Siliceous repair composition and related methods

Abstract

A repair composition has at least a first part and a second part. The first part includes an aqueous silicate, which may be an alkali silicate, ammonium silicate, or a combination of an alkali silicate and ammonium silicate. The second part includes a chemical curing agent and a liquid carrier. At least one of the first part or the second part includes particulate filler. At least one of the first part or the second part includes a humectant, and the humectant may or may not be the liquid carrier. Methods of using the repair composition and use of a cementitious repair composition for a non-cementitious damaged surface are also described.

Description

[0001] PA101655W002

[0002] SILICEOUS REPAIR COMPOSITION AND RELATED METHODS

[0003] Cross-Reference to Related Application

[0004] This application claims priority to U.S. Provisional Application Nos. 63 / 684.717. filed August 19, 2024, and 63 / 860.446. filed August 8, 2025, the disclosures of which are incorporated by reference in their entirety herein.

[0005] Background

[0006] Automobile body repair is often carried out with a body repair compound, also called body filler. A body repair compound can include a thermosetting resin, fillers, promoters, and other additives that are mixed with a catalyst to facilitate cross-linking at room temperature. After mixing, a technician spreads the body filler onto a damaged surface, allows the body filler to harden, and then sands the hardened body filler to conform to the desired surface contour. The process can be repeated two or more times until the damaged area of the vehicle is sufficiently filled, and the contour of the original surface is matched.

[0007] Automotive body fillers often include unsaturated polyester resins. Unsaturated polyester resins typically contain a,P-unsaturated polyesters and 30 to 50 percent by weight copolymerizable monomers. Styrene, due to its well-understood reactivity profiles with unsaturated polyester resins and other monomers and its relatively low cost, is by far the dominant copolymerizable monomer used in unsaturated polyester resins.

[0008] Some styrene-free body filler compositions have been described. See, for example, JP2005255937, published Sep. 22, 2005, U.S. Pat. No. 5.068.125 (Meixner et al.), and U.S. Pat. Appl. Pub Nos. 2020 / 0199400 (Xu et al.). 2022 / 0025122 (Yang et al.), 2022 / 0081556 (Yang et al.), 2022 / 0081555 (Xu et al.), and 2023 / 0051188 (Xu et al.).

[0009] Summary

[0010] The present disclosure provides a repair composition that includes at least a first part and a second part, the first part comprising an aqueous silicate and a second part comprising a chemical curing agent for the silicate. Typically, and advantageously, after combining the first part and the second part, the resulting composition is curable at a temperature of not more than 60 °C or. in some embodiments, room temperature and can provide adhesion and sanding properties comparable to existing body fillers.

[0011] In one aspect, the present disclosure provides a repair composition having at least a first part and a second part. The first part includes an aqueous silicate, which may be an alkali silicate, ammonium silicate, or a combination of an alkali silicate and ammonium silicate. The second part includes a chemical curing agent for the silicate and a liquid carrier. At least one of the first part or the second part comprises particulate filler. At least one of the first part or the second part comprises a humectant, and the humectant may or may not be the liquid carrier. In another aspect, the present disclosure provides the use of such a repair composition as a repair composition for a damaged surface.

[0012] In another aspect, the present disclosure provides method of repairing a damaged surface. The method includes combining the first part and the second part of the repair composition to provide a curable composition, applying the curable composition to the damaged surface, and curing the curable composition on the damaged surface to provide a cured composition.

[0013] In another aspect, the present disclosure provides the use of a cementitious composition as repair composition for a non-cementitious surface.

[0014] In another aspect, the present disclosure provides a method of repairing a non-cementitious damaged surface. The method includes applying a cementitious repair composition to the non- cementitious damaged surface and curing the repair composition on the non-cementitious damaged surface to provide a cured composition.

[0015] In another aspect, the present disclosure provides a kit comprising the first part and the second part of the repair composition. The first part and the second part are separately packaged.

[0016] In this application, terms such as "a", "an" and "the" are not intended to refer to only a singular entity but include the general class of which a specific example may be used for illustration. The terms "a", "an", and "the" are used interchangeably with the term "at least one".

[0017] The phrases "at least one of' and "comprises at least one of' followed by a list including the conjunction “of refers to any one of the items in the list and any combination of two or more items in tire list.

[0018] The term “ceramic" as used herein refers to glasses, cry stalline ceramics, glass-ceramics, and combinations thereof.

[0019] The term “aqueous silicate" refers to a silicate dissolved in water or a water-containing liquid.

[0020] The term “chemical curing agent” refers to a material that initiates and / or enhances solidification of an aqueous silicate solution; solidification implies polycondensation of dissolved silica into three- dimensional Si-O-Si bond network, with the possibility’ of other elements (e.g., Al, B, P) in die network, and / or crystallization of new phases; a chemical curing agent can be present at least partially as a reaction product of the formulated chemical curing agent and the silicate.

[0021] The term “humectant" refers to a material, which may or may not be hygroscopic, that reduces evaporation of water from cement.

[0022] A cementitious composition is a composition containing inorganic material that hardens through hydration.

[0023] A non-cementitious surface is a surface that is not cementitious and / or not formed from a cementitious composition as defined above.

[0024] The term “liquid” refers to being able to flow at room temperature.

[0025] The term “room temperature” as used herein refers to a temperature of about 20 °C to 25 °C. The terms "cure" and “curable” refer to making polymer chains from one or more monomers.

[0026] The term “crosslinked” refers to joining polymer chains together by bonds comprising covalent chemical bonds, ionic bonds, hydrophobic / hydrophilic associations, usually via crosslinking molecules or groups, to form a network. In the present case, formation of polymer chains and crosslinking of polymer chains can occur simultaneously. Therefore, in this disclosure the terms “cured” and “crosslinked” may be used interchangeably. The term “cured” encompasses partially cured.

[0027] The term “particulate filler” refers to a small distinct piece or individual part of a material (i.e., a primary particle) or aggregate thereof in finely divided form. Primary particles can include flakes, powders, and fibers, and may clump, physically intermesh, electrostatically associate, or otherwise associate to form aggregates. The particulate filler is not soluble in the first part, the second part, or the curable composition.

[0028] All numerical ranges are inclusive of their endpoints and integral and non-integral values between the endpoints unless otherwise stated (e.g. 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80. 4, and 5).

[0029] The above summary of the present disclosure is not intended to describe each disclosed embodiment or every implementation of the present disclosure. The description that follows more particularly exemplifies illustrative embodiments. It is to be understood, therefore, that the following description should not be read in a manner that would unduly limit the scope of this disclosure.

[0030] Detailed Description

[0031] The repair composition of the present disclosure comprises a first part and a second part. The first part comprises an aqueous silicate, and the second part comprises a chemical curing agent for the silicate and a liquid carrier. The repair composition may be a two-part composition of the first part and the second part, or it may have additional parts (e.g., third and fourth parts) that can be combined with the first part and the second part.

[0032] The first part comprises at least one of an alkali silicate or ammonium silicate. Suitable alkali silicates include cesium silicate, lithium silicate, a potassium silicate, a sodium silicate, and combinations thereof. In some embodiments, the alkali silicate comprises at least one of lithium silicate, sodium silicate, or potassium silicate. In some embodiments, the alkali silicate comprises sodium silicate.

[0033] Alkali silicates can be obtained, for example, as aqueous solutions or solid spray -dried powders from commercial sources, for example, PQ Corporation, Malvern, PA. Suitable lithium silicates can be obtained, for example, from PQ Corporation under the trade designations “LITHISIL 829” and “LITHISIL 25”. Further suitable alkali silicates are sodium silicates having a weight ratio of SiCCNazO in a range from 1.6 to 2.5 and potassium silicates with a weight ratio of SiCKfQO in a range from 1.6 to 2.5. Other suitable alkali silicates include sodium or ammonium stabilized silica sols such as those available from Nalco Company, Naperville, Ill. Useful concentrations in the silicate solutions include at least 40 % to 42 % by weight solids, and the weight ratio of silicon dioxide to lithium, sodium, or potassium oxide is typically in a range from 1:1 to 10:1. In some embodiments, the alkali silicate has a molar ratio of silicon to alkali metal of not more than 3.22 to 1. In the case of solid silicates, rapidly dissolving, spray dried powders can be useful. These powders typically contain approximately 20 wt. % water in their structures. Suitable alkali silicate powders include those available, for example, from PQ Corporation under trade designations "BRITESIL C 205” and “KASOLV 16”. When solid alkali silicate powders are used, water is typically added to make the aqueous silicate.

[0034] Ammonium silicate, also called ammonium metasilicate, has the chemical formula ('NH tySiCF. and is typically obtained as a solution in water. Ammonium silicate can be made from the reaction of sodium silicate and ammonium chloride.

[0035] The second part comprises a chemical curing agent for the silicate. Examples of suitable chemical curing agents include an aluminum phosphate (e.g., aluminum phosphate or aluminum dihydrogen phosphate), a fluorosilicate (e.g., NazSiFs. also called sodium silicofluoride), a borate (e.g., zinc borate, ammonium pentaborate, potassium pentaborate, potassium tetraborate), Portland cement, sulfoaluminate cement, magnesium phosphate cement, gypsum, a cry olite (e.g., NazAIF,,). dibasic esters, a multivalent salt of a weak acid, fluoroaluminosilicate, zinc aluminate, and combinations thereof. Examples of suitable dibasic esters includes diethyl succinate, dimethyl succinate, dimethyl glutarate, diethyl glutarate, diethyl adipate, dibutyl adipate, diethyl malonate, dimethyl azelate, diisobutyl adipate, and combinations thereof. Examples of suitable multivalent salts of weak acids, which may be used alone or in combination, include di- and trivalent salts of sulfurous acid, phosphoric acid, methonoic acid, hydrofluoric acid, hydrocyanic acid, carbonic acid, acetic acid, and nitrous acid in which examples of suitable cations include zinc, magnesium, calcium, iron, cobalt, boron, chromium, titanium, and beryllium. In some embodiments, the chemical curing agent comprises at least one of aluminum phosphate, aluminum dihydrogen phosphate, sodium fluorosilicate, fluoroaluminosilicate, or zinc borate.

[0036] Chemical curing agents such as aluminum phosphate or aluminum dihydrogen phosphate can be obtained from a variety of commercial sources such as BassTech International, Fort Lee. NJ. (which acquired Budenheim, Inc., Budenheim, Germany) under the trade designation "FABUT1T”; Solvay Fluorides. LLC, Houston, TX, USA. Chemical curing agents such as fluoroaluminosilicate can be obtained from a variety of commercial sources such as Schott North America. Inc., Rye Brook. NY, USA. Chemical curing agents such as sodium fluorosilicate and zinc borate can be obtained from a variety of commercial sources such as Solvay Fluorides, LLC, Houston. TX; BASF, Florham Park, NJ; and fine chemical suppliers.

[0037] In some embodiments, the chemical curing agent is reactive with the alkali silicate or ammonium silicate at a temperature of not more than 60 °C, in some embodiments, not more than 50 °C, 40 °C, 30 °C. or 25 °C. In some embodiments, advantageously, the chemical curing agent is reactive with the alkali silicate or ammonium silicate at room temperature.

[0038] Although aluminosilicate (e.g., metakaolin and kaolinite) are known curing agents for alkali silicates, these clays typically require an elevated temperature, for example, higher than 30 °C or higher than 60 °C, to react with an alkali silicate or an ammonium silicate. In some embodiments, the chemical curing agent is other than an aluminosilicate. In some embodiments, the second part is free of an aluminosilicate. In some embodiments, the chemical curing agent is other than attapulgite. In some embodiments, the second part is free of attapulgite.

[0039] As a two-part composition, the first part does not include the chemical curing agent or is essentially free of the chemical curing agent, and the second part does not include or is essentially free of the alkali silicate and / or ammonium silicate. The term “essentially free of’ means having not more than 0. 1 wt.%, 0.05 wt.%, 0.01 wt.%. or 0.001 wt.% of the chemical curing agent, based on the total weight of the first part. Likewise, the term “essentially free of’ means having not more than 0.1 wt.%, 0.05 wt.%. 0.01 wt.%. or 0.001 wt.% of alkali silicate and / or ammonium silicate, based on the total weight of the second part.

[0040] When the first part and the second part are combined, the silicate reacts with at least one chemical curing agent to form a siliceous netw ork. The reaction of the alkali silicate and the hardener typically produces an amorphous polymeric =Si-O-Si= netw ork, w ith the possibility of other elements (c.g., Al, B, P) in the network, structural water in form of OH groups, and crystalline byproducts such as MxFyand Mx(PO4)y or mixed salts thereof w here M is Li, Na, K, Ca, or Mg, and w herein x and y depend on the valence of the metal. The amorphous network is considered a gel. As used herein, a "gel" is a three- dimensional network of solids dispersed in a liquid. In some embodiments, in w hich the network includes Al, the network has a Si:Al ratio of at least 1 : 1 and up to 20: 1, 25: 1, 100: 1, 200: 1. or 300: 1. In some embodiments, the Si:Al ratio is greater than 15:1, greater than 20: 1, or at least 25: 1 and up to 100: 1. 200: 1. or 300: 1. A high Si: Al ratio (e.g., higher than 15: 1) may provide a more flexible network.

[0041] At least one of the first part or the second part of the repair composition of the present disclosure includes particulate filler. In some embodiments, the first part includes particulate filler. In some embodiments, both the first part and the second part include particulate filler. Particulate filler is a solid that is not soluble in the first part, the second part, or the combination thereof. In some embodiments, the particulate filler comprises at least one of ceramic beads (e.g.. glass beads), polymer beads, silica, hollow ceramic elements (e.g., hollow glass microspheres), hollow polymeric elements, alumina, zirconia, mica, dolomite, wollastonite, fibers (e.g., glass, crystalline ceramic, or polymeric), talc, calcium carbonate, sodium metaborate, or clay. Examples of useful fibers include poly crystalline aluminosilicate fibers, glass fibers such as e-glass, c-glass, r-glass, s-glass, and s2-glass, and refractory ceramic fiber. Such fillers, alone or in combination, can be present in the composition according to the present disclosure in a range from 10 percent by w eight to 70 percent by weight, in some embodiments. 20 percent by w eight to 60 percent by weight or 40 percent by w eight to 60 percent by weight, based on the total w eight of the composition. Silica, alumina, and zirconia, for example, can be of any desired size, including particles having an average size above 1 micrometer, between 100 nanometers and 1 micrometer, and below 100 nanometers. Silica can include nanosilica and amorphous fumed silica, for example. As noted above, when an aluminosilicate clay does not serve as a chemical curing agent in the repair composition, it may be present as a particulate filler.

[0042] Useful polymer beads, hollow elements, and fibers include those made from thermoplastic polymers (e.g., polycarbonate, polyetherimide, polyester, polyethylene, polysulfone, polystyrene, acrylonitrile-butadiene-styrene block copolymer, polypropylene, acetal polymers, polyurethanes, and nylon particles) and thermosetting polymers (e.g., phenolic bubbles, phenolic beads, and polyurethane foam particles). Pre-expanded polymeric microspheres are commercially available, for example, from Chase Corporation of Westwood, Mass., under the trade designation ‘"DU ALITE”. The pre-expanded polymeric microspheres may include a polymer shell comprising, for example, at least one of an acrylonitrile / acrylate copolymer or a vinylidenechloride / acrylonitrile copolymer. The shell encapsulates a core including, for example, one or more essentially gaseous hydrocarbons.

[0043] Hollow ceramic elements can include hollow spheres and spheroids. Examples of commercially available materials suitable for use as the hollow, ceramic elements include glass bubbles marketed by 3M Company, Saint Paul, Minnesota, as “3M GLASS BUBBLES” in grades KI, K15, K20, K25, K37, K46, S15, S22, S32, S35, S38, S38HS, S38XHS, S42HS, S42XHS, S60, S60HS, iM30K, iM16K, XLD3000, XLD6000, and G-65, and any of the HGS scries of “3M GLASS BUBBLES”; glass bubbles marketed by Potters Industries, Carlstadt, N.J., under the trade designations "Q-CEL HOLLOW SPHERES" (e.g., grades 30, 6014, 6019, 6028, 6036, 6042, 6048, 5019, 5023. and 5028); and hollow glass particles marketed by Silbrico Corp., Hodgkins, IL under the trade designation "SIL-CELL" (e.g., grades SIL 35 / 34, SIL-32, SIL-42, and SIL-43). The hollow, ceramic elements may also be made from ceramics such as alpha-alumina, zirconia, and alumina silicates. In some embodiments, the hollow, ceramic elements are aluminosilicate microspheres extracted from pulverized fuel ash collected from coal-fired power stations (i.e., cenospheres). Useful cenospheres include those marketed by Sphere One, Inc., Chattanooga, TN, under the trade designation "EXTENDOSPHERES HOLLOW SPHERES" (e g . grades SG, MG, CG. TG, HA, SLG, SL-150, 300 / 600, 350 and FM-1). Other useful hollow, ceramic spheroids include silica-alumina ceramic hollow spheres with thick walls marketed by Valentine Chemicals of Lockport, Louisiana, as ZEEOSPHERES CERAMIC MICROSPHERES in grades N-200, N-200PC. N-400, N-600. N-800, N1000, and N1200. The hollow ceramic elements may have one of a variety of useful sizes but typically has a maximum dimension, or average diameter, of less than 10 millimeters (mm), more typically less than one mm. In some embodiments, the hollow ceramic elements have a maximum dimension in a range from 0.1 micrometer to one mm. from one micrometer to 500 micrometers, from one micrometer to 300 micrometers, or even from one micrometer to 100 micrometers. The mean particle size of the hollow, ceramic elements may be. for example, in a range from 5 to 250 micrometers (in some embodiments from 10 to 110 micrometers, from 10 to 70 micrometers, or even from 20 to 40 micrometers). As used herein, the term size is considered to be equivalent with the diameter and height, for example, of glass bubbles. In some embodiments, each of the fdlers in the composition according to the present disclosure has a mean particle size up to 100 micrometers as described in U.S. Pat. No. 8.034,852 (Janssen et al.).

[0044] Compositions according to the present disclosure can also include dyes, pigments (e.g., iron oxide, titanium dioxide, certain clays, and carbon black), and rheology modifiers (e.g.. fumed silica or clay). Examples of useful clay pigments include kaolin clays, for example, obtained under the trade designation "BURGESS OPTIWHITE MX” and "BURGESS POLYCLAY” from Burgess Pigment Company, Sandersville. GA. Examples of suitable rheology modifiers include partially disordered / dehydrated kaolinite or halloysite (ALSi2O4OH) i). fibrous wollastonite (CaSiO,). and amorphous micro silica (SiOz), such as hydrophilic fumed silica. These additives, as a component of the particulate filler, may be present in an amount of up to five percent by weight, based on the total weight of first part, the second part, or the curable composition of the combined first part and second part.

[0045] In some embodiments, the particulate filler is other than metal particles. For example, in some embodiments, the particulate filler is other than aluminum, an aluminum alloy, zinc (e.g., zinc powder), iron, copper, silver, chromium, titanium, tungsten, nickel. In some embodiments, the first part, the second part, or the curable composition of the combined first part and second part is essentially free of or free of any of or all of these metal particles. The term “essentially free of’ metal particles means having not more than 1 wt.%, 0.5 wt.%, 0.1 wt.%, 0.05 wt.%, 0.01 wt.%, or 0.001 wt.% of any of these metal particles, based on the total weight of the first part, the second part, or the curable composition of the combined first part and the second part.

[0046] At least one of the first part or the second part of the repair composition of the present disclosure includes a humectant. In some embodiments, the second part includes a humectant. In some embodiments, both the first part and the second part include a humectant. Useful humectants include liquid humectants. When the humectant is liquid, it may be the liquid carrier in the second part of the repair composition or a component of the liquid carrier. In some embodiments, the humectant comprises at least one of 1,4-butanediol. propylene carbonate, glycerol, glycerin, glycerin carbonate, propylene glycol, ethylene glycol, dipropylene glycol, tripropylene glycol, or triethanolamine, each of which is a liquid. Useful humectants also include lactic acid and sugar alcohols, for example, at least one of sorbitol, maltitol, xylitol, or erythritol. Sorbitol can be obtained neat or as a solution in water (e.g.. 70 wt.% from WEGO Chemical Group. Great Neck. NY, USA). In some embodiments, the humectant comprises at least one of lactic acid, 1.4-butanediol, propylene carbonate, glycerol, glycerin carbonate, polypropylene glycol, dipropylene glycol, or tripropylene glycol. The humectant, which reduces evaporation of water from the cement, may be useful, for example, for preventing cracking of the repair composition resulting from the combination of the first part and the second part. The choice of humectant can alter the curing rate of the alkali silicate or ammonium silicate and the chemical curing agent.

[0047] The second part includes a liquid carrier. Suitable liquid carriers include the liquid humectants described above. In some embodiments, the liquid carrier comprises water. Water may be useful in the second part in combination with one or more liquid humectants described above. In some embodiments, water is present (as part of the aqueous silicate) in the first part in up to 80 (in some embodiments, up to 75, 70, 65, 60. 55, 50, 45, 40. 35. or up to 30) percent by weight, based on the total weight of the first part. In some embodiments, water is present in the first part in a range from 20 to 70, 20 to 60, or 20 to 55 percent by weight, based on the total weight of the first part. Having at least 10% by weight water in the first part facilitates the mixing of the first part and the second part. In some embodiments, an alkali or ammonium silicate (as part of the aqueous silicate) is present in the first part in up to 30 (in some embodiments, up to 25, 20, 15, 10. or up to 5) percent by weight, based on the total weight of the first part. In some embodiments, an alkali or ammonium silicate is present in the first part in a range from 2 to 30. 5 to 30. or 5 to 25 percent by weight, based on the total weight of the first part.

[0048] In some embodiments, particulate filler is present in the first part, the second part, or the curable composition of the combined first part and second part in up to 85, 80, 75. 70, 65, 60, 55, 50, 45, 40, 30, or 25 percent by weight, based on the total weight of the first part, the second part, or the curable composition. In some embodiments, particulate filler is present in the first part in a range from 10 to 85, 15 to 75, 20 to 60, or 25 to 50 percent by weight, based on the total weight of the first part, the second part, or the curable composition. In some embodiments, particulate filler is present in the first part in up to 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 30, or 25 percent by weight, based on the total weight of the first part. In some embodiments, particulate filler is present in tire first part in a range from 10 to 85, 15 to 75, 20 to 60, or 25 to 50 percent by weight, based on the total weight of the first part.

[0049] In some embodiments, the chemical curing agent is present in the second part in up to 80 (in some embodiments, up to 75, 70, 65, 60, 55. or up to 50) percent by weight, based on the total weight of the second part. In some embodiments, the chemical curing agent is present in the second part in a range from 30 to 80, 40 to 80, or 50 to 80 percent by weight, based on the total weight of the second part. In some embodiments, the liquid carrier, which may include the humectant, is present in the second part in at least 20 (in some embodiments, at least 25, 30, or 35) percent by weight, based on the total weight of the second part. In some embodiments, the liquid carrier is present in the second part in a range from 20 to 70, 2 to 60, or 20 to 50 percent by weight, based on the total weight of the second part.

[0050] The first part and the second part can be combined in any useful ratio. Useful ratios of chemical curing agent to silicate can vary depending on the desired composition of the siliceous network. In some embodiments, the ratio of silicate to chemical curing agent is in a range from 30: 1 to 1:2. Na2SiF6can be used in amount of 3 wt. % to 10 wt. % of the total amount of silicate and chemical curing agent, and aluminophosphates (e g., those obtained from BassTech International. Fort Lee, NJ, under the trade designation ‘TABUTIT”) can be used in amounts of 30% to 45% of SiO; in the aqueous silicate.

[0051] In some embodiments of the repair composition of the present disclosure, at least one of the first part or the second part further comprises at least one of a water-soluble organic polymer or a latex polymer. Such polymers can be useful for enhancing the flexibility or toughness of the siliceous network and / or improving the adhesion of the siliceous network to a substrate. The weight average molecular weight (Mw) of the water-soluble organic polymer or latex polymer can be in a range from, for example, 10,000 to 1,000,000 grams per mole, 50,000 to 500,000 grams per mole, or 50,000 to 200,000 grams per mole, as determined by gel permeation chromatography using a polystyrene standard. Generally, the water-soluble organic polymer and latex polymer are free of or essentially free of carbon-carbon double bonds (i.e.. aliphatic carbon-carbon double bonds), for example, that could crosslink when the first part and the second part are combined. In some embodiments, at least one of the first part or the second part is essentially free of or free of organic monomers, for example, those having reactive carbon-carbon double bonds. In some embodiments, at least one of the first part or the second part is essentially free of or free of organic polymers. “Essentially free of’ organic monomers or organic polymers means having not more than 1 wt.%, 0.5 wt.%, 0.1 wt.%, 0.05 wt.%, 0.01 wt.%. or 0.001 wt.% organic monomers or organic polymers, based on the total weight of the first part, the second part, or the curable composition of the combined first part and the second part.

[0052] In some embodiments, at least one of the water-soluble polymer or the latex polymer is present in the first part, the second part, or the curable composition of the first part combined with the second part in an amount of at least 0.05 percent by weight (wt.%) or not more than 25 wt.%, based on the total weight of the first part, the second part, or the curable composition. In some embodiments, the water-soluble polymer is present in the first part, the second part, or the curable composition in an amount of at least 0.05 wt.%, 0.075 wt.%, or 0.1 wt.%, based on the total weight of the first part, the second part, or the curable composition. In some embodiments, the water-soluble polymer is present in the composition in an amount of not more than 25 wt.%, 20 wt.%, 15 wt.%, 10 wt.%, or 5 wt.%, based on the total weight of the composition.

[0053] In some embodiments, at least one of the first part or the second part further comprises a water- soluble organic polymer. In some embodiments, the water-soluble polymer comprises at least one of polylactic acid, polyvinyl alcohol, polyethylene oxide), polyvinylpyrrolidone). poly(acrylic acid), poly acrylamide, or polyvinyl acetate. Such polymers can be obtained from a variety of commercial sources in a variety of molecular weights. For example, suitable, commercially available water-soluble polymers include polyvinyl alcohols from Kuraray, Okayama, Japan; polyacrylamides from Kemira, Helsinki, Finland; polyethylene oxide)s from DuPont. Collegeville, PA, and polyvinyl acetate available under the trade designation “VINNAPAS” from Wacker Chemical Corporation, Ann Arbor, MI. Polyvinyl acetate may be soluble in water or dispersible in water, depending on its molecular weight. In some embodiments, the water-soluble polymer comprises at least one of polyacrylamide. poly(ethylene oxide), or poly(vinylpyrrolidone). In some embodiments, the water-soluble polymer includes anionic and / or cationic groups. That is, the water-soluble polymer can be anionic, cationic, or both (i.e., amphoteric). In some embodiments, the water-soluble polymer does not include cationic groups. In some embodiments, the water-soluble polymer is nonionic.

[0054] In some embodiments, at least one of the first part or the second part further comprises a latex polymer. The polymer may be a liquid or a solid dispersed in water. By “dispersed”, it is meant that the polymer in water is a heterogeneous mixture of discrete particles or droplets in water. “Dispersed” does not encompass “dissolved”. Generally, therefore, the polymer in the latex is insoluble in water (that is. has a solubility of less than 5 grams (g) per liter, less than 1 g per liter, or less than 0.5 g per liter at 20 °C). Examples of suitable water-dispersible polymers include polyvinyl acetate (PVA), poly(meth)acrylates, (meth)acrylate-styrene copolymers, (meth)acrylate vinyl-acetate copolymers, copolymers of (meth)acrylates and vinyl esters of tertiary carboxylic acids and optionally vinyl-acetate, styrene-butadiene copolymers, carboxylated styrene-butadiene copolymers, styrene-isoprene copolymers, natural rubber, polyurethanes, polyurethane-acrylates, ethylene-vinyl acetate copolymers (EVA), copolymers of ethylene, vinyl-acetate and vinyl ester, ethylene-(meth)acrylate copolymers, ethylene- (meth)acrylic acid copolymers, ethylene-2 -ethylhexyl acrylate copolymers, polyolefin block-copolymers, and combinations thereof. The above-mentioned copolymers can be block-type copolymers or random copolymers. The latex polymer can also be functionalized, meaning they can contain further functional groups such as hydroxyl-, carboxyl, anhydride-, acrylate-, glycidyhnethacrylate-, and / or silane-groups. In some embodiments, the latex polymer is free of any of these groups. In some embodiments, the latex polymer comprises at least of a poly(meth)acrylate copolymer, a styrene-butadiene copolymer, a styrene- isoprcnc copolymer, polyvinyl acetate, ethylene -vinyl acetate copolymer, or a polyurethane.

[0055] In some embodiments, the latex polymer includes a poly(meth)acrylate. As used herein, "(meth)aci late", and like terms, is meant to encompass bodr acrylates and methacrylates. A variety of poly(nicth)acrylatcs may be useful. Some poly(meth)acrylates useful for practicing the present disclosure are commercially available, for example, as emulsions from Alberdingk Boley, Greensboro, N.C., under the trade designations “AC 2403”, “AC 3630”, and “AC 2514”, from Dow, Midland, Mich., under the trade designation “RHOPLEX” in grades “AC-1034”, “GL-618”, and CS-4000. from The Lubrizol Corporation. Wickliffe, Ohio, under the trade designation "CARBOSET GA 7487”, from BASF, Ludwigshafen. Germany, under the trade designation "ACRONAL”, and from Arkema, King of Prussia, PA, under the trade designation “ENCOR”. A poly(meth)acrylate dispersed in water can be made, for example, by emulsion polymerization in which monomers, such as any desired acrylates and methacrylates are polymerized in water, optionally in the presence of an emulsifier, catalyst, and / or a chain-transfer agent (e.g., carbon tetrabromide, alcohols, mercaptans such as, for example, isooctyl thioglycolate. and mixtures thereof). Further details can be found in the Examples, below.

[0056] Some natural rubber polymers and SBR polymers useful for practicing the present disclosure are commercially available, for example, as emulsions from Alcan Rubber and Chemical, New York. NY, under the trade designation “ALCANTEX” and from BASF under the trade designation “BUTOFAN”.

[0057] In some embodiments the water-soluble polymer or latex polymer can have polyoxyalkylene groups on side chain and ionic groups on main chain. Such polymers include those obtained under the trade designation “MALIALIM” from NOF Corporation, Tokyo. Japan, and can be useful as dispersants, for example, for the solids in the first part, the second part, or the curable composition of tire combined first part and second part. A variety of methods may be useful for making the first part and / or the second part of the repair composition of the present disclosure. One method for making the first part comprises, for example, mixing starting materials comprising a silicate, particulate filler, and water to make an aqueous dispersion. Optionally, other additives (e.g., humectants, water-soluble polymers, latexes, dispersants, and rheology modifiers) may be used in the preparation of the first part. The starting materials can be mixed together by any conventional technique which results in a uniform mixture. For example, the first part can be mixed with in a mechanical mixing device such as a planetary mixer and blended until a uniform mixture is achieved, typically 5 to 30 minutes. Similar methods can be useful for making the second part. For example, the chemical curing agent and liquid carrier can be mixed, and optionally other additives (e.g., humectants, particulate filler including rheology modifiers, and additional liquid) can be added. Centrifugal mixing and hand mixing, for example, may also be useful.

[0058] Compositions according to the present disclosure can be packaged, for example, as a two-part composition, if desired. A two-part composition can be packaged in a cartridge system, if desired. In such a two-part composition, the volumetric ratio of the first to second part may be, e.g., 10:1 or lower, 5 : 1 or lower, 2 : 1 , or even 1:1. In other embodiments, the first part and the second part can be packaged in any suitable separate containers. The present disclosure provides a kit including the first part and the second part.

[0059] The present disclosure provides a method of repairing a damaged surface. The method includes combining the first part and the second part of the repair composition to provide a curable composition, applying the curable composition to the damaged surface, and curing the curable composition on the damaged surface to provide a cured composition. Combining the first part and the second part of the repair composition can be carried out in a variety of ways, for example, using a static mixer or a dynamic mixing element, for example, having a rotating nozzle. Applying the curable composition to the damaged surface and curing the curable composition on the damaged surface may be carried out simultaneously and / or as one step. Applying can be carried out by any suitable method, for example, by hand, directly from the mixer described above, or with a suitable applicator (e.g., paint stick, squeegee, roller, brush, or nozzle). In some embodiments, the curing comprises curing at room temperature. In some embodiments, no heat or radiation is applied to accomplish the curing. In some embodiments, curing is carried out using heat, for example, an infrared lamp such as those used for paint curing. The infrared lamp may be a long or short wavelength infrared lamp. Hot air blowers such as heat guns may also be useful. In some embodiments, curing is carried out at a temperature of not more than 60 °C, in some embodiments, not more than 50 °C, 40 °C. 30 °C, or 25 °C. In some embodiments, curing is carried out at a temperature of at least 20 °C, in some embodiments, in a range from 20 °C to 60 °C, 20 °C to 50 °C, 20 °C to 40 °C, or 20 °C to 30 °C.

[0060] In the repair composition of the present disclosure, the reaction between an alkali silicate and the chemical curing agent generally does not require temperatures higher than room temperature. Heating at an elevated temperature, however, can be used to densify the structure and eliminate residual OH-groups, which can lead to enhanced degree of crosslinking. In some embodiments of the method of the present disclosure, the repair composition is not subjected to heating, for example, at a temperature above 60 °C, 55 °C. 50 °C, 45 °C, 40 "C. or 35 °C. The temperature of the repair composition a surface can be determined, for example, using an infrared thermometer such as a 3M Infrared Thermometer IR- 750 Standard Model, 3M Company. St. Paul. MN, USA.

[0061] Applications of repair compositions according to the present disclosure include curable body repair materials useful in the repair of damaged vehicles and other equipment (e.g.. cars, trucks, watercraft, windmill blades, aircraft, recreational vehicles, bathtubs, storage containers, and pipelines).

[0062] For repairing a vehicle, for example, a technician can mix the first part and the second part and then use a squeegee to spread the repair composition onto the surface of the vehicle to roughly match the contour of the surface. As the curable composition reacts, it hardens to a state where it can be shaped to match the contour of the vehicle before it was damaged. During this hardening process, the repair compound typically transitions from a state of soft, gelled material to a state of moderately hard material that is relatively easy to shape with an abrasive article (e.g., sandpaper) to a state of hard material. Premature sanding of body repair material before it has reached a critical amount of cure results in sandpaper becoming plugged reducing its effectiveness, the surface of the body repair material becoming rough, and sometimes the body repair material peeling away from the surface of the vehicle. If this situation occurs, typically the body repair material is partially removed (usually by sanding) such that another layer of body repair material can be put on top and properly shaped.

[0063] As shown in the Examples, below, repair compositions of the present disclosure cure at room temperature and are ready for sanding in a useful time window, which can be adjusted as desired by selecting components of the composition. For example, humectants such as 1,4-butanediol, propylene carbonate, glycerin carbonate, tripropylene glycol, and lactic acid can decrease the cure time. Lowering the pH (e.g.. with acids such as hydrochloric acid) can increase the time to sanding. Using a combination of chemical curing agents with different reactivities can be useful for adjusting the cure time. In some embodiments, the method of repairing a damaged surface of the present disclosure further comprises at least one of shaping or sanding the cured composition on the surface. The method can also include providing at least one of a coating or finish (e.g.. paint) over the cured composition.

[0064] Advantageously, and unexpectedly, in some embodiments, the repair composition of the present disclosure adheres well to non-cementitious surfaces. In some embodiments, the repair composition of the present disclosure adheres well to a variety of common repair surfaces (e g., metals such as aluminum and galvanized steel, E-coats, primers, paints, and ceramics).

[0065] In one aspect, the present disclosure provides the use of a cementitious composition as repair composition for a non-cementitious surface. Similarly, the present disclosure provides a method of repairing a non-cementitious damaged surface. The method includes applying a cementitious repair composition to the non-cementitious damaged surface and curing the repair composition on the non- cementitious damaged surface to provide a cured composition. The repair composition can be as described above in any of its embodiments. In some embodiments, the cementitious repair composition can be applied as a one-part composition including any of the components described above in any of their embodiments. In some embodiments, the cementitious repair composition can be provided as a dry composition including any of the components described above in dry or powder form, which may be mixed with water and any liquid humectants before application to the non-cementitious surface.

[0066] In some embodiments, it may be useful to treat the surface to improve adhesion to the surface. Silane coupling agents may be useful, for example, for treating a surface to improve the adhesion of the repair composition to the surface. In some embodiments, the methods of the present disclosure include applying a silane coupling agent to the damaged surface or the non-cementitious damaged surface.

[0067] In some embodiments, the silane coupling agent is represented by formula: R'f[Si(X)4 f]8wherein: g is 1 to 6, 1 to 2. or 1; f is 1 or 2, in some embodiments, 1 ; each R1is monovalent or multivalent and is independently alkyl, aryl, or ar lalkylenyl, wherein alky l and arylalkylcnyl arc each uninterrupted or interrupted with at least one catenated -O-, -N(R2)-, or combination thereof, optionally wherein at least one R1is substituted with at least one epoxy, (meth)acrylate, mercaptan, isocyanate, chloro. -NH(R2)-. or a combination thereof, and wherein R2is hydrogen, alkyl, aryl, or arylalkylenyl (in some embodiments, hydrogen); and

[0068] X is independently hydroxyl or a hydrolyzable group.

[0069] Examples of suitable silane coupling agents include 3-(2- aminoethyl)aminopropyltrimethoxysilane ), 3-aminopropyllnmcthoxysilanc. 3- aminopropyltriethoxy silane, 3-(2-(2-aminoethyl)aminoethyl)aminopropyltrimethoxy silane, 3- glycidoxypropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3- mercaptopropyltrimethoxysilane, N-phcnvIpropyltrimcthoxysilanc. and combinations thereof. Further examples of useful silanes include those obtained from Evonik Inductries AG, Essen. Germany, under the trade designations “VPS 4721”, “DYNASYLAN HYDROSIL 2926” and “DYNASYLAN HYDROSIL 1153”.

[0070] In some embodiments, the silane coupling agent, including any of those described above, is at least partially hydrolyzed, in some embodiments, at least partially hydrolyzed and condensed. In at least partially hydrolyzed silane coupling agents of formula R1f[Si(X)4.f]g, at least one X is hydroxyl. The water necessary for hydrolysis of hydrolyzable groups to form silanol groups may be added to the silane coupling agent, may be adventitious water in the solvent in a solution of the silane coupling agent, may be adsorbed to the surface of the substrate, or may be present in the atmosphere to which the silane coupling agent is exposed (c.g., an atmosphere having a relative humidity of at least 10%, 20%, 30%, 40%, or even at least 50%). The present disclosure provides a cured composition made from the curable composition according to any of the above embodiments as well as an article comprising the cured composition on a surface. In some embodiments of the method of the present disclosure, the damaged surface to be repaired is on at least a portion of a vehicle. Similarly, in some embodiments of the article of the present disclosure, the article is a portion of a vehicle.

[0071] Some Embodiments of the Disclosure

[0072] In a first embodiment, the present disclosure provides a repair composition comprising a first part and a second part, the first part comprising an aqueous silicate comprising at least one of an alkali silicate or ammonium silicate and the second part comprising a chemical curing agent for the at least one of the alkali silicate or ammonium silicate and a liquid carrier, wherein at least one of the first part or the second part comprises particulate filler, wherein at least one of the first part or the second part comprises a humectant, and wherein the humectant may be tire liquid carrier or other than the liquid carrier. In a second embodiment, the present disclosure provides the repair composition of the first embodiment, wherein the chemical curing agent is capable of reacting with the at least one of the alkali silicate or ammonium silicate at a temperature of not more than 60 °C, 50 °C, 40 °C, 30 °C, or at a temperature in a range from 20 °C to 30 °C. In a third embodiment, the present disclosure provides the repair composition of the first or second embodiment, wherein at least one of the first part or the second part further comprises a water-soluble organic polymer. In a fourth embodiment, the present disclosure provides the repair composition of any one of the third embodiment, wherein tire water-soluble polymer comprises at least one of polylactic acid, polyvinyl alcohol, polyethylene oxide, polyacrylic acid, polyvinylpyrrolidone, or polyacrylamide. In a fifth embodiment, the present disclosure provides the repair composition of anyone of the first to fourth embodiments, wherein at least one of tire first part or the second part further comprises a latex polymer. In a sixth embodiment, the present disclosure provides the repair composition of the fifth embodiment, wherein the latex polymer comprises at least one of an acrylic polymer, a rubber, polyvinyl acetate, ethylene -vinyl acetate, or a polyurethane. In a seventh embodiment, the present disclosure provides the repair composition of any one of the third to sixth embodiments, wherein the water-soluble organic polymer and / or latex polymer is essentially free of or free of reactive carbon-carbon double bonds (i.e., aliphatic carbon-carbon double bonds). In an eighth embodiment, the present disclosure provides the repair composition of any one of the first to seventh embodiments, wherein at least one of the first part, the second part, or the repair composition is essentially free of or free of organic monomers having reactive carbon-carbon double bonds. In a ninth embodiment, the present disclosure provides the repair composition of the first or second embodiment, wherein at least one of the first part, the second part, or the repair composition is essentially free of or free of organic polymers.

[0073] In a tenth embodiment, the present disclosure provides the repair composition of any one of the first to ninth embodiments, wherein the aqueous silicate is an alkali silicate comprising at least one of lithium silicate, sodium silicate, or potassium silicate. In an eleventh embodiment, the present disclosure provides the repair composition of any one of the first to tenth embodiments, wherein the alkali silicate has a molar ratio of silicon to alkali metal of not more than 3.22: 1. In a twelfth embodiment, the present disclosure provides the repair composition of any one of the first to eleventh embodiments, wherein the alkali silicate comprises sodium silicate. In a thirteenth embodiment, the present disclosure provides the repair composition of any one of the first to tw elfth embodiments, wherein the chemical curing agent comprises at least one of aluminum phosphate, aluminum dihydrogen phosphate, zinc borate, ammonium pentaborate, potassium pentaborate, potassium tetraborate, Portland cement, calcium sulfoaluminate cement, magnesium phosphate cement, gy psum, a dibasic ester, a multivalent salt of a w eak acid, zinc aluminate, sodium fluorosilicate, or fluoroaluminosilicate. In a fourteenth embodiment, the present disclosure provides the repair composition of any one of the first to thirteenth embodiments, wherein the chemical curing agent comprises at least one of aluminum phosphate, aluminum dihydrogen phosphate, zinc borate, fluoroaluminosilicate, or sodium fluorosilicate. In a fifteenth embodiment, the present disclosure provides the repair composition of any one of the first to fourteenth embodiments, w herein the first part combined w ith the second part provides a curable composition, w hich forms an amorphous polymeric =Si-O-Si= network, optionally containing at least one of Al, B, or P atoms. In a sixteenth embodiment, the present disclosure provides the repair composition of the fifteenth embodiment, wherein the chemical curing agent is other than an aluminosilicate and / or wherein the chemical curing agent is other than attapulgite.

[0074] In a seventeenth embodiment, the present disclosure provides the repair composition of any one of the first to sixteenth embodiments, wherein the humectant comprises at least one of 1.4-butanediol, propylene carbonate, glycerol, glycerin, glycerin carbonate, propylene glycol, ethylene glycol, tripropylene glycol, polypropylene glycol, lactic acid, a sugar alcohol, or triethanolamine. In an eighteenth embodiment, the present disclosure provides the repair composition of the seventeenth embodiment, wherein the humectant is the liquid carrier. In a nineteenth embodiment, the present disclosure provides the repair composition of any one of the first to eighteenth embodiments, wherein the humectant comprises at least one of 1,4-butanediol. propylene carbonate, glycerol, glycerin, glycerin carbonate, propylene glycol, ethylene glycol, tripropylene glycol, or polypropylene glycol. In a twentieth embodiment, the present disclosure provides the repair composition of any one of the first to nineteenth embodiments, wherein the liquid carrier comprises water.

[0075] In a twenty -first embodiment, the present disclosure provides the repair composition of any one of the first to twentieth embodiments, w herein the particulate filler comprises at least one of ceramic beads, polymer beads, silica, hollow ceramic elements, hollow polymeric elements, alumina, zirconia, mica, dolomite, wollastonite, fibers, ceramic fibers, talc, calcium carbonate, or clay. In a twenty-second embodiment, the present disclosure provides the repair composition of any one of the first to twenty -first embodiments, wherein the first part comprises the particulate filler. In a twenty -third embodiment, the present disclosure provides the repair composition of any one of the first to twenty-second embodiments, wherein at least one of the first part, the second part, or the repair composition is essentially free of metal particles. In a twenty -fourth embodiment, the present disclosure provides the repair composition of any one of the first to the twenty -third embodiments, wherein water is present in the first part in a range from 10 to 60, the alkali or ammonium silicate (as part of the aqueous silicate) is present in the first part in 2 to 30 percent by weight, and the particulate filler is present in the first part in a range from 10 to 85. based on the total weight of the first part. In a twenty -fifth embodiment, the present disclosure provides the repair composition of any one of the first to twenty -fourth embodiments, wherein the chemical curing agent is present in the second part in a range from 30 to 80 percent by weight and the liquid carrier is present in the second part in a range from 20 to 70 percent by weight, based on the total weight of the second part.

[0076] In a twenty -sixth embodiment, the present disclosure provides use of the repair composition of any one of the first to the twenty-fifth embodiments as a repair composition for a damaged surface. In a twenty -seventh embodiment, the present disclosure provides a method of repairing a damaged surface, the method comprising combining the first part and the second part of the repair composition of any one of the first to the twenty -fifth embodiments to provide a curable composition, applying the curable composition to the damaged surface, and curing the curable composition on the damaged surface to provide a cured composition. In a twenty -eighth embodiment, the present disclosure provides the use or method of the twenty -sixth or twenty -seventh embodiment, w herein the use or the curing is carried out at a temperature of not more than 60 °C, 50 °C, 40 °C, 30 °C, or 25 °C or in a range from 20 °C to 60 °C, 20 °C to 50 °C, 20 °C to 40 °C. or 20 °C to 30 °C. In a twenty -ninth embodiment, the present disclosure provides the use or method of any one of the twenty -sixth to twenty-eighth embodiments, wherein the use or the curing is carried out at room temperature. In a thirtieth embodiment, the present disclosure provides the use or method of any one of the twenty-sixth to twenty-ninth embodiments, wherein the damaged surface is a non-cementitious surface. In a thirty -first embodiment, the present disclosure provides the use or method of the thirtieth embodiment, wherein the damaged surface is a portion of a damaged vehicle or other equipment (in some embodiments, a car, truck, watercraft, windmill blades, aircraft, recreational vehicle, bathtub, storage container, or pipeline). In a thirty-second embodiment, the present disclosure provides the use or method of the thirty -first embodiment, wherein the damaged surface is a portion of a vehicle. In a thirty -third embodiment, the present disclosure provides the use or method of any one of the twenty-sixth to thirty-second embodiments, wherein the use or method further comprises sanding the cured composition. In a thirty -fourth embodiment, the present disclosure provides the use or method of any one of the twenty-sixth to thirty-third embodiments, wherein the use or method further comprises applying a silane coupling agent to the damaged surface before applying the curable composition to the damaged surface, wherein the silane coupling agent is optionally at least partially hydrolyzed.

[0077] In a thirty -fifth embodiment, the present disclosure provides use of a cementitious composition as a repair composition for a non-cementitious damaged surface. In a thirty -sixth embodiment, the present disclosure provides a method of repairing a non-cementitious damaged surface, the method comprising applying a cementitious repair composition to the non-cementitious damaged surface and curing the repair composition on the non-cementitious damaged surface to provide a cured composition. In a thirtyseventh embodiment, the present disclosure provides the use or method of the thirty -fifth or thirty-sixth embodiment, wherein the non-cementitious damaged surface is a portion of a damaged vehicle or other equipment (in some embodiments, a car, truck, watercraft, windmill blades, aircraft, recreational vehicle, bathtub, storage container, or pipeline). In a thirty-eighth embodiment, the present disclosure provides the use or method of the thirty-seventh embodiment, wherein the non-cementitious damaged surface is a portion of a vehicle. In a thirty -ninth embodiment, the present disclosure provides the use or method of any one of the thirty -fifth to thirty -eighth embodiments, wherein the use or the curing is carried out at a temperature of not more than 60 °C, 50 °C. 40 °C, 30 °C, or 25 °C or in a range from 20 °C to 60 °C. 20 °C to 50 °C. 20 °C to 40 °C, or 20 C to 30 °C. In a fortieth embodiment, the present disclosure provides the use or method of any one of the thirty -fifth to thirty -ninth embodiments, wherein the use or the curing is carried out at room temperature. In a forty -first embodiment, the present disclosure provides the use or method of any one of the thirty -fifth to fortieth embodiments, wherein the use or method further comprises sanding the cured composition. In a forty -second embodiment, the present disclosure provides the use or method of any one of the thirty-fifth to forty-first embodiments, wherein the use or method further comprises applying a silane coupling agent to tire non-cementitious damaged surface before applying the curable composition to the non-cementitious damaged surface, wherein the silane coupling agent is optionally at least partially hydrolyzed.

[0078] In a forty-third embodiment, tire present disclosure provides a kit comprising the first part and the second part of the repair composition of any one of the first to twenty -fifth embodiments, wherein the first part and the second part are separately packaged. In a forty -fourth embodiment, the present disclosure provides the kit of the forty-third embodiment, further comprising a silane coupling agent, packaged separately from the first part and the second part, wherein the silane coupling agent is optionally at least partially hydrolyzed.

[0079] In order that the present disclosure can be more fully understood, the following examples are set forth. It should be understood that these examples are for illustrative purposes only and are not to be construed as limiting this disclosure in any manner. For example, the particular materials and amounts thereof recited in these examples, as well as other conditions and details, should not be construed to unduly limit this disclosure.

[0080] EXAMPLES

[0081] Unless otherwise noted, all parts, percentages, ratios, etc. in the Examples and the rest of the specification are by weight. Unless stated otherwise, all other reagents were obtained, or are available from fine chemical vendors or may be synthesized by known methods.

[0082] In these Examples, °C refers to degrees Celsius, mL refers to milliliters, g refers to gram, rpm refers to revolutions per minute, mm refers to millimeter, mBar refers to millibar, Pa refers to Pascals, MPa refers to megapascals, wt. % refers to weight percent, cm refers to centimeter, and min refers to minute.

[0083] Table 1 : Materials used in the Examples

[0084] Preparation of Latex 5 (Lat 5), a copolymer of MM A, nBMA, and PMDSMA

[0085] A clean reaction flask was fitted with a mechanical stirrer, thermocouple, condenser, and nitrogen line and was charged with 79.8 parts by weight of MMA, 20 parts by weight of nBMA, 0.2 parts by weight of PMDSMA, 2 parts by weight of SDBS, 4 parts by weight of Surf, and 400 parts by weight of deionized water. The mixture was stirred and heated to 65 °C while being purged with nitrogen. When the temperature reached 40 °C, 1 part by weight of ammonium persulfate was added to the reaction mixture. The reaction was mildly exothermic, and the temperature rose to 72 °C. The reaction was allowed to proceed overnight at 65 °C. The next day, the reaction mixture was cooled to room temperature, and a percent solids analysis revealed 20.5% solids, indicating quantitative monomer conversion to polymer.

[0086] Preparation of First Parts Fl to F18

[0087] First part samples were prepared in 50-mL cups (Part # 5000000027) obtained from FlackTek, Landrum, SC. Components were measured on an analytical balance. All the dry components were measured and hand-mixed first and then alkali silicates were added and mixed in a dual asymmetric centrifugal mixer (Model # DAC 600 2 VAC-LR) obtained from FlackTek, under the trade designation “FLACKTEK SPEEDMIXER” at 800 rpm for 1 min followed by 1500 rpm for 2 min followed by 2000 rpm for 1 min. The mixing was performed at atmospheric pressure. The mixture was then allowed to sit until the mixture temperature reached 25 C. Dispersed air pockets were removed by vacuuming the samples in the FLACKTEK SPEEDMIXER centrifugal mixer at 900 mBar (90.000 Pa) / 800 rpm for 20 seconds, followed by 500 mBar (50.000 Pa) / 800 rpm for 40 seconds, followed by 50 mBar (50.000 Pa) / 900 rpm for 3 min, followed by 50 mBar(50.000 Pa) / 1000 rpm for 1 min.

[0088] Table 2. Composition of First Part, Fl to F7. All values are in g. Compositions of First Parts F8 to F18 each contained 5.72 g Mix, 1.64 g CC. 1.22 g RA, 3.92 g

[0089] Talc, and 15.00 g SS 3. Further components of the compositions of First Parts F8 to F17 are provided in Table 3, below.

[0090] Table 3. Composition of First Part F8 to F18 other than Mix, CC. RA, Talc, and SS 3. All values are in g. Preparation of Second Parts SI to S24

[0091] Second part samples were prepared using the same method for mixing and vacuuming described for First Parts Fl to Fl 7. The weight of the liquid components was determined from their densities, and the liquids were added using a micropipette. Second part samples SI to S15 included the components shown in Table 4, below.

[0092] Table 4: Composition of Second Part. SI to S15. All values are in g.

[0093] Compositions of Second Parts S16 to S23 each contained 3.0 g G, 6.0 g ZB, and 0.12 g dispersant. Second Part S24 contained 3.0 g G and 6.0 g ZB. Further components of the compositions of Second Parts S16 toS23 are provided in Table 5. below.

[0094] Table 5: Composition of Second Part other than G, ZB, and dispersant. S16 to S24. All values are in g.

[0095] Examples 1 to 38

[0096] Method A, hand-mixing on a mixing board: The First and Second Parts were mixed using a plastic spreader on a mixing board until the Second Part was incorporated into the First Part and no visible separation was observed.

[0097] Method B, mixing in a centrifugal mixer: The First and Second Parts were mixed in a cup obtained from FlackTek; the size of the cup depended on the amount of material being made. The mix cup was then spun at 800 rpm for 15 seconds at 677 mBar (67,700 Pa), followed by 1000 rpm for 15 seconds at 500 mBar (50,000 Pa), followed by 0 rpm for 10 seconds at 10 mBar (1000 Pa) in the FLACKTEK SPEEDMIXER centrifugal mixer to obtain a homogenous mix.

[0098] Examples 1 to 38 were prepared by mixing the first part and the second part using Method A or Method B as indicated in Table 6, below. Examples 1 to 38 were evaluated for Spreadability, Gel Time, Tack-free Time, Cure Time, Sand Time, and water resistance using the test methods described below. The results are in Table 6, below.

[0099] Table 6: Compositions for Examples 1 to 38 aSpreadability.bReported as minutes:seconds.cn.m. = not measured.dMeasured according to the Water Immersion Test.eCured at 60 °C.fThe Comparative Example was a two-part body filler obtained from 3M Company, St. Paul, MN, under the trade designation “3M PLATINUM PLUS FILLER”.

[0100] Example 14, Example 18. and the Comparative Example were further evaluated using methods indicated in Table 7, below. Table 7: Evaluations of Examples 14 and 18 and Comparative Example

[0101] Test Methods

[0102] Preparation of Stainless-Steel Substrates

[0103] Hot Dip Galvanized Steel Unexposed G 70 test panels (1 inch (2.54 cm) by 4 inches (10 cm) by 0.030 inch (0.076 cm)) obtained from ACT Test Panels LLC, Hillsdale, MI, were used to determine Spreadability, Gel Time, Tack-free Time, Cure Time, and Sand Time and for the Cylindrical Mandrel Bend Test and the Water Immersion Test. Electro Galvanized Steel Gardobond 24T Gardolene D6800) test panels (12 inch (30.5 cm) by 4 inches (10 cm) by 0.030 inch (0.076 cm)) obtained from ACT Test Panels LLC were used for the Corrosion Test.

[0104] The surface was cleaned on both sides of the metal substrates two times with acetone and a paper towel and allowed to dry’. The surface was then abraded using an 80-grit sandpaper. Freshly abraded samples were kept in a desiccator to inhibit surface oxidation.

[0105] Spreadability'

[0106] To test the comparative smoothness and ease of spreading and to check for any undispersed particles or other foreign contaminants, a spreadability test was performed. Approximately 25 g of each Example or Comparative Example were scooped out and spread on the panel by pressing in a downward direction and moving it up and down, repeatedly. It was spread in a thin film less than 1 / 16 inch thick to detect small particles. The material was then checked for smoothness and homogeneity according to, and the quality of spreadability was given a rating as shown in Table 8, below. Table 8: Rating for spreadability of Examples 1 to 36

[0107] Gel Time

[0108] A stopwatch was started as soon as the First and Second Parts were combined. After the mixing using Method A or B was complete, the mixed First Part and Second Part were then spread on a mixing board using a spreader. This mixture was spread again at 10-second intervals until the mixture started to become thick or solidified for the first time. The stopwatch was paused immediately, and the time was recorded as the gel time.

[0109] Tack-free Time

[0110] Just after the gel time was recorded, the stopwatch was started again. The surface was then touched with a tongue depressor every 10 seconds to record the instant when it stopped sticking to the tongue depressor. The stopwatch was then paused, and the time was recorded as the tack-free time.

[0111] Cure Time

[0112] After recording the tack-free time, the stopwatch was started again, and a small part of the surface was scratched at 30-second intervals with an 80-grit sandpaper until the layer of the composition closest to the surface rolled on itself. After this, the surface was scratched at 2 to 5-minute intervals until the particles that came off the surface were pickable (semi-dry). In a later stage, when the sanding particles started turning into crumbles, the time was recorded as the cure time.

[0113] Sand Time

[0114] After the cure time was recorded, the stopwatch kept recording time while a fresh 80-grit sandpaper was used to sand the surface of the cured filler. The time at which the sandpaper did not load with particles, and / or finer and softer particles were being sanded off, was recorded as the sand time.

[0115] Cylindrical Mandrel Bend Test

[0116] The test followed the ASTM D522 / D522M-17 procedure. The dried thickness of tire sample was approximately 0.018 inch (0.46 mm). Water Immersion Test

[0117] The samples were cured for 24 hours before they were immersed in water at ambient conditions. The samples were soaked in water for 24 hours. They were then removed from the water and air dried for 30 minutes. If the surface of the cured filler was completely removed and dissolved in the water, the evaluation was a fail. If the surface of the cured filler was intact, the evaluation was a pass.

[0118] Linear Shrinkage Test

[0119] The test method followed ASTM D2566-86. STONER ROCKET RELEASE E302 mold release obtained from Stoner Molding Solutions, Quarryville, PA, USA was used as a release agent to remove the cured filler out of the mold.

[0120] Overlap Shear Strength Test

[0121] Electro Galvanized Steel Gardobond 24T Gardolene D6800) test panels described above were cut to a size of 1 meh (2.54 cm) by 4 inches (10 cm) by 0.030 inch (0.076 cm). The surface of each coupon was cleaned on with acetone and abraded using an 80-grit sandpaper on a 1-inch (2.54 cm) by 1-inch (2.54-cm) end of the coupon. The abraded ends were coated within 2 hours of abrasion. Examples were mixed as described in Table 6, above. Each end of the coupon was coated with a mixed example or comparative example, and spacers (250-micrometer) were added. The ends were pressed together in 0.5- inch overlap and clamped, and excess material was wiped from the edges. The bonds were allowed to cure for 72 hours at approximately 23°C and approximately 50% relative humidity. The bonds were pulled at approximately 23 °C and approximately 50% relative humidity using an INSTRON model 5967 obtained from Instron, Norwood, MA, USA, using a pull rate of 10 rmn / min.

[0122] Corrosion Resistance

[0123] A 50-mil (1.27-mm) draw down (BYK) was used to spread the sample on the panel, and then the sample was allowed to dry for 72 hours. Primer obtained from 3M Company under the trade designation ’’MAR-HYDE 4.4 Ultimate 2K High Speed Primer” was applied to the edges of the panel to seal the corners, and then the primed sample was then allowed to cure for 48 horns. Finally, the sample was placed in a salt fog chamber obtained from Atlas Material Testing Solutions - SF series - AMETEK Measuring and Calibration Solutions as described in ASTM Bl 17. Samples were removed from the salt fog chamber at 1-, 7-. 14-, and 21 -day intervals (as described in ASTM Bl 17). The surface of the filler was then scraped off to see any underlying corrosion on the metal surface. If no corrosion was observed on the metal surface, then the composition was said to pass the test.

[0124] This disclosure is not limited to the above-described embodiments but is to be controlled by the limitations set forth in the following claims and any equivalents thereof. This disclosure may be suitably practiced in the absence of any element not specifically disclosed herein.

Claims

What is claimed is:

1. A repair composition comprising a first part and a second part, the first part comprising: an aqueous silicate comprising at least one of an alkali silicate or ammonium silicate; and the second part comprising: a chemical curing agent for the at least one of an alkali silicate or ammonium silicate; and a liquid carrier, wherein at least one of the first part or the second part comprises particulate filler, wherein at least one of the first part or the second part comprises a humectant, and wherein the humectant may be the liquid carrier or other than the liquid carrier.

2. The repair composition of claim 1, wherein the chemical curing agent is capable of reacting with the at least one of alkali silicate or ammonium silicate at a temperature of not more than 60 °C.

3. The repair composition of claim 1 or 2, wherein at least one of the first part or the second part further comprises at least one of a water-soluble organic polymer or a latex polymer.

4. The repair composition of claim 3, wherein the water-soluble polymer comprises at least one of polylactic acid, polyvinyl alcohol, polyethylene oxide, polyacrylic acid, polyvinylpyrrolidone, or polyacrylamide, and wherein the latex polymer comprises at least one of an acrylic polymer, a rubber, polyvinyl acetate, ethylene-vinyl acetate, or a polyurethane.

5. The repair composition of any one of claims 1 to 4, wherein the aqueous silicate is an alkali silicate comprising at least one of lithium silicate, sodium silicate, or potassium silicate.

6. The repair composition of any one of claims 1 to 5, wherein the chemical curing agent comprises at least one of aluminum phosphate, aluminum dihydrogen phosphate, zinc borate, ammonium pentaborate, potassium pentaborate, potassium tetraborate, Portland cement, calcium sulfoaluminate cement, magnesium phosphate cement, gypsum, a dibasic ester, a multivalent salt of a weak acid, zinc aluminate, sodium fluorosilicate, or fluoroaluminosilicate.

7. The repair composition of any one of claims 1 to 6. wherein the chemical curing agent comprises at least one of aluminum phosphate, aluminum dihydrogen phosphate, zinc borate, fluoroaluminosilicate, or sodium fluorosilicate.

8. The repair composition of any one of claims 1 to 7, wherein the humectant comprises at least one of 1,4-butanediol, propylene carbonate, glycerol, glycerin, glycerin carbonate, propylene glycol, ethylene glycol, tripropylene glycol, polypropylene glycol, lactic acid, or a sugar alcohol.

9. The repair composition of any one of claims 1 to 8. wherein the humectant is the liquid carrier.

10. The repair composition of any one of claims 1 to 9. wherein the liquid carrier comprises water.

11. The repair composition of any one of claims 1 to 10, wherein the particulate filler comprises at least one of ceramic beads, polymer beads, silica, hollow ceramic elements, hollow polymeric elements, alumina, zirconia, mica, dolomite, wollastonite, fibers, talc, calcium carbonate, or clay.

12. A method of repairing a damaged surface, the method comprising: combining the first part and the second part of the repair composition of any one of claims 1 to 11 to provide a curable composition; applying the curable composition to the damaged surface; and curing the curable composition on the damaged surface to provide a cured composition.

13. The method of claim 12, wherein the curing comprises curing at room temperature.

14. The method of claim 12 or 13, further comprising sanding the cured composition.

15. Use of a cementitious composition as a repair composition for a non-cementitious damaged surface.

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