MULTI-FUNCTIONAL SILIZANE-BASED COATINGS AND MATERIALS

Abstract

The present application is directed to a multifunctional coating for operation at temperatures in excess of 150° C., and up to 300+° C. The multifunctional coating includes: a) one or more polysilazanes (i.e., a group of silicon-based polymers) that include inorganic and/or organic functionalized polysilazane; b) one or more secondary polymeric additives one or more secondary polymeric additives (e.g., siloxane compounds and/or polysilane compounds); c) one or more optional functionalized nanoparticles and/or fillers; d) one or more optional additive polymers that include: i) Polysulfones (PSF) such as Polyethersulfone (PES) and/or Polyphenylene sulfide (PPS); ii) Polyimides (PI); iii) Polybenzimidazole (PBI); iv) Polybenzoxazoles (PBO); and/or v) fluoropolymers including Polytetrafluoroethylene (PTFE), Polyvinylidene fluoride or polyvinylidene difluoride (PVDF), Fluorinated ethylene propylene (FEP), and/or hexafluoropropylene (HFP); e) one or more optional additives (e.g., biocide, foaming agent, surface tension agent, pigment, curing agent, surface friction reducing agent, stabilizers, flexibilizers, inhibitors, flow control agents, anti-oxidants, degassing agents, dyes, coupling agent, dispersing agents, catalyst and/or hardeners; etc.); and f) one or more optional solvents; and which multifunctional coating is formulated such that it can optionally i) function as a high-temperature insulator, ii) have high elongation and/or improved hydrolytic stability, iii) have extreme weather resistance, iv) have high chemical resistance, v) have high impact and/or abrasion resistance, and/or vi) have improved thermal cycling resistance.

Claims

1. A multifunctional coating that can operate at temperatures in excess of 150° C.; said multifunction coating includes polysilazane, secondary polymeric additive, and one or more of filler, additive polymer and additive; said polysilazane constitutes at least wt. % of said multifunctional coating; said secondary polymeric additive constitutes at least 0.1 wt. % of said multifunctional coating; said secondary polymeric additive includes one or more polymers selected from the group consisting of siloxane compound and polysilane compounds; and wherein said multifunctional coating can i) function as a high-temperature insulator, ii) have high elongation and/or improved hydrolytic stability, iii) have extreme weather resistance, iv) have high chemical resistance, v) have high impact and/or abrasion resistance, and/or vi) have improved thermal cycling resistance.

2. The multifunctional coating as defined in claim 1, wherein said multifunctional coating includes at least 1 wt. % additive polymer; said additive polymer includes one or more compounds selected for the group consisting of polysulfones, polyimides, polybenzimidazole, polybenzoxazoles and fluoropolymers.

3. The multifunctional coating as defined in claim 1, wherein said multifunctional coating includes at least 1 wt. % filler; said filler includes one or more of nanoparticles, nanosheets and microspheres.

4. The multifunctional coating as defined in claim 1, wherein said multifunctional coating includes at least 1 wt. % additive; said additive includes one or more of biocide, foaming agent, surface tension agent, pigment, curing agent, surface friction reducing agent, stabilizers, flexibilizers, inhibitors, flow control agents, anti-oxidants, degassing agents, dyes, coupling agent, dispersing agents, catalyst and hardeners.

5. The multifunctional coating as defined in claim 1, wherein said polysilazane includes one or more compounds selected from the group consisting of trialkoxysilyl substituted polymethyl/polydimethylsilazane, propyltriethoxysilyl-substituted polymethyl (hydro)/polydimethylsilazane.

6. The multifunctional coating as defined in claim 1, wherein said siloxane includes one or more compounds selected from the group consisting of methylvinylsiloxanes, 1,3-divinyltetramethyldisiloxane, 1,3,5-trivinyl-1,3,5-trimethylcyclotrisiloxane, and 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane; said polysilane includes one or more compounds selected from the group consisting of tetraethyl-orthosilicate, methyltriethoxysilane, glycidyloxypropyltrimethoxysilane, 3-Aminopropyl triethoxysilane, dimethyl octadecylsilane, trimethoxymethylsilane, poly(dimethylsilylene), cyclopolysilanes, alkyltrihalosilane, trihalosilanes, phenyltrichlorosilane, tertiary butyltrichlorosilane, dodecyltrichlorosilane, poly(ethylene oxide-)-poly(1, 1-dimethyl-2, 2-dihexyldisilene), and poly(dimethylsilanediyl).

7. The multifunctional coating as defined in claim 1, wherein said multifunctional coating prior to be cured and/or hardened includes solvent; said solvent constitutes at least 1 wt. % of said multifunctional coating.

8. The multifunctional coating as defined in claim 1, wherein said multifunctional coating is corrosion resistance and has at least one additional functionality selected from the group consisting of a) high thermal conductivity of greater than 0.2 W-m-K, b) high dielectric breakdown strength above 500 V/mil, c) low flow resistance that is more than 30% lower than epoxy, d) a contact angle of greater than 90°, f) an oil contact angle of greater than 100°, g) reduced marine growth or adhesion of at least 30%, and h) a scratch resistance pencil hardness (ASTM D3363) of at least 6N.

9. The multifunctional coating as defined in claim 1, wherein said multifunctional coating is a high-temperature insulator that can be used to a) act as thermal insulators, thereby reducing the high exposure to temperature on the overlying layers, and therefore increasing thermal efficiency of the system while providing the necessary anti-corrosion protection, and/or b) act as a thermal insulator to the underlying layer(s), thereby serving to reduce the cold exposure temperature of the sea water, while possessing the physical properties necessary to resist damage during installation and service.

10. The multifunctional coating as defined in claim 1, wherein said multifunctional coating is used to prevent corrosion and fouling from marine growth to reduce energy use in shipping by at least 3% by reducing flow resistance.

11. The multifunctional coating as defined in claim 1, wherein said multifunctional coating remains bio-free over at least 50% of its surface after 9 months of seawater immersion, and where any growth after 12 months can be easily removed without abrasives.

12. The multifunctional coating as defined in claim 1, wherein said multifunctional coating is applied as a sealcoat over an epoxy or other corrosion-resistant coating, and which has a contact angle with water of greater than 100°.

13. The multifunctional coating as defined in claim 1, wherein said multifunctional coating can be used at at least 180° C. to replace a corrosion-resistant metal cladding in highly acidic environments including HCl and H.sub.2SO.sub.4.

14. The multifunctional coating as defined in claim 1, wherein said multifunctional coating has a thermal conductivity of at least 0.2 W/m-K, and is thermally stable to at least 250° C., with a breakdown strength of at least 500V/mil.

15. The multifunctional coating as defined in claim 1, wherein said multifunctional coating is formulated from neat or partially crosslinked resins added with a solvent where the solvent content is 3 to 7 lbs./gallon.

16. The multifunctional coating as defined in claim 1, wherein said multifunctional coating includes functionalized nanoparticle filler, said functionalized nanoparticle filler includes one or more materials selected from the group consisting of a fluorinated silane, silicone, or F-POSS (or precursor) functionalized inorganic particle with at least one dimension of less than 100 nm, said filler constituting at least 0.5 wt. % of said multifunctional coating.

17. The multifunctional coating as defined in claim 1, wherein said multifunctional coating includes inorganic fillers and pigments that constitute 1-30 wt. % of said multifunctional coating.

18. The multifunctional coating as defined in claim 1, wherein said multifunctional coating is used as a binder for magnetic particles.

19. The multifunctional coating as defined in claim 1, wherein said multifunctional coating is used as a thermal interface material or adhesive.

20. The multifunctional coating as defined in claim 1, wherein said multifunctional coating is formed as a thermoplastic film and applied by wrapping or extrusion onto a wire or other electrical conductor.

21. The multifunctional coating as defined in claim 1, wherein said multifunctional coating is formulated from neat or partially cross-linked resins added with a solvent where the solvent content is at least 1 lbs./gallon.

22. The multifunctional coating as defined in claim 21, wherein said solvent is absent reactive groups such as hydroxyl or amine groups.

23. The multifunctional coating as defined in claim 1, wherein a coating thickness of said multifunctional coating when dried is 0.1 to 20 mils.

24. The multifunctional coating as defined in claim 1, wherein said multifunctional coating includes functionalized nanoparticle filler, said functionalized nanoparticle filler includes one or more of fluorinated polyhedral oligomeric silsesquioxane (F-POSS), F-POSS (or precursor) functionalized inorganic particle, graphene, graphene oxide, fumed silica nano-ceramics, boron nitride nanosheets, carbon nanotubes, nanoclays, exfoliated nano-fillers, nano-cermets, and nanofibers including conductive nanofibers or other functionalized inorganic particle, said functionalized nanoparticle filler has at least one dimension of less than 100 nm.

25. The multifunctional coating as defined in claim 24, wherein said functionalized nanoparticle filler constitutes at least 0.5 wt. % of said multifunctional coating.

26. The multifunctional coating as defined in claim 24, wherein said functionalized nanoparticle filler is functionalized with a fluorinated silane or silicone.

27. The multifunctional coating as defined in claim 1, wherein said multifunctional coating includes inorganic fillers and pigments that constitute 1-30 vol. % of said multifunctional coating.

28. The multifunctional coating as defined in claim 1, wherein said multifunctional coating is formulated in liquid form.

29. The multifunctional coating as defined in claim 1, wherein said multifunctional coating is formulated in powder form.

30. The multifunctional coating as defined in claim 1, wherein said multifunctional coating hardened, converted, initiated, catalyzed, crosslinked, or otherwise cured, including multiple stage curing, by use of chemical catalyst, UV, IR, moisture, and/or thermal mechanisms.

31. The multifunctional coating as defined in claim 1, wherein said multifunctional coating can be applied by use of a brush, a roller, a pad, a wipe, vapor deposition, deposition, powder spray, and/or sprayer.

32. The multifunctional coating as defined in claim 1, wherein said multifunctional coating is of sufficient fluid characteristic or viscosity to seal microporosity in the underlying epoxy or other corrosion resistant coating.

33. The multifunctional coating as defined in claim 1, wherein said multifunctional coating is used to withstand abrasion and adhesive sticking or build-up of granular and particle materials such as plastic pellets, grain and related foodstuffs, ground minerals, and wood chips.

34. The multifunctional coating as defined in claim 1, wherein said multifunctional coating is applied to the interior of storage tanks, transport tanks, transport hoppers, ship hulls, rail cars, feed hoppers, silos, stacks, ducts, and secondary chemical containment dykes and/or trenches.

35. The multifunctional coating as defined in claim 1, wherein said multifunctional coating is applied to a wire, an electrical cable, a hose, and/or a flexible pipe.

36. The multifunctional coating as defined in claim 1, wherein said multifunctional coating is applied to metal, glass, ceramic, concrete, plastics, composites, reinforced composite plastics, and/or thermally resistant composite material.

Description

DETAILED DESCRIPTION OF THE DISCLOSURE

[0135] A more complete understanding of the articles/devices, processes and components disclosed herein can be obtained by reference to the accompanying drawings. These figures are merely schematic representations based on convenience and the ease of demonstrating the present disclosure, and are, therefore, not intended to indicate relative size and dimensions of the devices or components thereof and/or to define or limit the scope of the exemplary embodiments.

[0136] Although specific terms are used in the following description for the sake of clarity, these terms are intended to refer only to the particular structure of the embodiments selected for illustration in the drawings and are not intended to define or limit the scope of the disclosure. In the drawings and the following description below, it is to be understood that like numeric designations refer to components of like function.

[0137] The singular forms “a,” “an,” and “the” include plural referents unless the context clearly dictates otherwise.

[0138] As used in the specification and in the claims, the term “comprising” may include the embodiments “consisting of” and “consisting essentially of.” The terms “comprise(s),” “include(s),” “having,” “has,” “can,” “contain(s),” and variants thereof, as used herein, are intended to be open-ended transitional phrases, terms, or words that require the presence of the named ingredients/steps and permit the presence of other ingredients/steps. However, such description should be construed as also describing compositions or processes as “consisting of” and “consisting essentially of” the enumerated ingredients/steps, which allows the presence of only the named ingredients/steps, along with any unavoidable impurities that might result therefrom, and excludes other ingredients/steps.

[0139] Numerical values in the specification and claims of this application should be understood to include numerical values which are the same when reduced to the same number of significant figures and numerical values which differ from the stated value by less than the experimental error of conventional measurement technique of the type described in the present application to determine the value.

[0140] All ranges disclosed herein are inclusive of the recited endpoint and independently combinable (for example, the range of “from 2 grams to 10 grams” is inclusive of the endpoints, 2 grams and 10 grams, all the intermediate values and all intermediate ranges).

[0141] The terms “about” and “approximately” can be used to include any numerical value that can vary without changing the basic function of that value. When used with a range, “about” and “approximately” also disclose the range defined by the absolute values of the two endpoints, e.g., “about 2 to about 4” also discloses the range “from 2 to 4.” Generally, the terms “about” and “approximately” may refer to plus or minus 10% of the indicated number.

[0142] Percentages of elements should be assumed to be percent by weight of the stated element, unless expressly stated otherwise.

[0143] The present disclosure relates to functionalized silicone-based coating compositions that are formulated from certain silicone-based polymers combined with optimizing compatible chemistries and functionalized fillers to make high-performance coatings with advanced properties.

[0144] The multifunctional coating that can operate at temperatures in excess of 150° C. The multifunction coating includes polysilazane, secondary polymeric additive, and one or more of filler, additive polymer and additive. The polysilazane constitutes at least wt. % of the multifunctional coating. The secondary polymeric additive constitutes at least 0.1 wt. % of the multifunctional coating. The secondary polymeric additive includes one or more polymers selected from the group consisting of siloxane compound and polysilane compounds. The multifunctional coating can i) function as a high-temperature insulator, ii) have high elongation and/or improved hydrolytic stability, iii) have extreme weather resistance, iv) have high chemical resistance, v) have high impact and/or abrasion resistance, and/or vi) have improved thermal cycling resistance.

[0145] One non-limiting embodiment, the multifunctional coating can includes a) 3-40 wt. % (and all values and ranges therebetween) polysilazanes, b) 1-50 wt. % (and all values and ranges therebetween) polysiloxane compound and/or polysilane compound, c) optionally 3-60 wt. % (and all values and ranges therebetween) of one or more treated and/or surface functionalized platelet and/or non-platelet nanoparticle fillers having a size of 5-10,000 nm (and all values and ranges therebetween), wherein the filler includes, but is not limited to, fluorinated polyhedral oligomeric silsesquioxane (F-POSS), graphene, graphene oxide, fumed silica nano-ceramics, boron nitride nanosheets, carbon nanotubes, nanoclays, exfoliated nano-fillers, and/or nanofibers including conductive nanofibers, d) optionally 1-30 wt. % (and all values and ranges therebetween) additive polymer such as, but not limited to, a fluoropolymer, polysulfone, polyamide, polyimides, polybenzimidazole, or polybenzobisoazole, and e) optionally 1-40 wt. % (and all values and ranges therebetween) additives used to finished composition to complete its intended service such as, but not limited to, thermosetting or thermoplastic monomers and/or macromers, polymerized silane, oligomers, cyclic, polycyclic, heterocyclic, linear and/or branched polymer resins, crystalline, semi-crystalline, non-crystalline or amorphous thermoplastic or thermosetting resins, non-leaching biocides such as nano selenium, stabilizers, flexibilizers, inhibitors, curing agents including UV curing agents, liquid and solid resin catalysts, hardeners, flow control agents, anti-oxidants, degassing agents, ceramic microspheres, pigments, dyes, and/or dispersing agents.

[0146] The multifunctional coating composition may be optionally formulated using primarily dry solid components without the use of solvent where the compounds, functional additives, and curatives or hardener are blended in dry form and combined using a high-speed mixer. The mixed dry composition can be fed through an extrusion blender or equal thermal process at a preestablished temperature generally 50° C.-100° C. (and all values and ranges therebetween). Because of the fast operation of the extruder and relatively low temperature within the barrel, the composition which includes the curing agent(s) or hardener components will not undergo a significant chemical reaction. The multifunctional coating composition can be produced in pellet, bead or chip form, where it is ground using high speed grinders to a particle size generally less than 150 microns. Alternately, the curing agent(s) or hardener may be produced in powder form and dry blended or mixed separately and added to the ground composition in a separate blending process. Several types of curing agents or hardeners may be used either together or separately depending upon the composition and the additives. The selection of the curing agent(s) or hardener can have a significant impact on the cross-linking density, chemical resistance, brittleness, flexibility, etc. The powdered multifunctional coating composition can be applied to a prepared steel surface using conventional electrostatic spray at a thickness generally between 0.5 mils (12.5 microns and 20+ mils (500+ microns) (and all values and ranges therebetween). The steel surface is generally heated to a temperature of 210° C. to 240° C. (and all values and ranges therebetween) where the applied powder composition melts and solidifies to form a uniform dense protective layer.

[0147] Non-limiting examples of the multifunctional coating composition are set forth as follows in weight percent:

TABLE-US-00001 Component Ex. 1 Ex. 2 Ex. 3 Polysilazane 3-50% 10-50%  10-45%  Secondary polymeric 0.1-50%.sup.  0.1-50%.sup.  0.1-50%.sup.  additive Filler 0-60% 2-60% 3-60% Additive polymer 0-40% 1-40% 1-40% Additive 0-40% 1-40% 1-40% Solvent 1-50% 1-50% 1-50% Component Ex. 4 Ex. 5 Ex. 6 Polysilazane 20-40%  20-35%  25-35%  Secondary polymeric 1-30% 2-30% 5-25% additive Filler 3-50% 4-40% 5-30% Additive polymer 1-30% 2-30% 5-25% Additive 1-20% 1-20% 1-15% Solvent 5-40% 10-40%  10-35%  Component Ex. 7 Ex. 8 Ex. 9 Durazane ™ 1500 Fast Cure 20-35% 20-35% 20-35% Polysilane 10-35% 10-30% 12-30% Nanoparticles (e.g.,  2-25%  5-20%  5-15% silica, carbon, metal, carbon nanofiber) Polyimide or  8-30% 10-30% 10-25% Fluoropolymer Additive (e.g., coupling  1-20%  1-20%  1-15% agent, pigment, biocide, antifoaming agent, flow agent, surface tension agent, etc.) Solvent 10-40% 15-40% 15-35%

[0148] In Examples 1-9, it will be appreciated that all of the above ranges include any value between the range and any other range that is between the ranges set forth above.

Example 10

[0149] A multifunctional coating that is formulated to seal and protect high temperature steel surfaces up to 350° C. from corrosion commonly experienced under thermal insulation barriers. The multifunctional coating is formed of at least 30 wt. % polysilazane resin such as Durazane™ 1500 fast cure, at least 0.2 wt. % fluorosilane coupling agent such as Novec™ 1720, at least 10 wt. % polyimide such as compounded heterocyclic polyimide, at least 10 wt. % surface treated AL nanocomposite powder, at least 2 wt. % treated carbon nanofiber, at least 30 wt. % low moisture organic solvent such as ethyl acetate, butyl acetate, propylene glycol methyl ether acetate or fluoruos solvent, optionally at least 2 wt. % dicumyl peroxide as a curing agent, and optionally 1-2 wt. % additives to assist in flow, eliminate foaming, control surface tension, pigments, or as commonly used in the general practice. This unique multifunctional coating displays excellent physical and mechanical properties such as hardness, flexibility, impact resistance, adhesion, permeation resistance and chemical resistance. The multifunctional coating can be applied to a surface by spray or brush at a thickness ranging on average from 1.5 mils to 5 mils, allowed to dry, and thermally cures at a temperature greater than 250° C. (which can be achieved by an oven, induction heating, or in maintenance situations putting into service).

Example 11

[0150] A multifunctional coating can be formulated to resist growth of marine organisms while providing a smooth, high wear resistant, omniphobic to near super hydrophobic protective surface coating for marine vessels. The multifunctional coating is formed of at least 25 wt. % polysilazane such as Durazane™ 1500 fast cure, at least 10 wt. % polymerized polysilane, at least 10 wt. % fluorinated ethylene propylene (FEF), at least 0.2 wt. % fluorosilane coupling agent such as Novec™ 1720, at least 5 wt. % treated silica nanoparticles, at least 2 wt. % non-leaching biocide such treated selenium nanoparticles, at least 20 wt. % low moisture organic solvent such as ethyl acetate, butyl acetate, propylene glycol methyl ether acetate or fluoruos solvent, and optionally 1-2 wt. % additives to assist in flow, eliminate foaming, control surface tension, pigments, and at least 2 wt. % catalyst/hardening agent such as 1,8-Diazabicyclo(5.4.0)undec-7-ene (DBU).

Example 12

[0151] A multicomponent coating similar to Example 1 wherein a hardening agent is additionally added. The hardening can be added just prior to the application of the multifunctional coating to a surface. A hardening agent such as, but not limited to, at least 2 wt. % catalyst/hardening agent such as 1,8-Diazabicyclo(5.4.0)undec-7-ene (DBU). This multifunctional coating can be applied by spray or brush at a thickness ranging on average from 3 mils to 8 mils and allowed to cure for at least 8 hours at an average temperature of 21° C. prior to immersion.

[0152] It will thus be seen that the objects set forth above, among those made apparent from the preceding description, are efficiently attained, and since certain changes may be made in the constructions set forth without departing from the spirit and scope of the disclosure, it is intended that all matter contained in the above description and shown in the accompanying drawings shall be interpreted as illustrative and not in a limiting sense. The disclosure has been described with reference to preferred and alternate embodiments. Modifications and alterations will become apparent to those skilled in the art upon reading and understanding the detailed discussion of the disclosure provided herein. This disclosure is intended to include all such modifications and alterations insofar as they come within the scope of the present disclosure. It is also to be understood that the following claims are intended to cover all of the generic and specific features of the disclosure herein described and all statements of the scope of the disclosure which, as a matter of language, might be said to fall therebetween. The disclosure has been described with reference to the preferred embodiments. These and other modifications of the preferred embodiments, as well as other embodiments of the disclosure, will be obvious from the disclosure herein, whereby the foregoing descriptive matter is to be interpreted merely as illustrative of the disclosure and not as a limitation. It is intended to include all such modifications and alterations insofar as they come within the scope of the appended claims.