 204 to the CNT 201 to form a secondary amino group 208. In a similar fashion , the second molecule can link through the amine group 205 to the CNT 201 to form a secondary amino group 209.
    [0046] The spacer portion of the molecule can vary. For example, the spacer may be a propylene spacer as shown in FIGURE 2. The spacer may be different for the first and second molecules. The linkage of both the amino group 202 and the trialkoxydosiloxane group 203 can occur due to the functionalization of an amino group with either the amino group 202 or the trialkoxydosiloxane group 203. The amino group can be linked directly to the CNT 201, allowing both the group amino 202 or trialkoxysiloxane group 203 functionalize CNT 201.
    [0047] The amino group 202 can then provide a starting point for other epoxy and urethane functionalities, and the trialkoxydosiloxane group 203 can provide a starting point for silicone functionalities. Epoxy and urethane functionalities as well as other amino functionalities can provide rigidity and hardness to the CNT 201, while silicone functionalities can provide softness and flexibility to the CNT 201. Together, the multiple functionalities within the CNT 201 can provide properties and also a means to adjust the properties of a specific application. For example, an amino group can be polymerized with an epoxy monomer, epoxy oligomer, urethane monomer or urethane oligomer. In addition, the trialkoxysiloxane group can be polymerized with a silicone monomer or oligomer.
    [0048] The graphite material can be functionalized with at least one hardener of diaminobenzene, polypropylene diamine oxide, cyclohexane diamine derivatives and tall-oil amine. The graphite material can also be functionalized with another curing agent. Graphite material can also be functionalized in the absence of oxygen and water.
    [0049] FIGURE 3 shows several versions of CNT functionalized with polymers. A polymer can be attached through a primary or secondary amino group, a hydroxyl group or an epoxy group. The hydroxyl group can include a phenolic hydroxyl group. These functionalities can serve as starting points for polyurethane, polyacrylate, polyurea, epoxy resin, phenol-formaldehyde resin, polyacrylates or other polymers. One embodiment of the general principle of the method described herein is a CNT or graphene sheet functionalized with alkoxysilane or amino functionalities or simultaneously with both.
    [0050] Each functionalized CNT or graphene sheet may contain tens or hundreds of functional groups capable of binding each particle multiple times. Each functionalized CNT or graphene sheet can also bind multiple particles. Likewise, each functionalized CNT or graphene sheet can link multiple polymer chains. These features can be directly linked with CNTs or graphene, and spacers can also be used. The spacer can contain aliphatic, aromatic or heterocyclic moieties.
    [0051] In Figure 3A, the CNT 301 can be functionalized with only the 304 trialkoxysiloxane group. If only the 304 trialkoxysiloxane group can be used, only the silicone functions can be attached. In Figure 3B, the CNT 302 can be functionalized with only the 305 amino group. If only the 305 amino group can be used, only the epoxy, urethane and other amino functionalities can be attached. Although a mixture of the functionalized CNT 302 and CNT 302 can be used in one application, none of them provide both the amino group 305 and the 304 trialkoxysiloxane group within a single CNT or other graphite material. FIGURE 3C shows the method described herein, wherein CNT 303 can be functionalized with either the 305 amino group or the 304 trialkoxydosiloxane group.
    [0052] FIGURE 4 can illustrate how side chains can be grown in the graphite material. At the start of the reaction shown at the top of figure 4, the CNT 401 may contain both the amino group and the trialkoxysiloxane group attached to it. In this example, silicone 403 can be reacted in the presence of a catalytic amount of water. The reaction illustrated in Figure 4 can allow further polymerization of epoxide 402 and silicone 403, but the polyurethane can also be polymerized in place of epoxy 402. From this reaction, both the epoxy functionality 405 and the functionality of silicone 404 can, then provide different properties for the CNT 401.
    [0053] FIGURE 5 can provide three different pictorial representations of how the strands can be grown in the graphite material. In this figure, the graphite material can be CNT 501. In Figure 5A, CNT 501 can have multiple side chains from the silicone group 504. In Figure 5B, CNT 502 can have multiple side chains of epoxy or polyurethane 505. Figure 5C shows the CNT 503 which may include side chains of epoxy or polyurethane 505 and side chains of the silicone group 504. In general, these various side chains can be grafted to the CNT. Side chains can be branched. If the polymer chains are sufficiently different physically, chemically or physically and chemically, as in Figure 5C, the CNT 503 can separate and form the layered structure, as described below in Figure 6. These layers can be weakly or strongly linked if a biphasic CNT is added to a composition. This type of biphasic CNT can contain at least two types of branches, which are able to interact strongly with both layers, allowing the manufacture of self-stratifying coatings.
    [0054] Described here in FIGURE 5C, it may allow the combination of both hard and soft plastic composite materials and coating materials with the functionalized CNTs. The plastic compound can be thermosetting. Plastic compounds can include epoxies, polyurethanes, polyacrylates and phenolformaldehyde. These coatings can be impact and crack resistant. While abrasion resistance may be acceptable, it can be improved by covalently bonding nanoparticles or microparticles.
    [0055] In FIGURE 6, the multiple layers of CNTs can be demonstrated. The CNTs (601, 602 and 603) are shown within the figure. The separate layers of functionalized CNTs, labeled 608 and 610 within the figure, may be the result of layering the CNTs. An intermediate area 609 can be located within the separate CNT layers 608 and 610. Intermediate layer 609 can be used to bond the separate functionalized CNT layers 608 and 610 together. Layers can form when silicone layer 608 separates from epoxy layer 610. Specifically, methyl groups within the silicone can provide the layers. However, phenyl groups on silicone can prevent layering, especially if the phenyl groups have polar substituents such as methoxy. There can be only methyl groups within the silicone groups or only phenyl within the silicone. There can also be two methyl and phenyl groups within the silicone. If layers can be formed, they can be up to 10 nm thick. Layers can also be from about 50 nm to about 50 µm.
    [0056] The degree of functionalization of carbon nanotubes can be adjusted over a wide range of covalent bonding moieties per micrometer of a carbon nanotube. For example, functionalities can be amino groups that can initiate polymerization of an epoxy compound. Functionalities can also be amino groups that can initiate polymerization of a polyurethane compound. The functionalities can be trialkoxysiloxane groups that can initiate the polymerization of a silicone.
    [0057] Within the layers, there may be an interaction between the side chains of the amino group 605, 607 and the side chains of the trialkoxydosiloxane group 604 and 606. Due to these interactions, there may be bonding and crosslinking between the functionalized CNTs.
    [0058] The layered structure provided in FIGURE 6 can allow coatings that resist cracking, since they can be less rigid due to the silicone groups. The layered structure can also be useful in applications where they are advantageous. For example, these layered structures can be used in ship linings where barnacles can peel off at least one layer of lining at a time, but the layered structure can remain within the lining. Aromatic or aliphatic curing agents can also be used within the layered structure.
    [0059] The functionalized graphite material can be bonded with a polymer, a metal particle or both. The method described here may allow for more electrical conduction than simply mixing the components. If electrical contact between a graphite particulate material is desired, the spacer may be short.
    [0060] FIGURE 7 may provide an embodiment of a structural representation of a plastic or adjustable composite liner. Anti-corrosive coatings can be an application of the process described herein. The composition of the adjustable material in FIGURE 7 may comprise: 1) a thermoset plastic; 2) silicone; and 3) at least one functionalized graphite material of carbon nanotubes and graphene prepared by the method comprising the steps to: 1) provide a graphite material; 2) providing a first molecule comprising a first amino group, a spacer and a trialkoxydosiloxane group; 3) providing a second molecule, comprising a second amino group, a spacer and a third amino group; and 4) attaching the first amino group and the second amino group to the graphite material. Alternatively, the method for providing at least one functionalized graphite material can be prepared by other methods described above in FIGURE 2. The first molecule can be attached to the graphite material before the second molecule, or the second molecule can be attached to the graphite material before the first molecule. In addition, the first molecule comprising a first amino group, a spacer and a second trialkoxysiloxane group can simultaneously bind to the second molecule comprising a second amino group, a spacer and a third amino group, as described in the above method.
    [0061] FIGURE 7 can describe the molecular bonds for the methods described herein. Elastic polymer 704 can be represented as a spring (previously depicted in circles in Figure 5A). Elastic polymer 704 can include siloxane functionalities. The stiffer polymer 705 can be depicted with triangles in Figure 7. The stiffer polymer 705 can include epoxy, polyurethane, polyacrylates, and phenolformaldehyde. The three types of functionalized carbon nanotubes 701, 702, and 703 can correspond to 501, 502, and 503 in Figure 5. Polymer chains, including elastic polymer 704 and stiffer polymer 705, can form a bridge between two functionalized carbon nanotubes or attaching the functionalized CNT to a 706 and 707 particle. The 706 and 707 particles can be attached to the functionalized CNTs through a small spacer. Arrows show the binding of polymers (704 and 705) or functionalized CNTs (701, 702, and 703) to particles (706 and 707) or substrate 709. Polymer chains can be crosslinked. If the polymerization reactions are orthogonal, no block or graft polymers can be formed.
    [0062] The present description can further provide a method for preparing coatings. This method may comprise the steps to: 1) functionalize CNTs or graphene with amine hardener, aminopropyl trimethoxysilane, macroparticles, microparticles, nanoparticles or, 2) blend the functionalized CNT with epoxy to form a mixture, 3) coat the mold with the mixing, 4) injecting the epoxy mixture in large quantities into the mold, and 4) curing the mixture.
    [0063] The siloxane 704 segments within FIGURE 7 can be formed from monomers, or they can be oligomers, which can be partially prepolymerized. These components can be mixed with hardener or epoxy or both. Appropriate monomers can include di(methoxyphenyl), dimethoxysilane, dianisyl dimethoxysilane, dimethyl-dimethoxysilane, diphenyl diethoxysilane, aminopropyl trimethoxysilane (also known as APTMS) and tetraethoxysilicate (also known as TES). However, the monomers can also include virtually any aliphatic or aromatic part, as well as some of their functionalized forms, such as chlorinated and fluorinated derivatives. These monomers can be polymerized if there can be a catalytic amount of water present. APTMS and TES can provide branch points in the siloxane chain. APTMS can furthermore serve as a starting and ending point for the polymerization of siloxane. Too many covalent epoxy contacts can reduce or eliminate siloxane elasticity, the concentration of free APTMS where it cannot be bound to functionalized CNTs or nanoparticles may be less than about 10% of all silane components. Another type of silicone polymer can be formed, for example, from vinyl dimethylsilane in the presence of a catalytic amount of platinum. By varying the side groups, many other analogous monomers can be used. To provide a starting point in a functionalized carbon nanotube, aminopropyl dimethylsilane can be used. The endpoint can be functionalized with vinyl aminopropyl methylsilane. Several analogous molecules can be used in place of these examples. In addition, an amino group can serve as a starting and ending point for epoxy polymerization.
    [0064] Within a composition comprising a graphite material and metal particles, the electrical contact between the metal particle and the graphite material may be weak. This deficiency may be due to a polymer layer wrapped around the metal particle, the graphite material, or both. The method described here can increase electrical contact and can also provide the mechanism for chemical contact between the metal and polymer particles. By incorporating functionalized graphite materials, a stronger electrical connection can exist between the metal particle and the metallic substrate. Metal particles can be nanoparticles or microparticles. Within the method described here, orthogonal chemistries can aid in the fixation of metal particles and polymers with the graphitic material through covalent bonding. Orthogonal chemistries cannot interfere with each other. Orthogonal chemistries can happen under ambient conditions. However, orthogonal chemistries can also use UV, IR or some other healing method.
    [0065] FIGURE 8 can provide a means in which ceramic or metallic particles are bonded to the functionalized graphitic material. In addition to the polymer bonding described above, individual particles can also be bonded. In FIGURE 8, CNT 801 is shown. Both silica (SiO2) 802 and aluminum oxide (Al2O3) 803 can be bonded to CNT 801 through the trialkoxysiloxane group. Trimethoxysilane groups may also be capable of binding silica or aluminum oxide. In addition, a sacrificial metal particle can be attached to the trialkoxysiloxane group. The sacrificial metal particle can comprise at least one metal of zinc, magnesium, nickel, aluminum and cobalt. Within the methods described herein, the sacrificial metal particle can be in electrical contact with the graphite material. Within electrical contact, the spacer can be less than about 1 nm in length, and electron encapsulation can occur between the CNT 801 and a metallic particle.
    [0066] The method described here can provide a means to avoid the passivation of sacrificial particles. Most linking groups (for example, the third group 103 in Figure 1) cannot be linked by sacrificial particles. If the distance between these groups is from about 0.4 nm to about 2 nm on average, transfer of metal cations may be possible through ionic conductance. With ionic conductance, sacrificial metal cations can be removed from the particle surface after the oxidative reaction and the active metal surface can then be exposed. The third groups (shown as 103 in Figure 1) can be selective for sacrificial metal cations. This method can allow ionic and electronic conductance along the functionalized graphite material. However, a high degree of functionalization can decrease electrical conductance, especially if single-walled CNTs are used. The effect may be less for double-walled CNTs and multi-walled CNTs. The density of binders may be lower if polymeric ionic conductors are attached to the graphite material. Non-limiting examples of ionic conducting polymers can be polyethylene diamine oxide, polyallylamine, and polypyrrolidone.
    [0067] Figure 9 may provide a pictorial view of an embodiment of the adjustable material 801 as described herein. The composition of the adjustable material may include: 1) a thermoset plastic; 2) silicone; and 3) at least one functionalized graphite material of carbon nanotubes and graphene prepared by the method comprising the steps to: 1) provide a graphite material; 2) providing a first molecule comprising a first amino group, a spacer and a trialkoxydosiloxane group; 3) providing a second molecule, comprising a second amino group, a spacer and a third amino group; and 4) attaching the first amino group and the second amino group to the graphite material. Alternatively, the method for providing at least one functionalized graphite material can be prepared by other methods described above in FIGURE 2. The first molecule comprising a first amino group, a spacer and a trialkoxysiloxane group can be attached to the graphite material before of the second molecule comprising a second amino group, a spacer and a third amino group or the second molecule can be attached to the graphite material before the first molecule. In addition, the first molecule comprising a first amino group, a spacer and a second trialkoxysiloxane group can simultaneously bind to the second molecule comprising a second amino group, a spacer and a third amino group, as described in the above method. In addition, combinations of the above methods can also be used. As also described in FIGURE 7, other materials may be included in the composition of FIGURE 7. Tunable material 901 may also contain at least one particle of macroparticles 902, microparticles 903 and nanoparticles 904; a thermoset plastic; silicone; at least one graphite material from carbon nanotubes and graphene; and a means for providing at least one graphite material of carbon nanotubes and graphene by high hydrodynamic pressure injection.
    [0068] Within the adjustable material 901 in FIGURE 9, macroparticles 902, microparticles 903 and nanoparticles 904 can be dispersed through the thermosetting plastic 905. The thermosetting plastic can include at least one plastic of an epoxy resin, a polyurethane, a polyacrylate and a phenolformaldehyde. In FIGURE 9, at least one particle of 902 macroparticles, 903 microparticles, and 904 nanoparticles can be added. The 902 macroparticles can have dimensions from 100 µm to approximately 2 mm. 903 microparticles can range from 200 nm to approximately 100 µm. The 904 nanoparticles can be about 1 nm to 200 nm. The macroparticles 902 can comprise at least one macroparticle of sand, glass, basalt, alumina, silica, titanium dioxide, ceramic, graphite fibers and other metal particles. The microparticles 903 can comprise at least one microparticle of titanium dioxide, silica, ceramic, graphite, iron phosphate, alumina, nickel, cobalt, zinc, aluminum, magnesium, and other metal particles. The nanoparticles 904 can comprise at least nanoparticles of titanium dioxide, copper oxide, iron phosphate, silver, silica, alumina and other metal particles. Macroparticles 902, microparticles 903 and nanoparticles 904 can also provide the desired characteristics for the tunable material 901, depending on the application. For example, titanium dioxide, silica and alumina particles can increase surface rigidity and hardness. Additionally, titanium dioxide can be used to provide the 901 tunable material with a self-cleaning property and the Lotus effect. In addition, a sacrificial metal particle can be added to the adjustable material, where the sacrificial metal particle can comprise at least one metal of zinc, magnesium, nickel, aluminum and cobalt.
    [0069] In addition, glass and basalt fibers can be metal silicates containing mainly alkali metals, alkaline earth metals and aluminum. Glass can contain borate, while basalt fiber can contain several other metallic cations. APTMS can bind silicic acid or metal cations. APTMS can react slowly with the ionized form of silicic acid. Thus, treating glass and basalt fiber with an acid, gaseous or liquid, can improve the reaction time. These acids can include, but are not limited to, dilute hydrochloric acid, sulfuric acid, formic acid and acetic acid. Short treatment with hydrofluoric acid or ammonium fluoride is also possible. The carbon fiber within the adjustable material 801 may have oxygen containing functionalities such as carboxylic and hydroxyl groups and the trimethoxysilane group of APTMS may be able to bind these functionalities.
    [0070] The tunable material 901 may also comprise at least one functionalized graphitic material, including carbon and graphene nanotubes prepared from the methods described herein. The functionalized graphite material can be used to reinforce thermosetting resins, including, but not limited to, epoxy and polyurethane resins. Functionalized graphitic material, eg functionalized carbon nanotubes, can provide high tensile strength and stiffness. Improved tensile strength and rigidity can compensate for the 905 moldable thermoset plastic.
    [0071] Within the 901 tunable material, silicone can also be added. The silicone inside the adjustable material 901 can be used to adjust the elasticity within the material. The silicone within the adjustable material 901 may contain a siloxane structure, which may be soft and deformable. The amount of silicone within the adjustable material 901 can be adjusted to provide a durable material.
    [0072] Each component of the present 901 adjustable material can provide the functionality. A thermosetting resin 905 can constitute more than about 90% of the total mass of the composite. The range of 902 macroparticles, 903 microparticles, and 904 nanoparticles can be from about 5% to about 80%, depending on the hardness desired. The range of 902 macroparticles, 903 microparticles, and 904 nanoparticles can also be from about 10% to about 35%. The siloxane can have concentrations of around 0.05%, where it can act within the matrix and particle interface. Where the siloxane can act as a matrix component of the adjustable material 901, it can range from about 0.1% to about 50%, depending on the desired elasticity. Functionalized graphene can be from about 0.1% to about 5%. Mechanical properties can improve between about 0.3% and about 0.8%, but electrical conductivity can improve by about 2%. Within adjustable material 901, the composition may vary depending on the application and desired characteristics.
    [0073] Within the tunable material composition described here, titanium dioxide nanoparticles can electronically activate oxygen molecules to light. Activated oxygen may be able to oxidize organic impurities on the surface. Thus, the fabrication of self-cleaning surfaces may be possible. However, the surface itself can oxidize. Two methods can be used to prevent surface oxidation. The first method may be to increase the concentration of inorganic particles. The second method can be to add fluorinated compounds, such as carboxylic acids, polyfluorinated alcohols or chemically bonded aromatic compounds, for example, with functionalized carbon nanotubes or silicone.
    [0074] Particles can increase the hardness and abrasion resistance of a surface. Pigments can also be used to obtain a certain color. For example, titanium dioxide macroparticles and microparticles can provide a white color despite the presence of black functionalized carbon nanotubes. Titanium dioxide nanoparticles can also provide a self-cleaning surface.
    [0075] Within the 901 adjustable material, there may be a covalent bond within all components, including 905 thermosetting plastic, siloxane, functionalized carbon nanotubes, 902 macroparticles, 903 microparticles and 904 nanoparticles, including silica, alumina, oxide titanium, copper oxide, iron phosphate, carbon, glass and basalt fiber if these components are present. In a 901 tunable material, the components can be in close proximity to one another, and each component can provide molecular-level chemical coupling with the neighboring component. Trimethoxysilane groups may also be able to bind to fiberglass or basalt fiber, when the liquid mixture of epoxy and hardener can be brought into contact with these fibers, functionalizing the carbon nanotubes. This can be achieved by mixing APTMS with a diamine or polyamine hardener prior to functionalization.
    [0076] The surface may contain 902 macroparticles, which are incorporated and chemically bonded to a polymer matrix. Macroparticles 902 can be sand, glass powder, basalt, silica, alumina, titanium dioxide, graphite fibers or almost any ceramic material. The 903 microparticles can fill the voids between the 902 macroparticles and help make the surface smoother. The surface can have both micro and nano particle scale roughness. Micro scale roughness can aid aerodynamics and nanoscale roughness can provide a hydrophobic surface or Lotus effect. Nanoscale roughness can be achieved with 904 nanoparticles.
    [0077] Within the scope of the process described herein, the preparation of graphene or CNT can also incorporate at least one particle of nanoparticles and microparticles in the carbon dispersion, and at least one particle of nanoparticles and microparticles within the second dispersion of carbon. Both nanoparticles and microparticles can help with the exfoliation of graphene or CNT and can prevent the reassembly of graphene back to graphite. The addition of at least one of the nanoparticles and microparticles can include silica, alumina, carbon nanotubes and amorphous carbon.
    [0078] FIGURE 10 provides a schematic view of a surface structure of an abrasion and corrosion resistant coating 1001. The schematic in FIGURE 10 can show both micro and nanoscale surface roughness. This type of structure can be useful in certain applications, such as windmill blades. The microstructure can reduce friction against water 1004 and airflow. Air can then circulate in the micronized pockets 1005, which can act as a ball bearing between the solid surfaces. Nanoparticles 1003 within coating surface 1002 can create a nano-ripple that reduces the interaction between water and surface 1006 under the coating. The surface tension of water 1006 can prevent water from following nanoscale variations. Due to the weak interaction at the nanoscale, water may not be able to follow even the microscale corrugation, so the adhesion of water 1006 may be further reduced and water 1006 may not be able to penetrate the coating. corrosion resistant 1001. Thus, the water 1006 can be completely removed from the surface of the coating 1002 as well as the coating 1001 itself on the substrate. Dewatering 1006 may be necessary, both in wet and cold environments, where ice formation can make coating 1001 difficult.
    [0079] Coating materials 1001 may include conventional epoxies and polyurethanes. In addition, 1001 coating materials can be corrosion resistant as well as both chemically and physically durable. In typical coatings, corrosive liquids such as water, acids and alkalis can seep through nanocracks and corrode the underlying surface, potentially causing the coating to peel. This process can be reduced or avoided by using the present coating described herein. The thermal expansion and contraction cycles within the coating 1001 described here may not cause nanocracks because the carbon nanotubes within the coating 1001 can prevent this cracking. In addition, siloxane can help epoxy or polyurethane to be more plastic and resist cracking. If coating 1001 is used to protect the surface from water, including salt water, it may be necessary to use additional layers of protection. Carbon and graphene nanotubes can make the 1001 coating electrically conductive, although the concentration of carbon nanotubes and carbon nanotubes and graphene and graphene CNTs can be kept so low that the resistance becomes high.
    [0080] In addition to the tunable coating described herein, a system of corrosion resistant coatings can be provided in which the adjustable coating can be incorporated into the system. One embodiment of the method of manufacturing a corrosion resistant coating system may comprise the steps to: 1) generate a substrate; 2) applying to the substrate a first layer of an adjustable material composition comprising a thermoset plastic; and at least one functionalized graphite material of carbon nanotubes and graphene prepared by the method comprising the steps of: providing a graphite material; generating a first molecule comprising a first group, a spacer and a second group; generating a second molecule comprising a third group, a spacer and a fourth group, wherein said third group is a group different from said first group; and bonding the second group and the fourth group to the graphite material; 2) applying a second layer comprising an electrically insulating material with the first layer; and 3) applying to the second layer a third layer of an adjustable material composition comprising a thermoset plastic; and at least one functionalized graphite material of carbon nanotubes and graphene prepared by the method comprising the steps of: providing a graphite material; with a first molecule comprising a first group, a spacer and a second group; a second molecule comprising a third group, a spacer and a fourth group, wherein said third group is a group other than said first group; and bonding the second group and the fourth group to the graphite material. Within the process, the first group can comprise at least one hydroxyl, thiol, amino, epoxy, carboxyl and silyl group, and the second group can comprise at least one amino, epoxy, hydroxyl, carboxyl, silyl and thiol group. Also within the scope of the process described herein, the third group may comprise at least one thiol, carboxyl, trialkoxysilyl, phosphoryl ester, crown ether, cryptant, dioxime, and N-heterocycle group, and the fourth group may comprise at least one group of amino, epoxy, hydroxy, carboxy, silyl, and thiol.
    [0081] Another embodiment of the corrosion resistant coating system manufacturing method may comprise the steps to: 1) generate a substrate; 2) applying to the substrate a first layer of an adjustable material composition comprising a thermoset plastic; silicone and at least one functionalized graphite carbon nanotube material and graphene prepared by the method comprising the steps of: providing a graphite material; generating a first molecule comprising a first amino group, a spacer and a trialkoxydosiloxane group; generating a second molecule comprising a second amino group, a spacer and a third amino group, connecting the first amino group and the second amino group to the graphite material; 3) applying a second layer comprising an electrically insulating material to the first layer; and 4) applying to the second layer a third layer of an adjustable material composition comprising a thermoset plastic; silicone and at least one functionalized graphite carbon nanotube material and graphene prepared by the method comprising the steps of: providing a graphite material; with a first molecule comprising a first amino group, a spacer and a trialkoxydosiloxane group; a second molecule comprising a second amino group, a spacer and a third amino group and the attachment of the first amino group and the second amino group to the graphite material. Alternatively, the corrosion resistant coating system manufacturing method may comprise the steps to: 1) generate a substrate; 2) applying to the substrate a first layer of an adjustable material composition comprising a thermoset plastic; silicone and at least one functionalized graphite carbon nanotube material and graphene prepared by the method comprising the steps of: providing a graphite material; generating a first molecule comprising a second amino group, a spacer and a third amino group; generating a second molecule comprising a first amino group, a spacer and a trialkoxydosiloxane group, linking the first amino group and the second amino group to the graphite material; 3) applying a second layer comprising an electrically insulating material to the first layer; and 4) applying to the second layer a third layer of an adjustable material composition comprising a thermoset plastic; silicone and at least one functionalized graphite carbon nanotube material and graphene prepared by the method comprising the steps of: providing a graphite material; with a first molecule comprising a second amino group, a spacer and a third amino group; a second molecule comprising a first amino group, a spacer and a trialkoxydosiloxane group and the attachment of the first amino group and the second amino group to the graphite material. Within the functionalized graphite material of carbon nanotubes and graphene prepared by the methods described herein, the molecule comprising an amino group, a spacer, and a trialkoxy siloxane group can be added simultaneously with the molecule comprising an amino group, a spacer, and a group additional amino. In addition, combinations of the above methods can also be used.
    [0082] The bottom (first bottom layer) cannot sacrifice the physical integrity of the coating. The first lower layer may comprise a first composition of adjustable materials. The bottom may also contain at least one sacrificial metal particle of magnesium, zinc, nickel and cobalt. This first lower layer can provide protection against galvanic corrosion. The middle layer, or second layer, may be electrically insulating and may contain reinforcements, including, but not limited to, at least one reinforcement material from whiskers of silicon carbide, aluminum oxide, fibers or tubes, hydrogenated graphene, hydrogenated nanotubes and carbon nanotubes. The topcoat, or third layer, can contain at least one graphite carbon nanotube graphene material that can be functionalized within the second composition of the adjustable material. The top coat, or third layer, can also optionally contain a biocidal compound as well as particles that can make the coating self-healing and corrosion resistant. The top coat, or third layer, may or may not be identical to the first bottom layer, comprising the first composition of adjustable materials.
    [0083] The present coating described in Figures 9 and 10 and here can be used, among others, in applications in vehicles, boats, ships, oil and gas pipelines and mill blades. Adjustable material composition is used in anti-corrosive coatings on electromagnetic interference shields, magnetic shielding, conductors, supercapacitors, pre-impregnated compounds.
    [0084] The following examples illustrate the methods present in a practicable form, but as such, these examples are not to be construed as limitations on the general scope of the methods described herein. Example 1.
    [0085] The multi-walled CNTs (10g, Baytubes, Bayer, Germany) and 10g of aminopropyl-trimethoxysilane were sonicated in 1000g of Jeffamine ED-900 hardener (Huntsman, USA), using 1g of aluminum tripropoxide as catalyst. The power was 800 W and the time was about 10 min. This hardener, called the HNT hardener, was ready to be used with the bisphenol A epoxy which contained 80 ml of dimethyl-dimethoxy silane and 20 g of diphenyl-dimethoxy silane. Example 2.
    [0086] Multi-walled CNTs (10g, Baytubes, Bayer, Germany), 5g silica and 5g alumina nanoparticles and 10g aminopropyl-trimethoxysilane were ground for about 30 minutes in a mortar in 100 ml of Jeffamine ED-hardener. 900 (Huntsman, USA). This hardener was diluted to 1000g with pure Jeffamine HK-511 and called HNT-NP hardener, ready to be used with 1450g bisphenol A epoxy, which contained 80 ml of dimethyl-dimethoxy-silane and 20 g of diphenyl-dimethoxy-silane. Example 3.
    The material from Example 2 was diluted with 200 ml of isopropanol, filtered and washed with 100 ml of isopropanol. The solid was dried under vacuum. Functionalized CNTs were dispersed in 1000 ml of 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane. Example 4.
    [0088] In 1 kg of bisphenol A diglycidyl ether, 10 g of graphite powder (200 mesh, Alfa Aesar) were added USING a mechanical mixer. The mixture was degassed with an ultrasonic bath under a nitrogen atmosphere. The raw graphite dispersion was processed with an LV1 Microfluidizer Processor IDEX (Material Processing Technologies Group) three times using a pressure of 1500000 mmHg (2500 bar). Example 5.
    [0089] The product of Example 3 was mixed with 100g of zinc dust in a closed metal can, USING a roller mixer. The coated zinc powder was further mixed with a high speed mechanical mixer with Epon 828. Melamine curing agent was added and six test plates were coated with a 20 micron layer of this coating material. Polyurethane finish was applied on these boards. Six reference plates were also coated with a composition that contained the same components, but the CNTs were used in place of the amino-trimethoxy CNT. The plates were tested in a saline mist chamber for 1,000 hours. Rust was measured colorimetrically. The boards that were coated with this method had about 24 ± 11% less rust formation.
    [0090] The implementations were described above. It will be apparent to those skilled in the art that the above methods and apparatus can incorporate changes and modifications without departing from the general scope of these methods. It is intended to include all such modifications and changes as they come within the scope of the appended claims or equivalents.
    权利要求:
    Claims (8)
    [0001]
    1. PROCESS TO PREPARE AN ANTICORROSIVE COATING characterized by the fact that it comprises the steps of: providing a substrate; provide a sacrificial metal particle selected from the group consisting of zinc, magnesium, nickel, aluminum, cobalt and combinations thereof; chemically bonding a graphitic material to a first molecule, which comprises a first group, a first spacer and a second group, wherein the first group comprises at least one of hydroxyl, thiol, amino, epoxy, carboxyl and silyl, wherein the second group comprises at least one of amino, epoxy, hydroxyl, carboxyl, silyl and thiol; chemically bonding said graphitic material to a second molecule, comprising a third group, a second spacer and a fourth group, wherein the third group is a group different from said first group, wherein said third group comprises at least one of thiols carboxyl, trialkoxysilyl, phosphoryl-ester, crown ether, cryptant, dioxime and N-heterocycle, the fourth group comprising at least one of amino, epoxy, hydroxyl, carboxyl, silyl and thiol; attaching said sacrificial metal particle to said first group or to said third group; binding said first group or said third group with the substrate, wherein said group binding said substrate is different from said group binding the sacrificial metal particle; chemically bonding said second group and said fourth group to said graphite material; cultivate thermosetting resin with side chains in said graphite material; and cultivating siloxane with side chains on said graphitic material, the process further comprising the steps of providing a second graphitic material; bonding the first group and the third group to the second graphite material, forming a first layer of functionalized graphite material; providing a second layer of functionalized graphite material; and providing a third layer of functionalized graphite material between the first layer and the second layer of functionalized graphite material, wherein the third layer of functionalized graphite material joins with the first layer and second layer of functionalized graphite material .
    [0002]
    2. PROCESS according to claim 1, characterized in that said graphitic material comprises at least one material from a carbon nanotube and graphene, in which the first spacer and the second spacer are smaller than 1 nm, in which the third group comprises at least one crown ether, cryptant, dioxime and N-heterocycle.
    [0003]
    3. Process according to claim 1, characterized in that said first molecule comprises at least one molecule of diamino compound, diepoxy compound and amino alcohol compound.
    [0004]
    4. Process according to claim 1, characterized in that said second molecule comprises at least one molecule selected from the group consisting of a diester of O-phosphorylethanolamine and aminopropyl trialkoxysilane, in which the first group is the second spacers are less than 1 nm.
    [0005]
    5. PROCESS according to claim 1, characterized in that said connection is provided by at least one method of mechanical grinding, ultrasonic vibration and high pressure microfluid injection.
    [0006]
    6. PROCESS, according to claim 1, characterized in that it additionally comprises the step of: polymerizing the first group and the third group.
    [0007]
    7. PROCESS, according to claim 1, characterized in that an electrical contact is made between said sacrificial metal particle and said functionalized graphitic material.
    [0008]
    8. PROCESS, according to claim 1, characterized in that the substrate is macroscopic and said sacrificial metallic particles are microscopic.
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    同族专利:
    公开号 | 公开日
    JP6122492B2|2017-04-26|
    KR101937517B1|2019-01-10|
    KR20140043069A|2014-04-08|
    SG11201408561YA|2015-01-29|
    CA2877688C|2020-05-05|
    WO2013191809A1|2013-12-27|
    EP2864426A1|2015-04-29|
    CA2877688A1|2013-12-27|
    MX2015000006A|2015-07-09|
    BR112014032285A2|2017-06-27|
    KR20150011340A|2015-01-30|
    KR101444635B1|2014-09-26|
    JP2015529610A|2015-10-08|
    CN104508056B|2017-03-29|
    US20150183997A1|2015-07-02|
    MY173523A|2020-01-31|
    HK1209150A1|2016-03-24|
    US9725603B2|2017-08-08|
    CN104508056A|2015-04-08|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US7250147B2|2001-01-29|2007-07-31|Tour James M|Process for derivatizing carbon nanotubes with diazonium species|
    AU2002240159A1|2001-01-29|2002-08-12|William Marsh Rice University|Process for derivatizing carbon nanotubes with diazonium species and compositions thereof|
    KR100937085B1|2002-10-26|2010-01-15|삼성전자주식회사|Layering and Patterning Method for Carbon Nanotubes Using Chemical Self Assembly|
    KR100947702B1|2003-02-26|2010-03-16|삼성전자주식회사|Method for forming a patterned film and a polymeric complex of surface-modified carbon nanotubes having polymerizable moiety|
    JP4927319B2|2003-07-24|2012-05-09|韓国科学技術園|Biochip manufacturing method using high-density carbon nanotube film or pattern|
    EP1660405B1|2003-07-28|2012-11-28|William Marsh Rice University|Sidewall functionalization of carbon nanotubes with organosilanes for polymer composites|
    JP2007508439A|2003-10-27|2007-04-05|ポリワンコーポレイション|Cathodic protective coating containing carbonaceous conductive media|
    CN1284727C|2003-11-07|2006-11-15|中国科学院化学研究所|Method for carbon nanometer tube with chemical decoration|
    WO2005100466A1|2004-04-13|2005-10-27|Zyvex Corporation|Methods for the synthesis of modular poly and fine tuning the electronic properties thereof for the functionalization of nanomaterials|
    US8158203B2|2004-05-06|2012-04-17|William Marsh Rice University|Methods of attaching or grafting carbon nanotubes to silicon surfaces and composite structures derived therefrom|
    US20090318717A1|2004-10-12|2009-12-24|Jorma Virtanen|Novel hybride materials and related methods and devices|
    EP1828052A4|2004-10-12|2011-06-08|Amroy Europ Oy|Novel hybride materials and related methods and devices|
    US7790234B2|2006-05-31|2010-09-07|Michael Raymond Ayers|Low dielectric constant materials prepared from soluble fullerene clusters|
    DE102007041820A1|2007-09-03|2009-03-05|Universität Bielefeld|graphite layers|
    US8343450B2|2007-10-09|2013-01-01|Chemnano Materials, Ltd.|Functionalized carbon nanotubes, recovery of radionuclides and separation of actinides and lanthanides|
    CN100546905C|2007-11-08|2009-10-07|浙江大学|A kind of preparation method of carbon nanotube of water-soluble and high-biocompatibility|
    CN101264881B|2008-03-06|2011-04-27|广州大学|Cyclodextrin-carbon nano tube derivatives and preparation method thereof|
    EP2241593A1|2009-04-08|2010-10-20|Bayer MaterialScience AG|Polymer-functionalised carbon nanotubes, method for their manufacture and use|
    US8663506B2|2009-05-04|2014-03-04|Laird Technologies, Inc.|Process for uniform and higher loading of metallic fillers into a polymer matrix using a highly porous host material|
    US8574673B2|2009-07-31|2013-11-05|Nantero Inc.|Anisotropic nanotube fabric layers and films and methods of forming same|
    US8128993B2|2009-07-31|2012-03-06|Nantero Inc.|Anisotropic nanotube fabric layers and films and methods of forming same|
    JP4527194B1|2009-12-11|2010-08-18|エンパイアテクノロジーディベロップメントエルエルシー|Graphene structure, method for producing graphene structure, and electronic device|
    EP2523902A1|2010-01-16|2012-11-21|Bayer Intellectual Property GmbH|Process for the preparation of carbon nanotubes having hydroxyalkyl ester groups, and materials and dispersions containing these carbon nanotubes|
    KR101355954B1|2010-09-03|2014-02-12|국립대학법인 울산과학기술대학교 산학협력단|Modified graphite, graphite/thermosetting resin nanocomposite and method of manufacturing the sames|
    CN102331449B|2011-06-10|2013-05-08|西南大学|Electrochemical sensor and preparation method thereof|
    EP2864426A1|2012-06-21|2015-04-29|Tesla Nanocoatings Inc.|Tunable materials|CN1303610C|2000-07-07|2007-03-07|睦塞德技术公司|Method and appts. for synchronzation of row and column access operation|
    EP2864426A1|2012-06-21|2015-04-29|Tesla Nanocoatings Inc.|Tunable materials|
    CN105086758B|2013-03-06|2017-10-17|常州第六元素材料科技股份有限公司|A kind of preparation method of graphene anticorrosive paint|
    US9873800B2|2014-12-19|2018-01-23|Tesla Nanocoatings, Inc.|Tunable materials|
    US9421739B2|2015-01-05|2016-08-23|The Boeing Company|Graphene aerospace composites|
    US9518160B2|2015-01-05|2016-12-13|The Boeing Company|Graphene-augmented composite materials|
    US10875986B2|2015-01-05|2020-12-29|The Boeing Company|Graphene fiber for aerospace composites|
    US9434826B2|2015-01-05|2016-09-06|The Boeing Company|Graphene-augmented carbon fiber for aerospace composites|
    US10266677B2|2015-01-05|2019-04-23|The Boeing Company|Graphene-augmented composite materials|
    GB201517737D0|2015-10-07|2015-11-18|Cambridge Entpr Ltd|Layered materials and methods for their processing|
    DE102015120557A1|2015-11-26|2017-06-01|Daimler Ag|Pigment particles with a surface coating and coating composition with such pigment particles|
    WO2018011675A1|2016-07-13|2018-01-18|Semiconductor Energy Laboratory Co., Ltd.|Graphene compound, method for forming graphene compound, and power storage device|
    KR20180036107A|2016-09-30|2018-04-09|코오롱인더스트리 주식회사|Support, electrode for fuel cell, and membrane-electrode assembly, and fuel cell comprising the same|
    GB2565048A|2017-07-26|2019-02-06|Talga Tech Limited|Functionalised graphene composition|
    US20190119469A1|2017-10-24|2019-04-25|The Boeing Company|Compositions with coated carbon fibers and methods for manufacturing compositions with coated carbon fibers|
    US11214692B2|2017-12-04|2022-01-04|Hamilton Sundstrand Corporation|Increasing anti-corrosion through nanocomposite materials|
    CN109294407B|2018-09-14|2020-09-01|广东华科新材料研究院有限公司|Water-based anticorrosive paint and preparation method thereof|
    CN110211810B|2019-05-08|2021-07-06|广州理文科技有限公司|Crown ether supermolecule binding silver ion-based porous nano nickel network structure, super capacitor electrode and manufacturing method of super capacitor|
    CN110229588B|2019-07-16|2021-06-25|天津昌海新材料科技发展有限公司|Graphene composite nano-alloy underwater heavy-duty coating and preparation method thereof|
    JP2021057313A|2019-10-02|2021-04-08|矢崎総業株式会社|Terminal, terminal-attached electric wire using the same, and electrical connection member|
    US11021614B1|2020-03-10|2021-06-01|Tesla Nanocoatings, Inc.|Self-stratifying coatings|
    CN111253847A|2020-04-03|2020-06-09|中国南方电网有限责任公司超高压输电公司柳州局|Super corrosion-resistant composite anticorrosive paint and preparation method thereof|
    KR102324380B1|2020-04-17|2021-11-17|원광대학교산학협력단|Graphene nanoplate with high specific surface area and method for producing the same|
    CN113773732A|2021-09-10|2021-12-10|苏州己申隆新材料科技有限公司|Ice-coating-resistant super-slip polyurea coating for wind power blade and preparation method and application thereof|
    法律状态:
    2018-03-06| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2018-03-13| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2018-03-20| B06I| Publication of requirement cancelled [chapter 6.9 patent gazette]|Free format text: ANULADA A PUBLICACAO CODIGO 6.6.1 NA RPI NO 2462 DE 13/03/2018 POR TER SIDO INDEVIDA. |
    2018-03-27| B15K| Others concerning applications: alteration of classification|Ipc: C09C 1/46 (2006.01) |
    2021-03-16| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-04-20| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 30/01/2013, OBSERVADAS AS CONDICOES LEGAIS. |
    2022-02-22| B21F| Lapse acc. art. 78, item iv - on non-payment of the annual fees in time|Free format text: REFERENTE A 9A ANUIDADE. |
    优先权:
    申请号 | 申请日 | 专利标题
    USPCT/US2013/038852|2012-06-21|
    FI20120198|2012-06-21|
    PCT/US2013/038852|WO2013191809A1|2012-06-21|2013-04-30|Tunable materials|
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