WO2024095024A1

WO2024095024A1 - Thermal insulation aspartic ester polyurea compositions and coatings

Info

Publication number: WO2024095024A1
Application number: PCT/GR2022/000060
Authority: WO
Inventors: Ioannis ARAMPATZIS; Nikolaos TAMPOURIS
Original assignee: Nanophos Sa
Priority date: 2022-11-01
Filing date: 2022-11-01
Publication date: 2024-05-10

Abstract

Provided are thermally insulating aspartic ester polyuria coatings and coating compositions. A coated substrate according to some embodiments comprises a substrate and a coating on the substrate formed from a composition comprising: a secondary amino-functional co- reactant for polyisocyanates resin; one or more of a low density mineral or thermoplastic; heat-reflecting particles; and a hardener.

Description

THERMAL INSULATION ASPARTIC ESTER POLYUREA COMPOSITIONS AND COATINGS

FIELD

[0001] The present disclosure relates to waterproof coating compositions, and particularly, to aspartic ester polyurea (polyaspartic) coating compositions having thermal insulation properties.

BACKGROUND

[0002] For many centuries, the only waterproof coatings available were tar and asphalt. In more recent decades, materials such as liquid-applied membranes (LAMs), polyesters, epoxies, vinyls, and polyurethanes have been developed as alternative options.

[0003] More recently, polyurea has been developed for use as a waterproof coating, particularly in the automotive industry. Polyurea is produced when a primary polyamine base composition reacts with a diisocyanate hardener composition to yield a polyurea polymer. This reaction is shown below:

Reaction 1

[0004] Reaction 1 , above, shows the chemical modification of polyamine resin to yield polyurea. C represents carbon atoms, N represents carbon atoms, O represents oxygen atoms, H represents hydrogen atoms, k and m represent positive integers, R represents an isocyanate inert organic group, A represents alkyl or cycloalkyl or polyether or a combination thereof, organic groups.

[0005] Specifically, polyurea has been shown to have durability and mechanical strength, but can be difficult to apply to surfaces due to its short curing period and low weathering resistance.

SUMMARY

[0006] Provided herein are thermal insulating aspartic ester polyurea (polyaspartic) coating compositions, coated substrates prepared using aspartic ester polyurea (polyaspartic) coating compositions, and methods of preparing said compositions and coated substrates. Thermal insulating aspartic ester polyurea (polyaspartic) coatings disclosed herein having low thermal conductivity X, high emissivity g, and enhanced Total Solar Spectrum Reflectance p_e. The disclosed coatings prepared using compositions provided herein may be used for industries such as, but not limited to, building and construction, marine, industrial, and/or transportation applications. Specific applications might include roofs, masonry, metal facades, geotextiles for solar installations, metal pipes, heat exchangers, industrial heat reactors, tanks, vehicle fairings, refrigerated trucks, box containers, and the like. Further, compositions and coatings provided present suitable adhesion properties on the substrate applied. In some embodiments, no primer coating is required prior to applying a disclosed composition on a substrate.

[0007] Further, the compositions and coatings provided herein specifically integrate aspartic ester polyurea (polyaspartic) coatings with thermal insulation or a holistic energy management system. The presence of thermal insulation properties increases the useful life expectancy of polyurea (polyaspartic) coated substrates. Without adequate thermal insulation features, incident heat loads onto a polyaspartic coating increases the temperature of the coating and accelerates the aging process. Accordingly, fusing aspartic ester polyurea (polyaspartic) coating compositions with thermal insulation properties allows the waterproof coatings described herein to remain cooler for a prolonged life expectancy.

[0008] Unlike the waterproof coatings described above, and in particular, the polyurea compositions and coatings described above, the aspartic ester polyurea compositions and coatings prepared using said compositions described herein are designed to overcome the applicability challenges presented by polyurea-only compositions and coatings due to their short curing period and low weathering resistance.

[0009] Specifically, to prepare the compositions described herein, polyamine resins are modified to bear aspartic ester bonds according to the chemical reaction reproduced below:

Reaction 2

[0010] Reaction 2, above, shows the modification of polyamine resin to yield aspartic ester polyurea (polyaspartic). C represents carbon atoms, N represents carbon atoms, O represents oxygen atoms, H represents hydrogen atoms, k and m represent positive integers, R represents an isocyanate inert organic group, R¹ represents an isocyanate inert organic group, R² represents an isocyanate inert organic group, R^x represents an isocyanate inert organic group, R^Y represents an isocyanate inert organic group, Z represents alkyl or cycloalkyl or polyether or a combination thereof, organic groups.

[0011] The primary amine groups of the polyamine are partially substituted by an aspartic group (Asp), yielding a secondary polyamine, where amine groups are part of an aspartic moiety. This substitution of a primary amine hydrogen atom with aspartic ester results in a much more controlled reaction rate. A more controlled reaction rate allows for a slower reaction (e.g., minutes), which can allow for better applicability of a coating comprising the disclosed composition. Conversely and as explained above, conventional polyurea coatings are more difficult to apply to a surface or substrate due to their relatively fast reaction rate (e.g., seconds), particularly the reaction rate between the primary amine group and diisocyanates.

[0012] The development of aspartic ester polyurea (polyaspartic) coating compositions has been demonstrated as liquid-applied membranes for waterproofing purposes. Thermal properties for a coating can be quantified by the simultaneous (a) reduction of thermal conductivity , (b) increase of ultraviolet (UV), visible (VIS), and near infra-red (NIR) reflectance (Total Solar Spectrum Reflectance p_e), and (c) increase of emissivity s value. Heavy heat loads result from solar irradiance in actual life conditions (e.g., buildings or metal container boxes). Of the light that reaches Earth's surface, infrared (heat) radiation makes up to 50%, while visible light provides 42%. Ultraviolet radiation makes up just 8% of the total solar radiation. Therefore, developing highly heat reflective (cool) is essential to prevent heat transmission.

[0013] The emissivity s of the surface of a coating is its effectiveness in emitting energy as thermal radiation. Thermal radiation is electromagnetic radiation that may include visible and infrared radiation. Thermal shielding (insulation) requires coatings of very high emissivity £ (close to or above 80%) to facilitate radiative cooling and protection of the underlying structure. Finally, reducing thermal conductivity X delays heat energy that was not previously reflected or emitted to reach the underlying structure (substrate to be heat-protected), enhancing its resilience to intense heating. Thermal insulation requires the combined effect of reduced thermal conductivity , increased Total Solar Spectrum Reflectance p_e, and increased emissivity e.

[0014] Accordingly, and as described in further detail below, the compositions and coatings prepared from the described compositions present the following advantages over conventional waterproof coatings, and in particular, polyurea and other polyaspartic coatings: thermal insulation features that result in better energy management solutions than conventional aspartic ester polyurea (polyaspartic) coatings; enhanced weathering coating durability; and cost-effectiveness due to reducing the thermal insulating aspartic ester polyurea (polyaspartic) coating composition density compared to conventional aspartic ester polyurea (polyaspartic) coating compositions.

[0015] In some embodiments, provided is an aspartic ester polyurea composition, the composition comprising: a secondary amino-functional co-reactant for polyisocyanates; one or more of a low-density mineral or thermoplastic; heat-reflecting particles; and a hardener.

[0016] In some embodiments of the composition, the composition comprises 5-25 wt. % pigments, or fillers, or dyes.

[0017] In some embodiments of the composition, the pigments, or fillers, or dyes comprises rutile titanium dioxide.

[0018] In some embodiments of the composition, the composition comprises 0-1 wt. % ultraviolet absorber or stabilizer additive.

[0019] In some embodiments of the composition, the ultraviolet absorber comprises of Tinuvin® 292.

[0020] In some embodiments of the composition, the composition comprises 0-1 wt. % algicide or fungicide additive.

[0021] In some embodiments of the composition, the algicide or fungicide additive comprises Zinc Omadine®. [0022] In some embodiments of the composition, the composition comprises 0-3 wt. % rheology additive.

[0023] In some embodiments of the composition, the rheology additive comprises

RHEOBYK® 7410 ET.

[0024] In some embodiments of the composition, the composition comprises 0-40 wt. % solvent.

[0025] In some embodiments of the composition, the solvent comprises xylene.

[0026] In some embodiments of the composition, the composition comprises 10-70 wt. % a secondary amino-functional co-reactant for polyisocyanates resin.

[0027] In some embodiments of the composition, the composition comprises 1-30 wt. % one or more of a low density mineral or thermoplastic.

[0028] In some embodiments of the composition, the composition comprises 0.01-5 wt. % heat-reflecting particles.

[0029] In some embodiments of the composition, the composition comprises 10-50 wt. % hardener.

[0030] In some embodiments of the composition, the hardener comprises a polyisocyanate resin hardener.

[0031] In some embodiments of the composition, the composition comprises 5-15 wt. % one or more of anticorrosive metal oxides or phosphates.

[0032] In some embodiments of the composition, the one or more of anticorrosive metal oxides or phosphates comprises zinc oxide, zinc phosphates, tin(IV) oxide, SiCh, or Fe20 .

[0033] In some embodiments, provided is a coated substrate, the coated substrate comprising: a substrate; and a coating on the substrate, wherein the coating is formed from a composition comprising: a secondary amino-functional co-reactant for polyisocyanates resin; one or more of a low density mineral or thermoplastic; heat-reflecting particles; and a hardener.

[0034] In some embodiments of the coated substrate, the composition comprises 10-70 wt. % a secondary amino-functional co-reactant for polyisocyanates resin. [0035] In some embodiments of the coated substrate, the composition comprises 0.05-3 wt.

% rheology additive.

[0036] In some embodiments of the coated substrate, the composition comprises 1-30 wt. % one or more of a low density mineral or thermoplastic.

[0037] In some embodiments of the coated substrate, the composition comprises 0.01-5 wt.

% heat-reflecting particles.

[0038] In some embodiments of the coated substrate, the composition comprises 10-50 wt. % hardener.

[0039] In some embodiments of the coated substrate, the hardener comprises a polyisocyanate resin hardener.

[0040] In some embodiments of the coated substrate, the composition comprises 5-15 wt. % one or more of anticorrosive metal oxides or phosphates.

[0041] In some embodiments of the coated substrate, the one or more of anticorrosive metal oxides or phosphates comprises zinc oxide, zinc phosphates, tin(IV) oxide, SiO2, or Fe2O3.

[0042] In some embodiments of the coated substrate, the composition comprises 0.1-25 wt. % solvent.

[0043] In some embodiments of the coated substrate, the solvent comprises one or more of methyl ethyl ketone, methyl isobutyl ketone, xylene, methoxy propyl acetate, butyl acetate, or glycol esters.

[0044] In some embodiments of the coated substrate, the coated substrate has a surface roughness of 10-60 pm.

[0045] In some embodiments of the coated substrate, the coated substrate has a thickness of 900-1100 pm.

[0046] In some embodiments of the coated substrate, the coated substrate has a cross-plane thermal conductivity of 0.6-1 W/m-K.

[0047] In some embodiments of the coated substrate, the coated substrate has an extension at 23oC = 73.4oF of greater than 200%. [0048] In some embodiments of the coated substrate, the coated substrate has an emissivity greater of 0.9.

[0049] In some embodiments of the coated substrate, the coated substrate has a total solar spectrum reflectance of greater of 0.9.

[0050] In some embodiments of the coated substrate, the substrate comprises one or more of a roof, masonry, a metal, a geotextile, a heat exchanger, an industrial heat reactor, a tank, a vehicle fairing, a refrigerated truck, or a box container.

[0051] In some embodiments, any one or more of the features, characteristics, or elements discussed above with respect to any of the embodiments may be incorporated into any of the other embodiments mentioned above or described elsewhere herein.

BRIEF DESCRIPTION OF THE FIGURES

[0052] FIG. 1 A shows a thermal insulating aspartic ester polyurea (polyaspartic) coating composition being applied on a cementitious rooftop by roller brush, according to some embodiments;

[0053] FIG. I B shows a thermal insulating aspartic ester polyurea (polyaspartic) coating composition being applied on a cementitious rooftop by airless sprayer, according to some embodiments;

[0054] FIG. 2 shows a flow chart of the preparation of a coating composition, according to some embodiments;

[0055] FIGS. 3A-3D show the topography and the three-dimensional structure of a thermal insulating aspartic ester polyurea (polyaspartic) coating by means of Scanning Electron Microscopy (SEM) and Energy-Dispersive X-ray (EDX) techniques, according to some embodiments;

[0056] FIG. 4 shows the strain (%) of a thermal insulating aspartic ester polyurea (polyaspartic) coating as a function of stress (MPa) applied at different temperatures, according to some embodiments; [0057] FIG. 5 depicts the storage modulus (MPa) and Tan5 as a function of temperature for a thermal insulating aspartic ester polyurea (polyaspartic) coating, according to some embodiments;

[0058] FIG. 6 depicts the extension (%) under tensile strain as a function of the tensile stress (MPa), obtained at 23°C = 73.4°F for a thermal insulating aspartic ester polyurea (polyaspartic) coating, according to some embodiments; and

[0059] FIG. 7 shows the surface free energy plot obtained after determination of water and isopropanol contact angles on a thermal insulating aspartic ester polyurea (polyaspartic) coating, according to some embodiments.

DETAILED DESCRIPTION

[0060] Provided herein are thermal insulating aspartic ester polyurea (polyaspartic) compositions, thermal insulating aspartic ester polyurea (polyaspartic) coatings prepared from said compositions, and methods of preparing thermal insulating aspartic ester polyurea (polyaspartic) compositions and coatings. The thermal insulating aspartic ester polyurea (polyaspartic) compositions and protective coatings described herein may be used for industries including, but not limited to, building and construction, marine, industrial, and/or transportation. More specifically, the compositions described herein may be applied to surfaces/substrates such as, but not limited to, roofs, masonry, metal facades, geotextiles for solar installations, metal pipes, heat exchangers, industrial heat reactors, tanks, vehicle fairings, refrigerated trucks, and box containers.

[0061] Specifically, the thermal insulating aspartic ester polyurea (polyaspartic) compositions and coatings described herein may have desirable properties and features for specific applications.

[0062] For example, the polyaspartic compositions and coatings provided herein may simultaneously include extended workability time, low thermal conductivity , high Total Solar Spectrum Reflectance pe, high thermal emissivity £, high elasticity for gap bridging, enhanced abrasion resistance for pedestrian or vehicle traffic, and/or enhanced durability against weathering. As described above, coatings comprising some and/or all of these properties can help reduce the surface temperature of application substrates. Reducing the surface temperature of the application substrates (i.e., the substrate upon which a polyaspartic composition described herein is applied) can thermally insulate the structures or objects below the application substrates and reduce the energy required to maintain the thermal comfort of the structures or objects below the application substrates. Such properties are particularly beneficial in industries such as building and construction, marine, industrial, transportation, and energy management. Additionally, the compositions described herein present improved adhesion properties on the substrate applied. In some embodiments, no primer coating is required before applying disclosed compositions on a substrate.

[0063] As used herein, a “composition” is a fluid mixture of a plurality of components described herein. A “coating” is formed when the “composition” is applied to a surface/ substrate and subsequently dried.

[0064] In some embodiments, a polyaspartic composition is prepared by first forming two separation compositions: a first component (liquid base) and a second component (hardener). The first component, or liquid base, may comprise a secondary amino-functional co-reactant for polyisocyanates resin, rheology additive, low-density minerals or thermoplastics, heatreflecting particles, pigments, or fillers, or dyes, one or more anticorrosive metal oxides, or phosphates and organic solvents. The second component, or hardener, comprises polyisocyanate resin or resins and organic solvents. This preparation method is described in further detail below.

[0065] Polyaspartic compositions according to embodiments described herein can provide thermal insulation properties when applied as a coating onto a surface. The produced system is used for the preparation of a coating with the following characteristics: (a) solid, high- density coating, without surface imperfections, (b) absence of post-deposition heating step, (c) possibility of absence of primer-coat step, (d) high elasticity, (e) high adhesion, (f) flexibility, (g) low thermal conductivity X, (h) high Total Solar Spectrum Reflectance p_e, (i) high thermal emissivity s, (j) high surface smoothness, and (k) extended workability time of the liquid composition before the application on the relevant substrate.

Thermal Insulating Aspartic Ester Polyurea (Polyaspartic) Compositions

[0066] In some embodiments, a composition may comprise a secondary amino-functional coreactant for polyisocyanates resin, a rheology additive, a low-density mineral or thermoplastic, heat-reflecting particles, a pigment or dye, a filler, an anticorrosive metal oxide, a phosphates, an organic solvent, and a polyisocyanate resin hardener. In some embodiments, a composition may include an ultraviolet absorber, and an organic algicide or fungicide. Each component is described in detail below.

[0067] A secondary amino-functional co-reactant for polyisocyanates may be included in compositions described herein. A secondary amino-functional co-reactant for polyisocyanates resin is an organic molecule or polymer presenting a polyaspartic ester secondary aminereactive group, such as that illustrated below.

[0068] In the above structure, C represents carbon atoms, N represents carbon atoms, O represents oxygen atoms, H represents hydrogen atoms, n represents an integer of minimum 2, R¹ represents an isocyanate inert organic group, R² represents an isocyanate inert organic group, R^x represents an isocyanate inert organic group, R^Y represents an isocyanate inert organic group and Z represents an alkyl or cycloalkyl or polyether or a combination thereof, organic group.

[0069] The polyaspartic ester secondary amine-reactive group allows for efficient crosslinking with curing agents (e.g., isocyanates). The specific type and content of the polyaspartic ester secondary amine-reactive group can also determine the pot life (i.e., the time from mixing the two components of the thermal insulating aspartic ester polyurea (polyaspartic) coating composition together to the point at which the mixed components are no longer useable or applicable on the substrate, due to setting or viscosity increase or formulation curing). In some embodiments, thermal insulating aspartic ester polyurea (polyaspartic) coating compositions provided herein may comprise from 10-70 wt. %, 20-60 wt. %, 30-50 wt. %, or 35-45 wt. % secondary amino-functional co-reactant for polyisocyanates. In some embodiments, thermal insulating aspartic ester polyurea (polyaspartic) coating compositions provided herein may comprise less than or equal to 70 wt. %, less than or equal to 65 wt. %, less than or equal to 60 wt. %, less than or equal to 55 wt. %, less than or equal to 50 wt. %, less than or equal to 50 wt. %, less than or equal to 45 wt. %, less than or equal to 40 wt. %, less than or equal to 35 wt. %, less than or equal to 30 wt. %, or less than or equal to 25 wt. % secondary amino-functional co-reactant for polyisocyanates. In some embodiments, thermal insulating aspartic ester polyurea (polyaspartic) coating compositions provided herein may comprise more than or equal to 10 wt. %, more than or equal to 15 wt. %, more than or equal to 20 wt. %, more than or equal to 25 wt. %, more than or equal to 30 wt. %, more than or equal to 35 wt. %, more than or equal to 40 wt. %, more than or equal to 45 wt. %, more than or equal to 50 wt. %, or more than or equal to 55 wt. % secondary amino-functional co-reactant for polyisocyanates. Suitable commercially-available secondary amino-functional co-reactant for polyisocyanates may include Desmophen® NH1420, Desmophen® NH1520, Desmophen® NH2850, Feispartic® F520, Feispartic® F2850, Izasp® 14, Izasp® 15, Izasp® 151 , Izasp® 285, Teraspartic® 277 or Teraspartic® 292.

[0070] In some embodiments, a rheology additive may be included in a polyaspartic composition described herein. Rheology additives are often used to thicken a liquid composition to achieve specific rheological properties of the composition, including preventing sagging during the application, adjusting thickness upon application, facilitating spreading, improving leveling, and/or preventing sedimentation of filler. In some embodiments, a polyaspartic coating composition comprising too much rheology additive may exhibit undesirable flow/rheologic properties (e.g., may be too thick, making it difficult to apply). In some embodiments, a polyaspartic coating composition comprising too little rheology additive may also exhibit undesirable flow/rheologic properties (e.g., may be too thin, making it difficult to apply). In some embodiments, thermal insulating aspartic ester polyurea (polyaspartic) coating compositions provided herein may comprise 0 - 3 wt. %, 0.1- 2 wt. %, 0.1-1 wt. %, or 0.1-0.25 wt. % rheology additive. In some embodiments, a coating composition described herein may comprise less than or equal to 3 wt. %, less than or equal to 2.5 wt. %, less than or equal to 2 wt. %, less than or equal to 1.5 wt. %, less than or equal to 1 wt. %, less than or equal to 0.75 wt. %, less than or equal to 0.5 wt. %, or less than or equal to 0.25 wt. % rheology additive. In some embodiments, a coating composition described herein may comprise more than or equal to 0 wt. %, more than or equal to 0.1 wt. %, more than or equal to 0.15 wt. %, more than or equal to 0.2 wt. %, more than or equal to 0.25 wt. %, more than or equal to 0.5 wt. %, more than or equal to 0.75 wt. %, more than or equal to 1 wt. %, more than or equal to 2 wt. % rheology additive. Suitable commercially- available rheology additives can include TEGO® Flow 425, TEGO® Glide 100, RHEOBYK® 7410 ET, DISPERBYK®-2152, BYK-052 N, BYK®-354, or AEROSIL® 200. [0071] In some embodiments, a low-density mineral or thermoplastic may be included in a coating composition described herein. Low-density minerals or thermoplastics are solid chemical additives that do not dissolve, but reduce density in a liquid composition. The reduced density results in a low coating density after liquid formulation application on a substrate. Subsequently, reduced density results in low thermal conductivity of a dry-film coating formed from the coating compositions described herein. In some embodiments, coating compositions provided herein may include 1-30 wt. %, or 10-20 wt. % low-density minerals or thermoplastics. In some embodiments, coating compositions provided herein may comprise less than or equal to 30 wt. %, less than or equal to 25 wt. %, less than or equal to 20 wt. %, less than or equal to 15 wt. %, less than or equal to 10 wt. %, or less than or equal to 5 wt. % low-density minerals or thermoplastics. In some embodiments, coating compositions provided herein may comprise more than or equal to 1 wt. %, more than or equal to 5 wt. %, more than or equal to 10 wt. %, more than or equal to 15 wt. %, more than or equal to 20 wt. %, or more than or equal to 25 wt. % low-density minerals or thermoplastics. Suitable commercially-available low-density minerals or thermoplastics can include 3M® Glass Bubbles, Poraver® Expanded glass, Sphericel® hollow glass microspheres, Hollowlite®, Expancel®, or diatomaceous earth. The incorporation of a low- density additive can allow the density of the composition to be 30-50% lower than that of a composition without a low-density additive (all else being equal).

[0072] In some embodiments, heat-reflecting particles may be included in coating compositions described herein. Heat-reflecting particles may comprise metal oxides/salts/complexes that have the ability to reflect visible and near-infrared (heat or thermal reflectance from 400nm to 2,500nm) radiation. Some of the heat-reflecting particles may comprise Zinc Oxide (ZnO), and/or Indium Tin Oxide (In2-_pSn_pO3, wherein p can be any positive number less than 2). The heat-reflecting particles have the ability to be embedded on the low-density minerals or thermoplastics, creating a composite compound that presents low thermal conductivity X and high thermal reflectance from 400nm to 2,500nm. In some embodiments, coating compositions provided herein may include 0 - 5 wt. % heat-reflecting particles. In some embodiments, coating compositions provided herein may comprise less than or equal to 5 wt. %, less than or equal to 4 wt. %, less than or equal to 3 wt. %, less than or equal to 2 wt. %, less than or equal to 1 wt. % heat-reflecting particles. In some embodiments, coating compositions provided herein may comprise more than or equal to 0 wt. %, more than or equal to 1 wt. %, more than or equal to 2 wt. %, more than or equal to 3 wt. %, more than or equal to 4 wt. % heat-reflecting particles. Suitable commercially- available heat-reflecting particles can include Evonik® VP ITO IR5, NanoPhos' proprietary sol-gel preparation product of nanosized Zinc Oxide, CHROMA-CHEM® Spartacryl PM®, CHROMA-CHEM® 50-990, or Novapint® D.

[0073] In some embodiments, coating compositions provided herein may comprise a colorant. For example, the colorant may include one or more of a pigment, filler, or dye. In some embodiments, thermal insulating aspartic ester polyurea (polyaspartic) coating compositions provided herein may include 5-25 wt. % colorant. In some embodiments, coating compositions provided herein may comprise less than or equal to 25 wt. %, less than or equal to 20 wt. %, less than or equal to 15 wt. %, or less than or equal to 10 wt. % colorant. In some embodiments, thermal insulating aspartic ester polyurea (polyaspartic) coating compositions provided herein may comprise more than or equal to 5 wt. %, more than or equal to 10 wt. %, more than or equal to 15 wt. %, more than or equal to 20 wt. % pigments, or fillers, or dyes. Suitable commercially-available pigments, or fillers, or dyes can include rutile titanium dioxide, Tronox® CR-826, Tronox® CR-828, Kronos® 2160, Kronos® 2360, Kronos® 2160, Kronos® 2310, Ti-Pure® R-902+, Ti-Pure® R-746, Sodasil® P95, or Sibelite® M4000.

[0074] Thermal insulating aspartic ester polyurea (polyaspartic) coating compositions provided herein comprise a polyi so cyanate resin hardener. Polyisocyanate resin hardener is an organic molecule or polymer that abides a minimum of two functional and reactive groups of isocyanates (-N=C=O). The functional and reactive isocyanate groups react with the secondary amino-functional co-reactant resin to yield aspartic ester polyurea (polyaspartic) coatings. Their type and content are responsible for determining the Pot Life, i.e., the time from mixing the two components of the thermal insulating aspartic ester polyurea (polyaspartic) coating formulation together to the point at which the mixed components are no longer useable or applicable on the substrate, due to setting or viscosity increase or formulation curing. Suitable commercially-available polyisocyanate resin hardener can include Desmodur® N3600, Desmodur® E2863XP, Teracure® NX-16, Teracure® NX-19, Wannate® HT-600, Tolonate® X FLO 100 or Tolonate® HDT. In some embodiments, thermal insulating aspartic ester polyurea (polyaspartic) coating compositions provided herein may comprise 10-50 wt. % polyisocyanate resin hardener. In some embodiments, thermal insulating aspartic ester polyurea (polyaspartic) coating compositions may comprise less than or equal to 50 wt. %, less than or equal to 45 wt. %, less than or equal to 40 wt. %, or less than or equal to 35 wt. % polyisocyanate resin hardener. In some embodiments, thermal insulating aspartic ester polyurea (polyaspartic) coating compositions may comprise more than or equal to 10 wt. %, more than or equal to 15 wt. %, more than or equal to 20 wt. %, or more than or equal to 25 wt. % polyisocyanate resin hardener.

[0075] In some embodiments, the thermal insulating aspartic ester polyurea (polyaspartic) coating formulation provided herein may comprise one or more anticorrosive metal oxides or phosphates. Metal oxides and/or phosphates can help prevent premature and/or excessive corrosion of thermal insulating aspartic ester polyurea (polyaspartic) formulation coatings provided herein. When metal oxides/phosphates are incorporated into polyaspartic resins, the corrosion rate can be reduced because the particles can occupy minor defects and increase the cross-linking density. This increase in cross-linking density can cause improved durability of the coating. Suitable metal oxides include zinc oxide, zinc phosphates, tin(IV) oxide, SiCh, Fe2O3, and mixtures. Thermal insulating aspartic ester polyurea (polyaspartic) coating formulation comprising too much, or too little metal oxide/phosphate may not have desirable anticorrosive properties. In some embodiments, thermal insulating aspartic ester polyurea (polyaspartic) coating compositions provided herein may comprise 0 - 20 wt. % or 5-15 wt. % metal oxide and/or phosphate. In some embodiments, thermal insulating aspartic ester polyurea (polyaspartic) coating compositions may comprise less than or equal to 20 wt. %, less than or equal to 15 wt. %, less than or equal to 10 wt. %, less than or equal to 5 wt. %, or less than or equal to 1 wt. % metal oxide and/or phosphate. In some embodiments, thermal insulating aspartic ester polyurea (polyaspartic) coating compositions may comprise more than or equal to 0.00 wt. %, more than or equal to 0.1 wt. %, more than or equal to 1 wt. %, more than or equal to 5 wt. %, more than or equal to 10 wt. %, or more than or equal to 15 wt. % metal oxide and/or phosphate.

[0076] In some embodiments, thermal insulating aspartic ester polyurea (polyaspartic) coating compositions may include an organic solvent. For example, suitable organic solvents can include at least one of Methyl Ethyl Ketone, Methyl isobutyl ketone, Xylene, Methoxy propyl acetate, butyl acetate, or glycol esters. In some embodiments, a thermal insulating aspartic ester polyurea (polyaspartic) coating composition may comprise 0 - 40 wt. % or 10- 30 wt. % organic solvent. In some embodiments, a thermal insulating aspartic ester polyurea (polyaspartic) coating compositions may comprise less than or equal to 40 wt. %, less than or equal to 30 wt. %, less than or equal to 20 wt. %, less than or equal to 10 wt. %, or less than or equal to 5 wt. % solvent. In some embodiments, a thermal insulating aspartic ester polyurea (polyaspartic) coating compositions may comprise more than or equal to 0 wt. %, more than or equal to 5 wt. %, more than or equal to 10 wt. %, more than or equal to 20 wt. %, or more than or equal to 30 wt. % organic solvent.

[0077] In some embodiments, thermal insulating aspartic ester polyurea (polyaspartic) coating compositions may include an ultraviolet absorber or stabilizer additive. Ultraviolet absorber or stabilizer additives protect cured coating by converting absorbed ultraviolet irradiation into low-impact heat. Ultraviolet absorber or stabilizer additives are mainly used to curtail photodegradation in coatings by playing a key role in suppressing the generation of radicals that cause resins to degrade. In some embodiments, thermal insulating aspartic ester polyurea (polyaspartic) coating compositions provided herein may comprise 0- 1 wt. % ultraviolet absorber or stabilizer additive. In some embodiments, thermal insulating aspartic ester polyurea (polyaspartic) coating compositions may comprise less than or equal to 1 wt. %, less than or equal to 0.8 wt. %, less than or equal to 0.6 wt. %, or less than or equal to 0.4 wt. % ultraviolet absorber or stabilizer additive. In some embodiments, thermal insulating aspartic ester polyurea (polyaspartic) coating compositions may comprise more than or equal to 0 wt. %, more than or equal to 0.2 wt. %, more than or equal to 0.4 wt. %, or more than or equal to 0.6 wt. % ultraviolet absorber or stabilizer additive. Suitable commercially-available ultraviolet absorber or stabilizer additives may include molecules of benzophenone, or benzotriazole, or HALS (Hindered Amine Light Stabilizers) family. Ultraviolet absorber or stabilizer additives may include Tinuvin®, Riasorb®, Songsorb®, or Ruva®.

[0078] In some embodiments, thermal insulating aspartic ester polyurea (polyaspartic) coating compositions may include one or more of an algicide or a fungicide additive. Algicide or fungicide additives protect cured coating by the development of algae or fungi fouling. In some embodiments, thermal insulating aspartic ester polyurea (polyaspartic) coating compositions provided herein may comprise 0-1 wt. % algicide or a fungicide additive. In some embodiments, thermal insulating aspartic ester polyurea (polyaspartic) coating compositions may comprise less than or equal to 1 wt. %, less than or equal to 0.8 wt. %, less than or equal to 0.6 wt. %, or less than or equal to 0.4 wt. % algicide or a fungicide additive. In some embodiments, thermal insulating aspartic ester polyurea (polyaspartic) coating compositions may comprise more than or equal to 0 wt. %, more than or equal to 0.2 wt. %, more than or equal to 0.4 wt. %, or more than or equal to 0.6 wt. % algicide or a fungicide additive. Suitable commercially-available algicide or fungicide additives may include molecules of chlorothalonil, lodopropynyl Butyl Carbamate, octyl isothiazolone, zinc pyrithione, heterocyclic N, S compounds and N-haloalkyl thiol compounds family. Algicide or fungicide additives may include MuffaControl®, Fungitrol®, Troysan®, or Zinc Omadine®.

[0079] The table below provides a list of each of the suitable components of a coating composition provided herein:

Thermal Insulating Aspartic Ester Polyurea (Polyaspartic) Coated Substrates

[0080] The above-described thermal insulating aspartic ester polyurea (polyaspartic) coating compositions can be used to prepare protective coatings used for building & construction, marine, industrial, and/or transportation applications, including, but not limited to roofs, masonry, metal facades, geotextiles for solar installations, metal pipes, heat exchangers, industrial heat reactors, tanks, vehicle fairings, refrigerated trucks, and box containers. Discussed below are various application/deposition methods for preparing protective coatings.

[0081] FIG. 1 A shows a thermal insulating aspartic ester polyurea (polyaspartic) coating composition according to some embodiments. Specifically, the coating formulation has been applied on a cementitious rooftop by roller brush.

[0082] FIG. IB shows a thermal insulating aspartic ester polyurea (polyaspartic) coating composition according to some embodiments that has been applied on a cementitious rooftop by airless sprayer (nozzle orifice size: 0.017" -0.019", Pressure settings: 3000 pounds per square inch). [0083] Substrates coated with the thermal insulating aspartic ester polyurea (polyaspartic) coating compositions provided herein may present decreased surface roughness, after the coating formulation has cured. The decreased surface roughness is attributed to the inherent capacity of the aspartic ester polyurea (polyaspartic) resins to successfully encage pigments or fillers, preventing them from forming surface defects, in the form of high surface peaks. A reduced roughness can improve dirt pick-up and improve long-term Total Solar Spectrum Reflectance p_e properties. According to The American Society of Mechanical Engineers (ASME) publication Y 14.36 - 2018: Surface Texture Symbols, the roughness (R_z) is the average distance between the highest peak and lowest valley in each sampling length. In some embodiments, the roughness of a substrate coated with a thermal insulating aspartic ester polyurea (polyaspartic) coating composition provided herein may be 10-60 pm, 20-50 pm, or 30-40 pm. In some embodiments, the roughness of a substrate coated with a thermal insulating aspartic ester polyurea (polyaspartic) coating composition provided herein may be less than or equal to 60, 55, 50, 45, 40, 35, 30, 25, 20, or 15 pm. In some embodiments, the roughness of a substrate coated with a thermal insulating aspartic ester polyurea (polyaspartic) coating composition provided herein may be more than or equal to 10, 15, 20, 25, 30, 35, 40, 45, 50, or 55 pm.

[0084] In some embodiments, a coating on a substrate and prepared using a coating composition as described herein has a cross-plane thermal conductivity of 0.5- 1.5 W/m-K. In some embodiments, the cross-plane thermal conductivity of a coating may be less than or equal to 1.5, 1.25, 1, or 0.75 W/m-K. In some embodiments, the cross plane thermal conductivity may be greater than or equal to 0.5, 0.75, 1 , or 1.25 W/m- K.

[0085] In some embodiments, a coating on a substrate and prepared using a coating composition as described herein presents an emissivity value greater of 0.6. In some embodiments, the emissivity of a coating may be greater than or equal to 0.6, 0.7, 0.8, or 0.9.

[0086] In some embodiments, a coating on a substrate and prepared using a coating composition as described herein has a total reflectance value in the total solar spectrum (p_e) greater of 0.6. In some embodiments, the total reflectance value in the total solar spectrum (p_e) of a coating may be greater than or equal to 0.6, 0.7, 0.8, or 0.9.

[0087] In some embodiments, a coating on a substrate and prepared using a coating composition as described herein has a thickness of 500-1500 pm. In some embodiments, the thickness of the coating may be less than or equal to 1500, 1400, 1300, 1200, 1100, 1000, 900, 800, 700, or 600 pm. In some embodiments, the thickness of the coating may be greater than or equal to 500, 600, 700, 800, 900, 1000, 1 100, 1200, 1300, or 1400 pm.

Methods of Preparing Thermal Insulating Aspartic Ester Polyurea Coating Compositions

[0088] FIG. 2 shows a flow chart for preparing a coating composition, according to some embodiments. As shown, various components are combined to form a base composition 216. For example, a secondary amino-functional co-reactant for polyisocyanates resin 202, a rheology additive 204, a low-density mineral or thermoplastic 206, heat- reflecting particles 208, colorants 210, anticorrosive metal oxides and/or phosphates 212, and/or solvent 214. Each of these components may be mixed to form base composition 216. In some embodiments, the density of the base composition 216 is in the range of 0.90-1.10 Kg-L'¹.

[0089] A hardener composition 222 is formed by mixing a hardener 218 and a solvent 220. In some embodiments, the density of the hardener composition 222 is in the range of 0.90-1.20 Kg-L-¹.

[0090] Once the base composition 216 and hardener composition 222 are formed, they are mixed together to form the final product, a coating composition 224 according to embodiments provided herein.

[0091] The mixing ratio of the base composition 216 to the hardener composition 222 can depend on the stoichiometry of the reaction between the secondary amino-functional coreactant for polyisocyanates resin in the base composition 216 and the polyisocyanates resin hardener of the hardener composition 212.

[0092] In some embodiments, the coating composition may comprise 40-85 wt. % base composition 216. In some embodiments, the coating composition may comprise less than or equal to 85, 80, 75, 70, 65, 60, 55, 50, or 45 wt. % base composition 216. In some embodiments, the coating composition may comprise more than or equal to 40, 45, 50, 55, 60, 65, 70, 75, or 80 wt. % base composition 216. In some embodiments, the coating composition may include 15-60 wt. % hardener composition 222. In some embodiments, the coating composition may include less than or equal to 60, 55, 50, 45, 40, 35, 30, 25, or 30 wt. % hardener composition 222. In some embodiments, the coating composition may include more than or equal to 15, 20, 25, 30, 35, 40, 45, 50, or 55 wt. % hardener composition 222. [0093] Specific examples of preparing a coating composition according to some embodiments are further described below.

EXAMPLES

[0094] Example 1 : Composition preparation and application to form a coating

[0095] In a 200L stainless-steel reactor, 114.0 kg of Desmophen® 1420 and 1 .0 kg of RHEOBYK® 7410 ET is combined. The mixture was stirred at 600 rpm for 4 minutes. Subsequently, 22.0 kg of rutile titanium dioxide (Ti-Pure® R-902+) was added, together with 6.0Kg Sodasil® P95, 6.0Kg heat-reflecting Zinc Oxide particles (NanoPhos preparation by sol-gel method, annealing at 210°C, hexagonal phase of Wurtzite type, dso = 58nm) and 20.0Kg Sibelite® M4000. The mixture was dispersed (ground) at 1200 rpm for 12 minutes. After the grinding phase, the dispersion speed was reduced to mixing (200rpm) and the addition of 20.0 kg of diatomaceous Earth, 1.0 kg of 3M® Glass Bubbles KI, 6.0 kg of 3M® Glass Bubbles K37, and 4.0 kg of 3M ^R Glass Bubbles S22 took place. The let-down phase of liquid base composition was concluded after 15 minutes of slow mixing (200rpm). The preparation was allowed to cool down at 20°C (68°F) ambient temperature.

[0096] The hardener composition was prepared in a 200L stainless-steel reactor by combining 50.0 kg of Desmodur® N3600 and 150.0 kg Desmodur® E2863XP. The mixture was stirred at 600 rpm for 10 minutes and allowed to cool down at an ambient temperature of 20°C (68°F).

[0097] A thermal insulating aspartic ester polyurea (polyaspartic) coating formulation was obtained by mixing 10.0 kg of the liquid base composition with 6.5 kg of the hardener composition. The resulting mixture was stirred thoroughly using a motor blade mixer at 300rpm for 2±1 minutes and presented a density of 0.97Kg-L’¹ at an ambient temperature of 20°C (68°F). The solids by volume (SV) ratio of the thermal insulating aspartic ester polyurea (polyaspartic) coating composition is 100%, and thus the composition is a high-solids, solvent-free composition. Solids by volume (SV) refer to the percent ratio of the volume of dissolved solids (non-fluid particles) in a given mixture or solution relative to the overall three-dimensional linear space (i.e., total volume) that is occupied by said fluid mixture.

[0098] The coating composition was applied to a dry and clean surface using an airless spraying gun (Airless sprayer - Paint pressure pot with power agitator, double air regulators, moisture trap, 1/2" ID fluid hose, 5/16" ID air hose, DeVilbiss 510 gun, "E" tip and needle, 74 or 78 air cap. Minimum: 30: 1 pump, Nozzle tip: 0.019"). The surface preparation was completed according to ISO 8502-3: 1992, and the surface was tested for cleanliness. To avoid condensation, the composition was applied to the surface at a temperature above the dew point. The airless spraying gun was used with a nozzle tip (inch/ 1000) of 19 and a pressure at Nozzle (minimum) of 150 bar/2100 psi. Adequate ventilation was provided during application and drying, and the application took place at temperatures above 5°C (32°F). The temperature of the surface and that of the final composition itself was also above this limit. Curing requires a relative humidity of 30-85%, even though relative humidity values above 60% reduce the available pot life (workability time) to half the expected 45min. Windy weather conditions might adversely affect the end coating properties. To adequately apply the composition to the surface, the spray gun trigger was squeezed while the gun was off to the side of the application area, and then the spray gun was moved onto the work. The spraying gun was moved parallel to the surface and kept perpendicular to the surface. The spraying gun was moved quickly over the surface to prevent runs or final composition sagging. The final wet film thickness was less than 340 microns, and spraying strokes overlapped 20 to 30 percent. Three repetitive spraying applications (coats) yielded a final dry film thickness of 1000±50 pm. Each application cycle was performed 120min after the previous one (recoating interval). The coating was cured under ambient conditions for a minimum of 140 hours.

[0099] Example 2: Composition preparation and application to form a coating

[0100] In a 200L stainless-steel reactor, the liquid base composition initially combines 50.0 kg of N,N’-[methylenebis(2-methyl-4,l -cyclohexanediyl)] bis-1,1 ’,4, 4’-tetraethyl ester (CAS No.: 136210-32-7, Feispartic® F520), 50.0 kg of aspartic polyether ester (CAS No.: 152637- 10-0, Feispartic® F2850), and 1.0 kg of RHEOBYK® 7410 ET. The mixture was stirred at 600 rpm for 4 minutes. Subsequently, 36.0 kg of rutile titanium dioxide (Tronox® CR-828) was added, together with 3.0Kg Indium Tin Oxide (Evonik® VP ITO IR5) and lO.OKg Sibelite® M4000. The mixture was dispersed (ground) at 1200 rpm for 12 minutes. After the grinding phase, the dispersion speed was reduced to mixing (200rpm) and the addition of 18.0 kg Xylene, 20.0 kg of diatomaceous Earth, 2.0 kg ofNouryon Expancel 031 DU 40, and 10.0 kg of Hollowlite® HL60S took place. The let-down phase of liquid base composition was concluded after 15 minutes of slow mixing (200rpm). The preparation was allowed to cool down at 20°C (68°F) ambient temperature. [0101] In a 200L stainless-steel reactor, the hardener composition is prepared by combining 160.0 kg of Wannate® HT 600 and 40.0 kg Xylene. The mixture was stirred at 600 rpm for 10 minutes and allowed to cool down at an ambient temperature of 20°C (68°F).

[0102] The thermal insulating aspartic ester polyurea (polyaspartic) coating formulation was obtained by mixing 10.0 kg of Example 2 liquid base composition with 3.7 kg of hardener composition. The resulting mixture was stirred thoroughly using a motor blade mixer at 300rpm for 2±1 minutes and presented a density of 0.95Kg- 1/¹ at an ambient temperature of 20°C (68°F). The solids by volume (SV) ratio of the thermal insulating aspartic ester polyurea (polyaspartic) coating composition is 92%, and thus the composition is a high-solids, solvent- free composition. Solids by volume (SV) refer to the percent ratio of the volume of dissolved solids (non-fluid particles) in a given mixture or solution relative to the overall three- dimensional linear space (i.e., total volume) that is occupied by said fluid mixture.

[0103] The coating composition was applied to a dry and clean surface using an airless spraying gun (Airless sprayer - Paint pressure pot with power agitator, double air regulators, moisture trap, 1/2" ID fluid hose, 5/16" ID air hose, DeVilbiss 510 gun, "E" tip and needle, 74 or 78 air cap. Minimum: 30: 1 pump, Nozzle tip: 0.019"). The surface preparation was completed according to ISO 8502-3:1992, and the surface was tested for cleanliness. To avoid condensation, the composition was applied to the surface at a temperature above the dew point. The airless spraying gun was used with a nozzle tip (inch/ 1000) of 19 and a pressure at Nozzle (minimum) of 150 bar/2100 psi. Adequate ventilation was provided during application and drying, and the application took place at temperatures above 5°C (32°F). The temperature of the surface and that of the final composition itself was also above this limit. Curing requires a relative humidity of 30-85%, even though relative humidity values above 60% reduce the available pot life (workability time) to half the expected 45min. Windy weather conditions might adversely affect the end coating properties. To adequately apply the composition to the surface, the spray gun trigger was squeezed while the gun was off to the side of the application area, and then the spray gun was moved onto the work. The spraying gun was moved parallel to the surface and kept perpendicular to the surface. The spraying gun was moved quickly over the surface to prevent runs or final composition sagging. The final wet film thickness was less than 380 microns, and spraying strokes overlapped 20 to 30 percent. Three repetitive spraying applications (coats) yielded a final dry film thickness of 1000±50 pm. Each application cycle was performed 180min after the previous one (recoating interval). The coating was cured under ambient conditions for a minimum of 140 hours. [0104] Example 3: Composition preparation and application to form a coating

[0105] In a 200L stainless-steel reactor, the liquid base composition is formed by initially combining 80.0 kg of Teraspartic® 277, 50.0 kg of Teraspartic® 292, 1.0 kg of DISPERBYK®-2152, 1.0 kg of BYK-052 N, and 1.0 kg of BYK®-354. The mixture was stirred at 600 rpm for 4 minutes. Subsequently, 14.0 kg of rutile titanium dioxide (Kronos® 2360) was added with lO.OKg Sodasil® P95 and 16.0Kg heat-reflecting Zinc Oxide particles (NanoPhos preparation by sol-gel method, annealing at 210°C, hexagonal phase of Wurtzite type, dso = 58nm). The mixture was dispersed (ground) at 1200 rpm for 12 minutes. After the grinding stage, the dispersion speed was reduced to mixing (200rpm), and the addition of 24.0 kg of diatomaceous Earth and 1,0 kg of Poraver® 0.1-0.3 took place. The let-down phase of the liquid base composition was concluded after 15 minutes of slow mixing (200rpm). The preparation was allowed to cool down at 20°C (68°F) ambient temperature.

[0106] The hardener composition is prepared in a 200L stainless-steel reactor by combining 130.0 kg of Tolonate® HDT and 70.0 kg Tolonate® X FLO 100. The mixture was stirred at 600 rpm for 10 minutes and allowed to cool down at an ambient temperature of 20°C (68°F).

[0107] The thermal insulating aspartic ester polyurea (polyaspartic) coating formulation was obtained by mixing 10.0 kg of Example 3 liquid base composition with 5.5 kg of Example 3 hardener composition. The resulting mixture was stirred thoroughly using a motor blade mixer at 300rpm for 2±1 minutes and presented a density of 1.08Kg- L'¹ at an ambient temperature of 20°C (68°F). The solids by volume (SV) ratio of the thermal insulating aspartic ester polyurea (polyaspartic) coating composition is 98%, and thus the composition is a high-solids, solvent-free composition. Solids by volume (SV) refer to the percent ratio of the volume of dissolved solids (non-fluid particles) in a given mixture or solution relative to the overall three-dimensional linear space (i.e., total volume) that is occupied by said fluid mixture.

[0108] The composition was applied to a dry and clean surface using an airless spraying gun (Airless sprayer - Paint pressure pot with power agitator, double air regulators, moisture trap, 1/2" ID fluid hose, 5/16" ID air hose, DeVilbiss 510 gun, "E" tip and needle, 74 or 78 air cap. Minimum: 30: 1 pump, Nozzle tip: 0.019"). The surface preparation was completed according to ISO 8502-3: 1992, and the surface was tested for cleanliness. To avoid condensation, the composition was applied to the surface at a temperature above the dew point. The airless spraying gun was used with a nozzle tip (inch/ 1000) of 19 and a pressure at Nozzle (minimum) of 150 bar/2100 psi. Adequate ventilation was provided during application and drying, and the application took place at temperatures above 5°C (32°F). The temperature of the surface and that of the final composition itself was also above this limit. Curing requires a relative humidity of 30-85%, even though relative humidity values above 60% reduce the available pot life (workability time) to half the expected 45min. Windy weather conditions might adversely affect the end coating properties. To adequately apply the composition to the surface, the spray gun trigger was squeezed while the gun was off to the side of the application area, and then the spray gun was moved onto the work. The spraying gun was moved parallel to the surface and kept perpendicular to the surface. The spraying gun was moved quickly over the surface to prevent runs or final composition sagging. The final wet film thickness was less than 340 microns, and spraying strokes overlapped 20 to 30 percent. Three repetitive spraying applications (coats) yielded a final dry film thickness of 1000±50 pm. Each application cycle was performed 240min after the previous one (recoating interval). The coating was cured under ambient conditions for a minimum of 140 hours.

[0109] Example 4: Reflectance of the aspartic ester polyurea (polyaspartic) coatings

[0110] To determine the thermal properties of the disclosed thermal insulating aspartic ester polyurea (polyaspartic) coating compositions, four rectangular coating samples were prepared using the coating composition described in Example 1, with dimensions of 55mm by 55mm, for the determination of solar direct absorptance a_e (300nm - 2,500nm), according to international testing standard DIN EN 410, 2011 Edition, April 2011 - Glass in building - Determination of luminous and solar characteristics of glazing. The test method involves the determination of spectral normal - hemispherical reflectance p_e in the wavelength range between 300nm and 2,500nm, using a Perkin-Elmer double monochromator spectrometer Lambda 19 with a 150mm integrating sphere. As the experimental solar transmittance r_e for a disclosed thermal insulating aspartic ester polyurea (polyaspartic) formulation coatings of any embodiments are determined to be zero, the equations a_e + T_e + Pe = 1 or a_e% + _e% + p_e% = 100% are modified to a_e + pe = 1 or a_e% + p_e% = 100%.

[0111] Table 2, below, presents the experimental determination of reflectance in the total solar spectrum (p_e), the ultraviolet UV spectrum region (pe.uv, 300nm - 380nm), the visible VIS spectrum region (pe.vis, 380nm - 780nm), the near-infrared NIR spectrum region of (pe,NiR, 380nm - 780nm) and the modified visible VIS spectrum region (p_v, 380nm - 780nm), according to DIN EN 410, 2011 Edition, April 2011 international testing standard Table 1 and considering the relative spectral distribution of illuminant D65 multiplied by the spectral sensitivity of the human eye.

Spectrum Region . Reflectance p solar direct energy

Table 2

[0112] Example 5 : Thermal emissivity of thermal insulating aspartic ester polyurea (polyaspartic) coatings

[0113] To determine the thermal emissivity of the disclosed thermal insulating aspartic ester polyurea (polyaspartic) coatings, four rectangular coating samples were prepared using the coating composition described in Example 1, with dimensions of 55mm by 55mm, for the determination of the hemispherical thermal emissivity s, from the near-normal hemispherical reflectance R of the medium-infrared NIR spectrum region (2,500nm - 25,000nm), determined employing a Bruker Vertex 70 FTIR spectrophotometer with a gold-coated integrating sphere. Normalization of equation s = 1 - R was based on Planck body radiation spectrum at the temperature of 283°K (10°C = 50°F), as per the International testing standard ISO EN 12898:2019 - Glass in building - Determination of the emissivity 8. The thermal emissivity s was determined to be 0.93.

[0114] Example 6: Solar reflective index of thermal insulating aspartic ester polyurea (polyaspartic) coatings

[0115] The Solar Reflectance Index (SRI) of the coating composition described in Example Iwas tested using the international ASTM (American Society for Testing and Materials) testing method El 980-11(2019) - Standard Practice for Calculating Solar Reflectance Index of Horizontal and Low-Sloped Opaque Surfaces. Based on the determination of total solar spectrum reflectance (Example 4) and thermal emissivity (Example 5) and according to ASTM testing method El 980-11(2019), the SRI index for the disclosed thermal insulating aspartic ester polyurea (polyaspartic) coating formulation coatings is 121.1 (Low-wind, 0-2 m-s-1), 119.0 (Medium-wind, 2-6 m-s-1), and 118.0 (High-wind, 6-10 m- s-1).

Example 7: Cross-plane thermal conductivity of thermal insulating aspartic ester polyurea (polyaspartic) coatings

[0116] Five rectangular coating samples using the coating composition described in Example 1, with dimensions of 50mm by 50mm, were prepared to determine the cross-plane thermal conductivity % of the disclosed thermal insulating aspartic ester polyurea (polyaspartic) coatings. The temperature drop across the samples determines the cross-plane thermal conductivity X. The samples, presenting a thickness of df = l,000±50pm, are deposited onto a polished silicon wafer substrate with high thermal conductivity X and minor surface roughness. A metallic (Cr/Au film) strip is then deposited onto the sample. During the experiment, the metallic strip is heated by a direct current. The metallic strip serves as an electrical heater and a sensor to measure its temperature. Another sensor is used to directly measure the temperature at the bottom side of the dry film sample. A two- dimensional heat conduction model is then used to infer the substrate temperature rise at the heater/sensor location from the measured substrate temperature rise at the sensor location and subsequently determine the cross-plane thermal conductivity % (Borca-Tasciuc, T., Chen, G., Thermal Conductivity (ed. Tritt, T.M.), pg. 205-237, ISBN 978-0-306-48327-1, Springer, Boston, MA, USA, 2004). The cross-plane thermal conductivity average of twenty-five measurements (five samples, five repeated measurements, each) is reported herein. The crossplane thermal conductivity X of the disclosed thermal insulating aspartic ester polyurea (polyaspartic) coatings of certain embodiments is determined to be X = 0.083±0.007 W m’

[0117] Example 8: Topography and three-dimensional structure of thermal insulating aspartic ester polyurea (polyaspartic) coatings

[0118] To determine the topography and understand the three-dimensional structure of the disclosed thermal insulating aspartic ester polyurea (polyaspartic) coating formulation coatings of certain embodiments, a coating sample using the coating composition described in Example 1 was analyzed by means of Scanning Electron Microscopy (SEM) and Energy- Dispersive X-ray (EDX) techniques, as shown in FIGs. 3A-3D. The sample had dimensions of 50mm by 50mm and a thickness of df = l,000±50pm and was deposited onto a Teflon® substrate and allowed to cure at room temperature (25°C = 77°F) for seven days. Instead of blade sliced, the sample was hand torn into two pieces to prevent destructive force on the low-density minerals or thermoplastics. Scanning Electron Microscopy (SEM) and Energy- Dispersive X-ray (EDX) analysis were performed on the l,000±50pm thick, sliced side of the coating sample by a JEOL JSM-6510LV Series Scanning Electron Microscope. Depending on the atomic number, which is a unique property of every element, the X-ray produced by the Scanning Electron Microscope (SEM) has energy attributed to the energy difference of atomic electron transitions. Using this method, X-rays serve as a “fingerprint” of each element and can be employed to map atoms on the sample's surface under examination. This technique is Energy-Dispersive X-ray (EDX) analysis provided by the same analysis equipment.

[0119] Figure 3 A depicts the surface of the thermal insulating aspartic ester polyurea (polyaspartic) coating that was revealed after tearing the coating. Therefore, the arrangement of the particle on the surface of a cured coating is not typical, as it may be affected by the application method, self-leveling properties, etc. Therefore, tearing the coating and observing its inner mass proves a better method for understanding the arrangement of the particles contained. Several spherical ceramic shapes have been revealed, sizing from a few micrometers to almost 50 micrometers. The spherical structures are typical of the low-density minerals or thermoplastics ceramic components that are included in some embodiments. It is also revealed that certain spherical structures are shattered, which is attributed to the tearing preparation of the samples. Yet, it proves that those ceramic spheres are hollow and contribute to lowering the density of the coating composition and, eventually, reducing the thermal conductivity X to values below X = 0.100 W-nr'T ¹.

[0120] Figure 3B reveals the topography of the silicon atoms. The surface density of the silicon atoms is increased in the areas where the low-density minerals or thermoplastics spheres exist. This is explained by the fact that low-density minerals or thermoplastics may be of ceramic nature, as ceramic materials significantly compose silicon atoms.

[0121] Figure 3C maps the carbon atoms, mainly found in the resin component of the thermal insulating aspartic ester polyurea (polyaspartic) coating formulations. Therefore, the diffuse and vague surface density appears rational. The resin fastens all ingredients together; thus, its occurrence should not be concentrated in specific areas. [0122] Finally, the existence of heat-reflecting particles is evident in Figure 3D, as zinc oxide nanoparticles cannot be observed in the SEM surface analysis, but they are abundant in EDX analysis.

Example 9: Mechanical Properties

[0123] To investigate various mechanical properties of coatings described herein, a sample of coating sample prepared using the coating composition described in Example 1 is clamped in the measurement head of a DMA instrument. During measurement, sinusoidal force is applied to the sample via the probe. Deformation caused by the sinusoidal force is detected, and the relationship between the deformation and the applied force is measured. Properties such as elasticity and viscosity are calculated from the applied stress and strain plotted as a function of temperature or time.

[0124] For example, FIG. 4 shows the strain (%) of a thermal insulating aspartic ester polyurea (polyaspartic) coating as a function of stress (MPa) applied at different temperatures, ranging from -40°C = -40°F to 60°C = 140°F. This shows that the polymer structure of a coating of certain embodiments becomes stiffer at lower temperatures revealing a minor strain (%) change as a function of the stress (MPa) applied. On the other side, the strain (%) change increases sharply at elevated temperatures, with only minor changes in stress (MPa) applied.

[0125] FIG. 5 depicts the storage modulus (MPa) and Tan8, as a function of temperature for a coating. The storage modulus (MPa) relates to the material's ability to store energy elastically. Tan8 represents the ratio of the viscous to elastic response of a viscoelastic material or, in other words, the energy dissipation potential of a material. Tan8 relates to vibration damping of thermal insulating aspartic ester polyurea (polyaspartic) formulation coatings of certain embodiments. For vibration damping (or energy dissipation), high Tan8 is needed. Tan6 can provide information on the overall flexibility and the interactions between the components of coating of certain embodiments. The height and area under TanS curve indicate the total energy that a material can absorb. Based on the experimental results of FIG. 6, the glass transition temperature T_g is determined at 32°C = 89.6°F. A glass transition temperature (T_g) is when a coating transforms from ductile to a hard, brittle material. It is the temperature at which carbon chains start to move. At this stage, the amorphous region experiences a transition from a rigid state to a relaxed state, with the temperature at the border of the solid state-changing it to more of a viscoelastic (rubbery) one. The free volume, or the gap between the molecular chains, increases by 2.5 times at this temperature.

[0126] FIG. 6 depicts the extension (%) under tensile strain as a function of the tensile stress (MPa), obtained at 23°C = 73.4°F for thermal insulating aspartic ester polyurea (polyaspartic) coating formulation coatings of certain embodiments. The experimental results indicate that the coating sample can exceed 612% extension at 23°C = 73.4°F, being able to bridge cracks of 6mm when the coating sample thickness equals or exceeds a thickness of df = l,000±50pm.

Example 10: Surface Characteristics

[0127] In order to determine the surface characteristics of a coating prepared using the coating composition described in Example 1 , the surface free energy of the planar surface of a thermal insulating aspartic ester polyurea (polyaspartic) coating formulation coating was determined, as per Owens, Wendt, Rabel, and Kalble (OWRK) method. The OWRK method is a standard method for calculating the surface free energy of a thermal insulating aspartic ester polyurea (polyaspartic) coating formulation coatings of certain embodiments from the contact angle with several liquids. In doing so, the surface free energy is divided into a polar part and a disperse part. FIG. 7 shows the surface free energy plot obtained after determination of water, cyclohexane, and n-propanol contact angles on a thermal insulating aspartic ester polyurea (polyaspartic) coating formulation coating of certain embodiments sample. FIG. 7 plot and OWRK data extrapolation indicate that the surface free energy of the planar surface of a thermal insulating aspartic ester polyurea (polyaspartic) coating formulation coating sample is 29.97mN-m‘^l.

Example 11 : Weather Testing

[0128] The accelerated weathering tester reproduces the damage caused by sunlight, rain, and dew. After 5.000h of testing, the tester can reproduce the damage over fifteen years of operational life. The accelerated tester exposes a coated substrate to alternating UV light and moisture cycles to simulate outdoor weathering at controlled, elevated temperatures. It simulates the effects of sunlight using special fluorescent UV lamps. It simulates dew and rain with condensing humidity and water spray. A coating prepared using the coating composition described in Example 1 was exposed under UV-B (Q-Lab QUV chamber equipped with UVB-313 lamps with an emission maximum at 313nm) testing for 5.000h. No cracking, yellowing, coating defect (as defined in Fitz's Atlas 2 of coating defects, by Brendan Fitzsimons ISBN: 0951394029), or any loss of original properties was revealed, indicating that the useful lifetime of the resulting coating exceeds fifteen years.

Example 12: Electrical Consumption

[0129] Coatings prepared using the coating composition described in Example Iwere applied as thermal insulation and waterproofing on 180m² of a metal rooftop warehouse located in Athens, Attica, Greece. The warehouse remains continuously air-conditioned at 20°C (68°F) to preserve medical treatment compositions stored therein. No other activity is observed therein, regularly. Thus, the total electrical consumption is directly linked to the electrical consumption of the air-conditioning equipment to maintain a stable indoor temperature at 20°C (68°F). The total electrical consumption was observed for six consecutive months (April, May, June, July, August, and September). It was compared to the same months before applying the disclosed thermal insulating aspartic ester polyurea (polyaspartic) coating. The electrical consumption was reduced by 39.2%, supporting that the disclosed thermal insulating aspartic ester polyurea (polyaspartic) coating yielded energy savings of 39.2%.

[0130] The foregoing description, for the purpose of explanation, has been described with reference to specific embodiments. However, the illustrative discussions above are not intended to be exhaustive or to limit the invention to the precise forms disclosed. Many modifications and variations are possible in view of the above teachings. The embodiments were chosen and described in order to best explain the principles of the techniques and their practical applications. Others skilled in the art are thereby enabled to best utilize the techniques and various embodiments with various modifications as are suited to the particular use contemplated.

[0131] Although the disclosure and examples have been fully described with reference to the accompanying figures, it is to be noted that various changes and modifications will become apparent to those skilled in the art. Such changes and modifications are to be understood as being included within the scope of the disclosure and examples as defined by the claims. Finally, the entire disclosure of the patents and publications referred to in this application are hereby incorporated herein by reference. [0132] Any of the systems, methods, techniques, and/or features disclosed herein may be combined, in whole or in part, with any other systems, methods, techniques, and/or features disclosed herein.

Claims

1. An aspartic ester polyurea composition comprising: a secondary amino-functional co-reactant for polyisocyanates; one or more of a low-density mineral or thermoplastic; heat-reflecting particles; and a hardener.

2. The composition of claim 1, comprising 5-25 wt. % pigments, or fillers, or dyes.

3. The composition of claim 2, wherein the pigments, or fillers, or dyes comprises rutile titanium dioxide.

4. The composition of claim 3, comprising 0-1 wt. % ultraviolet absorber or stabilizer additive.

5. The composition of claim 4, wherein the ultraviolet absorber comprises of Tinuvin® 292.

6. The composition of any of claims 1-5, comprising 0-1 wt. % algicide or fungicide additive.

7. The composition of claim 6, wherein the algicide or fungicide additive comprises Zinc Omadine®.

8. The composition of any of claims 1-7, comprising 0-3 wt. % rheology additive.

9. The composition of claim 8, wherein the rheology additive comprises RHEOBYK® 7410 ET.

10. The composition of any of claims 1-9, comprising 0-40 wt. % solvent.

11. The composition of claim 10, wherein the solvent comprises xylene.

12. The composition of any of claims 1-11, comprising 10-70 wt. % a secondary aminofunctional co-reactant for polyisocyanates resin.

13. The composition of any of claims 1-12, comprising 1-30 wt. % one or more of a low density mineral or thermoplastic.

14. The composition of any of claims 1-13, comprising 0.01-5 wt. % heat-reflecting particles.

15. The composition of any of claims 1-14, comprising 10-50 wt. % hardener.

16. The composition of claim 15, wherein the hardener comprises a polyisocyanate resin hardener.

17. The composition of any of claims 1-16, comprising 5-15 wt. % one or more of anticorrosive metal oxides or phosphates.

18. The composition of claim 17, wherein the one or more of anticorrosive metal oxides or phosphates comprises zinc oxide, zinc phosphates, tin(lV) oxide, SiCh, or Fe2<D3.

19. A coated substrate comprising: a substrate; and a coating on the substrate, wherein the coating is formed from a composition comprising: a secondary amino-functional co-reactant for polyisocyanates resin; one or more of a low density mineral or thermoplastic; heat-reflecting particles; and a hardener.

20. The coated substrate of any of claims 19, wherein the composition comprises 10-70 wt. % a secondary amino-functional co-reactant for polyisocyanates resin.

21. The coated substrate of any of claims 19 or 20, wherein the composition comprises 0.05-3 wt. % rheology additive.

22. The coated substrate of any of claims 19-21, wherein the composition comprises 1-30 wt. % one or more of a low density mineral or thermoplastic.

23. The coated substrate of any of claims 19-22, wherein the composition comprises 0.01- 5 wt. % heat-reflecting particles.

24. The coated substrate of any of claims 19-23, wherein the composition comprises 10- 50 wt. % hardener.

25. The coated substrate of claim 24, wherein the hardener comprises a polyisocyanate resin hardener.

26. The coated substrate of any of claims 19-25, wherein the composition comprises 5-15 wt. % one or more of anticorrosive metal oxides or phosphates.

27. The coated substrate of claim 26, wherein the one or more of anticorrosive metal oxides or phosphates comprises zinc oxide, zinc phosphates, tin(IV) oxide, SiCh, or Fe Ch.

28. The coated substrate of any of claims 19-27, wherein the composition comprises 0.1 - 25 wt. % solvent.

29. The coated substrate of claim 28, wherein the solvent comprises one or more of methyl ethyl ketone, methyl isobutyl ketone, xylene, methoxy propyl acetate, butyl acetate, or glycol esters.

30. The coated substrate of any of claims 19-29, having a surface roughness of 10-60 pm.

31. The coated substrate of any of claims 19-30, having a thickness of 900-1100 pm.

32. The coated substrate of any of claims 19-31, having a cross-plane thermal conductivity of 0.6-1 W/m-K.

33. The coated substrate of any of claims 19-32, having an extension at 23°C = 73.4°F of greater than 200%.

34. The coated substrate of any of claims 18-33, having an emissivity greater of 0.9.

35. The coated substrate of any of claims 18-34, having a total solar spectrum reflectance of greater of 0.9.

36. The coated substrate of any of claims 18-35, wherein the substrate comprises one or more of a roof, masonry, a metal, a geotextile, a heat exchanger, an industrial heat reactor, a tank, a vehicle fairing, a refrigerated truck, or a box container.