Polysilazane coating method and apparatus

Abstract

The present invention relates to a polysilazane coating formulation, a polysilazane coating method for limiting fragmentation of the polysilazane, and an assembly for carrying out the polysilazane coating method for limiting fragmentation of the polysilazane.

Description

[Technical Field]

[0001] The present invention relates to the formation of polysilazane coatings. The present invention provides a polysilazane coating method for limiting polysilazane fragmentation, and an assembly for carrying out the polysilazane coating method for limiting polysilazane fragmentation. [Background technology]

[0002] Polysilazanes, a group of polymers characterized by a Si-N-Si backbone, have recently attracted increasing interest for their use in coatings. Depending on the coating type and formulation, polysilazane coatings can exhibit a variety of desirable properties. Their high reactivity can result in coatings with, for example, high hardness and weatherability, excellent adhesion and scratch and abrasion resistance, low surface roughness, and high gloss. Excellent heat, chemical, and UV resistance have been demonstrated. Organic polysilazane coatings are reported to have a pencil hardness of 5H when cured at room temperature, in contrast to the more widely used polysiloxane coatings, which have a pencil hardness of 5B using the same curing conditions. Other polysilazane coatings have coefficients of friction of 0.03–0.05, similar to the renowned anti-stick properties of Teflon® (0.04), but with much better scratch and abrasion resistance. Coating hardnesses as high as 3 GPa have been reported for inorganic perhydropolysilazane coatings (yielding SiO2) cured at room temperature, and an astonishing 13 GPa upon further treatment at 700-1000 °C, evidence of the depth of cross-linking in the polysilazane functional units. Distinguished from other common polymers such as polysiloxanes (silicones), polyurethanes, epoxy resins, and PMMA, which are often used for their ease of use and / or low reactivity at ambient conditions, polysilazanes have been called the ultimate binders in their class (polymers used in wet chemistry formulations) due to their high reactivity.

[0003] Although their high reactivity is responsible for their excellent coating properties, the reactivity of polysilazanes also poses challenges and is a major factor preventing their wider use. Polysilazanes must be handled and used with care, avoiding moisture and heat. Furthermore, their reactivity limits the use of additives such as catalysts, which may be necessary to enhance coating performance. Reaction of polysilazane Si-H functional units with additives bearing nucleophilic groups, such as hydroxyl, carbonyl, carboxyl, amine, or other reactive functional units, can lead to degradation of the polymer backbone. Even adding the post-coating curing additive (3-aminopropyl)triethoxysilane (APTES) just before coating application results in significant fragmentation and loss of coating material (polysilazane fragments) of up to 23–31%, depending on humidity, compared to organopolysilazanes without APTES. Fragmentation can result in a reduction in the anti-stick coating properties of organopolysilazane-based coatings, especially when cured at low humidity, because the volatile fragments likely evaporate before reacting with the non-volatile fragments or the polymer backbone. Furthermore, in addition to material loss, fragmentation often causes lower coating hardness and undesirably high coating surface roughness. Because of this, coating quality often leaves something to be desired—either reactive additives that would improve quality are omitted, these additives are included at the expense of fragmentation and / or reduced coating properties, or these additives are added in amounts that are insufficient to affect maximum benefit.

[0004] Therefore, efforts to improve the properties of polysilazane coatings have focused significantly on additive selection, curing methods, and post-application coating manipulation. For example, Furtat et al. [J. Mater. Chem. A, 2017, 5, 25509-25521] improved the hydrophobicity, inertness, and chemical resistance of organopolysilazane Durazane 1800 coatings by first reacting them with fluoroalcohol in the presence of a solution crosslinking catalyst to avoid and / or reverse fragmentation, quenching the catalytic action, and then filtering the polymer-fluoroalcohol hybrid, which was redissolved and applied as a coating. Despite this intriguing approach, the method involves a time-consuming process and is primarily suitable for Durazane 1800, which has low reactivity due to steric hindrance. This work highlights several challenges in the formation of polysilazane coatings: with highly reactive polysilazanes, the entire process must be carried out in an inert environment. Furthermore, scaling up with more reactive polysilazanes requires challenging processes, such as fragmentation over crosslinking and the formation of insoluble precipitates, due to the need to use very dilute solutions to avoid too rapid a reaction. These obstacles can be avoided by using coating additives containing functional groups that do not spontaneously react with polysilazanes, such as vinyl groups, that undergo post-coating radical reactions with Si-H using appropriate catalysts and activators such as UV light, plasma, or heat. However, this approach is inherently self-limiting, as some of the additives do not covalently bond with the polymer and / or are solid-state reactions that carry the risk of phase separation (e.g., fluorinated additives may accumulate only on top of the coating). Furthermore, the types of additives that can be used are significantly limited.

[0005] Therefore, limitations on the types of additives remain a challenge, as do the material losses mentioned above. As a result, to expand the large-scale use of polysilazane coatings, new methods are needed to enhance the properties of polysilazane coatings by broadening the range of applicable additives as well as minimizing the formation of volatile fragments. Furthermore, methods are needed for better control of the porosity and surface roughness of the coatings, and for reducing the processing time and tack-free time after coating. Summary of the Invention

[0006] The present inventors have also realized that the above-mentioned problems can be solved by controlling the reactivity of polysilazanes when the components are introduced into a coating formulation, thereby minimizing or eliminating fragment formation. The present inventors have invented a process for the "in-situ" mixing of the components of a polysilazane-based coating composition in a predetermined order, stepwise, and time-controlled manner, just prior to and / or during application of the coating to a substrate. The various components are selected based on the desired properties of the coating, and the mixing order depends on the sensitivity and / or reactivity of the various components with each other. Thus, the present method allows for the use of a wider range of additives, and the time-controlled mixing limits material loss and / or excessive reaction, both of which result in polysilazane coatings with improved quality compared to known polysilazane coatings. The present method also allows for better control of the porosity and surface roughness of the coating, and allows for the production of coatings with shorter post-coating processing times and faster tack-free times than conventionally used polysilazane coatings.

[0007] In one embodiment, the present invention provides a method for coating polysilazane to limit fragmentation of the polysilazane, the method comprising: i) preparing a coating composition, the preparation of the coating composition comprising: a. introducing component A into a coating composition container; b. introducing component B into a coating composition container and mixing component B with component A; c. introducing component C into the coating composition container and mixing component C with components A and B. wherein components A, B, and C are each selected from the group of polysilazanes, the group of catalysts, or the group of reactive molecules that can react spontaneously with the reactive nanomaterial and / or polysilazane polymer backbone to cause fragmentation; wherein the components A, B, and C are all selected from different groups; The introduction in the sub-step ic) is carried out after the introduction in the sub-step ib) for a predetermined time t c Starts with ;t c is 0 <t c < 900 seconds, t c and the selection of groups for each of the components is predetermined based on the known reactivities of the components with one another. preparing a coating composition; ii) applying the coating composition to a substrate; Including, The step ii) is performed after a predetermined time t ii , starts at 1 to 1200 seconds, t ii is predetermined based on the known reactivities of the components with one another. A polysilazane coating method is provided.

[0008] In another aspect, the present invention provides an assembly for carrying out a polysilazane coating method for limiting fragmentation of the polysilazane.

[0009] Further advantageous effects are set forth in the dependent claims. [Brief explanation of the drawings]

[0010] In order that the present invention may be more readily understood, the following description makes reference to the accompanying drawings.

[0011] [Figure 1] 1 is a flow chart illustrating a method according to the present invention. [Figure 2] 1 is a flow chart illustrating an embodiment of a method according to the present invention. [Figure 3] 1 is a schematic diagram of an assembly according to the present invention; [Figure 4] 1 is a schematic diagram of one embodiment of an assembly according to the present invention; [Figure 5] Schematic of a mixing means for a coating composition container; a) flow redirection barrier (FBR); b) coiled flow path (CFP); c) abrupt increase in diameter. DETAILED DESCRIPTION OF THE INVENTION

[0012] Unless otherwise defined, all technical terms, notations, and other scientific or scientific terms used herein are intended to have the meanings commonly understood by those skilled in the art to which this invention pertains. In some cases, terms having commonly understood meanings are defined herein for clarity and / or ready reference, and the inclusion of such definitions herein should not necessarily be construed as indicating a substantial deviation from what is commonly understood in the art.

[0013] As used herein, the term "polysilazane" refers to a polymer in which alternating silicon and nitrogen atoms form a backbone of the formula [R 1 R 2 Si-NR 3 ] n refers to a polymer containing chains and / or rings of the formula: 1 , R 2 , and R 3may be hydrogen atoms and / or the same or different organic substituents. The term polysilazane may be used to refer to any one of inorganic polysilazanes, organic polysilazanes, polyborosilazanes, polysiloxazanes, or any combination thereof, or any crosspolymer containing any of these or combinations thereof, or any copolymer containing a -Si-N-Si- backbone and Si-H and NH functional units.

[0014] The terms "perhydropolysilazanes" ("PHPS") and "inorganic polysilazanes" refer to compounds of the formula [H2Si-NH] n The term "polysilazane" is used interchangeably to refer to any polysilazane of the type

[0015] The term "organopolysilazane" ("OPSZ") refers to a compound having the formula [R 1 R 2 Si-NR 3 ] n where R 1 , R 2 , and R 3 At least one of is an organic substituent, which is defined as any substituent that contains carbon.

[0016] As used herein, the term "polysilazane coating composition" refers to any composition that includes polysilazane and that can be used to coat a substrate.

[0017] The term "component" is used herein to refer to any compound or material that is or will be included in the polysilazane coating composition. Thus, the term "component" includes any material, compound, additive, etc. that one of ordinary skill in the art would consider for inclusion in a polysilazane coating composition.

[0018] As used herein, the term "reactive" when used with respect to a particular component refers to the ability of that component to participate in a spontaneous chemical reaction or physical interaction (such as aggregation) resulting in a chemical or physical transformation with any other component that is or may be present in the polysilazane coating composition over a time scale t for preparing or storing the polysilazane coating composition. t may be in hours, such as 5 hours, such as 3 hours, such as 2 hours. t may be in minutes, such as 60 minutes, such as 30 minutes, such as 10 minutes, such as 5 minutes, such as 2 minutes. t may be in seconds, such as 60 seconds, such as 30 seconds.

[0019] As used herein, the terms "spontaneous" and "spontaneously" when used with respect to a reaction refer to a reaction that occurs at a temperature T and a pressure p to prepare a polysilazane coating composition without the need for a catalyst or any other activator. T may be ambient temperature, and p may be ambient pressure.

[0020] As used herein, the term "concurrently" refers to any two or more processes occurring at or near the same time, and is not to be interpreted strictly. It is not intended that the processes must start at the same time, nor that the processes must end at the same time.

[0021] As used herein, the term "vessel" refers to any type of vessel, container, tube, pipe, manifold, channel, or other device suitable for receiving and / or containing and / or transporting coating components and / or coating compositions.

[0022] As used herein, the term "mixing" or any variation thereof refers to any method of combining the components of a coating composition, such as, but not limited to, mixing, contacting, blending, stirring, or intermixing, contacting, blending, agitating, etc.

[0023] As used herein, the term "fragmentation" refers to the cleavage of backbone Si-N bonds in polysilazane polymers.

[0024] As used herein, the term "applicator" refers to any means for applying a coating composition to a substrate.

[0025] As used herein, the term "solvent" refers to a liquid substance in which a compound is sufficiently soluble at a given concentration to dissolve the compound. Unless otherwise indicated in the context, the term refers to both solvent mixtures (i.e., solvents consisting of multiple components) and pure compounds (i.e., solvents consisting of a single component).

[0026] As used herein, the term "anhydrous conditions" refers to the avoidance of any significant amount of moisture in the reaction mixture, such as a reaction mixture containing less than 0.5% water by weight, but is not intended to imply the complete absence of moisture.

[0027] As used herein, the term "anhydrous solvent" refers to a solvent that contains less than 0.5% water by weight and that can be maintained or handled under nitrogen or argon gas during the reaction.

[0028] In the following, certain exemplary embodiments as well as general embodiments of the present invention are described. Reference is made to the accompanying drawings. It should be noted, however, that the drawings are exemplary embodiments only, and that other features and embodiments are well within the scope of the invention as claimed.

[0029] It will also be apparent to those skilled in the art that in addition to the coatings disclosed herein, a wide variety of other polysilazane-based coatings can be formed on substrates in accordance with the present invention using the disclosed methods and / or assemblies.

[0030] Generally, there are two types of polysilazanes: inorganic perhydropolysilazanes (PHPS) and organic polysilazanes (OPSZ), which contain organic pendant groups on some of the Si atoms. The organic pendant groups can be or contain reactive centers. The well-known Durazane 1800 contains vinyl groups as pendant groups. Hydrogen (Si-H and NH) attached to the backbone elements makes polysilazanes highly reactive. Polysilazanes can undergo hydrolysis and crosslinking to form SiO2 or crosslink by dehydrogenation to form stable Si-N and Si-Si bonds. Si-H can also undergo hydrosilylation reactions and / or crosslinking with vinyl centers in Durazane 1800 to form, for example, Si-C bonds. These reactions can be accelerated in solution or after coating using catalysts or curing additives such as hydrolysis accelerators (heat, moisture, acid, base, hydrogen peroxide, etc.).

[0031] The high reactivity of the Si-H and Si-NH-Si groups of polysilazanes with moisture and polar surfaces is the reason for their use in coatings, resulting in polysilazane coatings with high crosslink density and, therefore, superior properties to isoelectric polysiloxanes. Many metals, glasses, ceramics, and plastics with hydroxyl groups on their surfaces are easily wetted by polysilazanes. PHPS, in particular, is highly reactive because its functional units are much less affected by steric hindrance than those of organopolysilazanes. Therefore, PHPS polymers can achieve high crosslink density even at room temperature.

[0032] The following have been identified as possible routes for thermal curing of polysilazanes: Hydrosilylation - reaction between vinyl groups and Si-H; Dehydrogenation - a reaction between two Si-H groups or between Si-H and NH; and Polymerization of vinyl groups Hydrosilylation can be carried out at or near room temperature using metal complexes as catalysts. When exposed to moisture, Si-H and Si-NH-Si groups hydrolyze to form silanols, which then crosslink to form Si-O-Si bonds. These reactions can also be accelerated using additives, such as APTES, which rapidly hydrolyze upon exposure to air. This is particularly important for OPSZ, because their reactivity is limited by steric hindrance. Alkoxy groups can also be grafted onto polysilazane molecules to speed up hydrolysis and crosslinking.

[0033] The hydrolysis and crosslinking of polysilazanes are the most important reactions, occurring at or near room temperature. DCP and alkoxy-bearing additives, or grafted groups, are used to further enhance the reactivity of OPSZ. Room-temperature crosslinking in solution (liquid, homogeneous) can also be promoted using nucleophiles (e.g., tetra-n-butylammonium fluoride (TBAF)), dicumyl peroxide (DCP), and metal complexes to produce Si-N and Si-C bonds. Therefore, the silicon, nitrogen, and carbon centers crosslinked in solution are unavailable for further reactions, such as post-coating curing.

[0034] Additives are necessary to enhance the properties of polysilazane coatings, such as hardness, hydrophobicity, coefficient of friction, scratch resistance, and abrasion resistance, or to impart new features, such as pathogen resistance, flexural strength, magnetism, superhydrophobicity, icephobicity, thermal and electrical conductivity. Furthermore, it is important that the additives are not simply physically associated with the polysilazane molecule, but rather are bound to it, preferably covalently; that is, they must react with the polysilazane. When such a reaction occurs, the presence of a crosslinking catalyst, such as TBAF, is crucial to avoid fragmentation. Extensive crosslinking over time usually leads to precipitation and thus to destabilization of the coating formation. Therefore, both the reaction with the additives and the crosslinking of the polysilazane functional groups must be managed and processed in a time-controlled manner.

[0035] The high reactivity of polysilazanes presents significant challenges in additive selection. Polysilazanes are incompatible with all materials containing reactive functional groups, such as hydroxyl groups, including moisture, polar protic solvents, acids, bases, and nanomaterials. Depending on the type of polysilazane (steric hindrance effects) and the chemical environment of the functional groups, polysilazanes may also be incompatible with functional groups such as carbonylamines. The shelf life of polysilazanes decreases with increasing exposure to atmospheric moisture, as well as to materials containing the aforementioned reactive groups. Therefore, for medium- to large-scale industrial applications, constant exposure of polysilazane-based coating formulations to uncontrolled environments is not beneficial. Furthermore, the addition of nanomaterials or other additives containing reactive functional groups can cause polysilazanes to fragment, resulting in volatile components and significant material loss; even curing agents such as APTES cause fragmentation, even when added immediately before coating application. OPSZ formulations may only contain common curing additives such as APTES and DCP; PHPS is too reactive. Therefore, there is limited ability to enhance coating properties through additives with synergistic effects, such as nanomaterials for antibacterial, superhydrophobic, or solid lubricating effects, or additives to accelerate curing, especially at low temperatures and thus reduce processing time.

[0036] Fragmentation refers to the decomposition of the polysilazane backbone to produce volatile or nonvolatile fragments. These fragments may or may not be reactive. The loss of volatile fragments contributes significantly to reduced coating yields. APTES, a post-coating curing additive, is often added to certain types of OPSZ or grafted onto the polymer backbone. The inclusion of APTES results in significant fragmentation and loss of coating material. The more reactive hydroxyl groups cause violent fragmentation reactions in OPSZ, resulting in a significant reduction in coating hardness and other mechanical properties.

[0037] In general, fragmentation of polysilazanes during the coating process can result in the following: Losses of coating materials and high demands on systems for waste disposal, Reduction of coating hardness due to further reduction of molecular weight through fragmentation; and Undesirable large roughness (micro-areas) of the coating surface at low humidity, which always adversely affects the coating properties in terms of anti-stick properties and coefficient of friction

[0038] The present inventors have invented a method for forming a polysilazane coating and an assembly for carrying out the method that solves the above-mentioned problems associated with polysilazane coatings, including eliminating or at least limiting fragmentation. There is no need to prepare and store unstable polysilazane formulations. The method of the present invention achieves the desired level of crosslinking while avoiding extreme or costly conditions, making it a practical, cost-effective method, particularly for industrial use.

[0039] Controlled solution crosslinking allows for a reduction in the time required for post-coating crosslinking. Using other methods, PHPS coatings can be converted to nearly fully functionalized coatings with high hardness and precise optical properties / refractive index in a 10-minute exposure, such as to H2O2. The method of the present invention allows for controlled pre-crosslinking in solution without compromising coating quality. Reducing post-coating crosslinking time is important for industrial-scale coatings and high production yields.

[0040] In one embodiment, the present invention provides a method for coating polysilazane to limit fragmentation of the polysilazane.

[0041] In some embodiments, the present invention provides a method of coating polysilazane to limit fragmentation of the polysilazane, the method comprising: i) mixing a polysilazane with a catalyst; ii) applying the coating composition to a substrate; Including, wherein step ii) is initiated at a predetermined time after step i); A polysilazane coating method is provided.

[0042] In some embodiments, the present invention provides a method of coating polysilazane to limit fragmentation of the polysilazane, the method comprising: i) stepwise mixing of polysilazane, catalyst, and additional components, the order of mixing steps and the time between mixing steps being predetermined based on the known reactivities of the polysilazane, catalyst, and additional coating components with one another; ii) applying the coating composition to a substrate; Including, wherein step ii) is initiated at a predetermined time after step i); A polysilazane coating method is provided.

[0043] In some embodiments, the present invention provides a method of coating polysilazane to limit fragmentation of the polysilazane, the method comprising: i) stepwise mixing of polysilazane, catalyst, and reactive nanomaterial, wherein the order of mixing steps and the time between mixing steps are predetermined based on the known reactivities of the polysilazane, the catalyst, and the reactive nanomaterial with one another; ii) applying the coating composition to a substrate; Including, wherein step ii) is initiated at a predetermined time after step i); A polysilazane coating method is provided.

[0044] In some embodiments, the present invention provides a method of coating polysilazane to limit fragmentation of the polysilazane, the method comprising: i) preparing a coating composition, the preparation of the coating composition comprising: a. introducing component A into a coating composition container; b. introducing component B into a coating composition container and mixing component B with component A; c. introducing component C into the coating composition container and mixing component C with components A and B; wherein one of components A, B, and C comprises one or more polysilazanes; The introduction in the sub-step ic) is carried out after the introduction in the sub-step ib) for a predetermined time t c Starts with ; and t c is 0 <t c Selected to be < 900 seconds; t for each of the above components c and the selection of the group is predetermined based on the known reactivities of the components with each other. preparing a coating composition; ii) applying the coating composition to a substrate; Including, Here, step ii) is performed after a predetermined time t after the start or completion of the last sub-step of step ii). ii , starts at 1 to 1200 seconds, and t ii is predetermined based on the known reactivities of the components with one another; A polysilazane coating method is provided.

[0045] In some embodiments, the present invention provides a method of coating polysilazane to limit fragmentation of the polysilazane, the method comprising: i) preparing a coating composition, the preparation of the coating composition comprising: a. introducing component A into a coating composition container; b. introducing component B into a coating composition container and mixing component B with component A; c. introducing component C into the coating composition container and mixing component C with components A and B; wherein one of components A, B, and C comprises one or more polysilazanes, and another of components A, B, and C is a catalyst; The introduction in the sub-step ic) is carried out after the introduction in the sub-step ib) for a predetermined time t c Starts with ; and t c is 0 <t c Selected to be < 900 seconds; t c and the selection of groups for each of the components is predetermined based on the known reactivities of the components with one another. preparing a coating composition; ii) applying the coating composition to a substrate; Including, Step ii) is performed after the start or completion of the last sub-step of step ii) at a predetermined time t ii , starts at 1 to 1200 seconds, and t ii is predetermined based on the known reactivities of the components with one another; A polysilazane coating method is provided.

[0046] In some embodiments, the present invention provides a method of coating polysilazane to limit fragmentation of the polysilazane, the method comprising: i) preparing a coating composition, the preparation of the coating composition comprising: a. introducing component A into a coating composition container; b. introducing component B into a coating composition container and mixing component B with component A; c. introducing component C into the coating composition container and mixing component C with components A and B; wherein components A, B, and C are each selected from the group of polysilazanes, the group of catalysts, or the group of reactive molecules that can react spontaneously with the reactive nanomaterial and / or polysilazane polymer backbone to cause fragmentation; wherein said components A, B, and C are all selected from different groups; The introduction in the sub-step ic) is carried out after the introduction in the sub-step ib) for a predetermined time t c Starts with ; and t c is 0 <t c Selected to be <180 seconds; t c and the selection of groups for each of the components is predetermined based on the known reactivities of the components with one another. preparing a coating composition; ii) applying the coating composition to a substrate; Including, The step ii) is performed after a predetermined time t ii , starts between 1 and 180 seconds, and t ii is predetermined based on the known reactivities of the components with one another; A polysilazane coating method is provided.

[0047] In some embodiments, the present invention provides a method of coating polysilazane to limit fragmentation of the polysilazane, the method comprising: i) preparing a coating composition, the preparation of the coating composition comprising: a. introducing component A into a coating composition container; b. introducing component B into a coating composition container and mixing component B with component A; c. introducing component C into the coating composition container and mixing component C with components A and B; wherein components A, B, and C are each selected from the group of polysilazanes, the group of catalysts, or the group of reactive nanomaterials and / or reactive molecules that can spontaneously react with the polysilazane polymer backbone and cause fragmentation; wherein the above components A, B, and C are all selected from different groups; The introduction in the sub-step ic) is carried out after the introduction in the sub-step ib) for a predetermined time t c Starts with ; and t c is 0 <t c Selected to be < 900 seconds preparing a coating composition; ii) applying the coating composition to a substrate; Including, The step ii) is performed after a predetermined time t ii ,Starting from 1 to 1200 seconds, A polysilazane coating method is provided.

[0048] In some embodiments, the present invention provides a method of coating polysilazane to limit fragmentation of the polysilazane, the method comprising: i) preparing a coating composition, the preparation of the coating composition comprising: a. introducing component A into a coating composition container; b. introducing component B into a coating composition container and mixing component B with component A; c. introducing component C into the coating composition container and mixing component C with components A and B; wherein components A, B, and C are each selected from the group of polysilazanes, the group of catalysts, or the group of reactive nanomaterials; wherein said components A, B, and C are all selected from different groups; The introduction in the sub-step ic) is carried out after the introduction in the sub-step ib) for a predetermined time t c Starts with ; and t c is 0 <tc Selected to be <900 seconds; t c and the selection of groups for each of the components is predetermined based on the known reactivities of the components with one another. preparing a coating composition; ii) applying the coating composition to a substrate; Including, The step ii) is performed after a predetermined time t ii , starts at 1 to 900 seconds; and t ii is predetermined based on the known reactivities of the components with one another; A polysilazane coating method is provided.

[0049] In some embodiments, as shown in FIG. 1, the present invention provides a method for coating polysilazane to limit fragmentation of the polysilazane, the method comprising: i) preparing a coating composition, the preparation of the coating composition comprising: a. introducing component A into a coating composition container; b. introducing component B into a coating composition container and mixing component B with component A; c. introducing component C into the coating composition container and mixing component C with components A and B; wherein components A, B, and C are each selected from the group of polysilazanes, the group of catalysts, or the group of reactive molecules that can react spontaneously with the reactive nanomaterial and / or polysilazane polymer backbone to cause fragmentation; wherein said components A, B, and C are all selected from different groups; The introduction in the sub-step ic) is carried out after the introduction in the sub-step ib) for a predetermined time t c Starts with ; and t c is 0 <t c Selected to be <900 seconds; tc and the selection of groups for each of the components is predetermined based on the known reactivities of the components with one another. preparing a coating composition; ii) applying the coating composition to a substrate; Including, The step ii) is performed after a predetermined time t ii , starts at 1 to 900 seconds; and t ii is predetermined based on the known reactivities of the above components with respect to one another. A polysilazane coating method is provided.

[0050] In some embodiments, the present invention provides a method of coating polysilazane to limit fragmentation of the polysilazane, the method comprising: iii) preparing a coating composition, the preparation of the coating composition comprising: a. introducing component A into a coating composition container; b. introducing component B into a coating composition container and mixing component B with component A; c. introducing component C into the coating composition container and mixing component C with components A and B; wherein components A, B, and C are each selected from the group of polysilazanes, the group of catalysts, or the group of reactive nanomaterials; wherein said components A, B, and C are all selected from different groups; The introduction in the sub-step ic) is carried out after the introduction in the sub-step ib) for a predetermined time t c Starts with ; and t c is 0 <t c Selected to be <900 seconds; t c and the selection of groups for each of the components is predetermined based on the known reactivities of the components with one another. preparing a coating composition; iv) applying the coating composition to a substrate; Including, Step ii) is performed after the start or completion of the last sub-step of step ii) at a predetermined time t ii , starts at 1 to 900 seconds, t ii is predetermined based on the known reactivities of the components with one another; A polysilazane coating method is provided.

[0051] In some embodiments, as shown in FIG. 1, the present invention provides a method for coating polysilazane to limit fragmentation of the polysilazane, the method comprising: iii) preparing a coating composition, the preparation of the coating composition comprising: a. introducing component A into a coating composition container; b. introducing component B into a coating composition container and mixing component B with component A; c. introducing component C into the coating composition container and mixing component C with components A and B; wherein components A, B, and C are each selected from the group of polysilazanes, the group of catalysts, or the group of reactive molecules that can react spontaneously with the reactive nanomaterial and / or polysilazane polymer backbone to cause fragmentation; wherein the components A, B, and C are all selected from different groups; The introduction in the sub-step ic) is carried out after the introduction in the sub-step ib) for a predetermined time t c Starts with ; and t c is 0 <t c < 900 seconds, t c and the selection of groups for each of the components is predetermined based on the known reactivities of the components with one another. preparing a coating composition; iv) applying the coating composition to a substrate; Including, Step ii) is performed after the start or completion of the last sub-step of step ii) at a predetermined time t ii , starts at 1 to 1200 seconds, t ii is predetermined based on the known reactivities of the components with one another; A polysilazane coating method is provided.

[0052] In some embodiments, the method further comprises a further step iii) carried out after step ii). In certain embodiments, step iii) comprises curing the coating composition. Curing may be assisted by one or more of HO vapor, atmospheric humidity, thermally, UV or visible light, particularly by a photoinitiator used as an additive.

[0053] In some embodiments, the catalyst is a crosslinking catalyst, such as a catalyst for crosslinking polysilazanes, hi some embodiments, the catalyst is a crosslinking catalyst or a catalyst for promoting a reaction between the polysilazane and any other components present in the coating composition.

[0054] In some embodiments, the vessel used in the method of the present invention is a vessel having a single opening, such as a beaker, flask, reactor, etc. In such embodiments, the components of the coating composition may be introduced batchwise rather than continuously. The components may be mixed, e.g., as a result of introduction, e.g., by active mixing.

[0055] In a preferred embodiment, the container used in the method of the present invention is an elongated device with multiple openings, such as a tube or manifold with multiple injection ports. The dimensions of the container can be selected to allow for sufficient mixing. In such an embodiment, the coating composition is pumped or otherwise flowed through the container toward an applicator or the like. In certain embodiments, the introduction of components and the movement of the coating composition through the container is a continuous flow process. In certain embodiments, such as batch operations, the continuous flow process often includes temporary interruptions. The time t between steps and substeps is ii and t c may be controlled by the timing of the introduction of the components, the shape and volume of the coating composition container, and the flow rate of the coating composition through the container.

[0056] Those skilled in the art are knowledgeable in how to select the appropriate introduction rate and volume for each of the above components for a selected container. In certain embodiments, a pressure generator, such as a pump, is used to achieve the introduction of the components. The relative proportions of the components are controlled by their concentrations and relative flow rates.

[0057] In some embodiments, mixing of the components results solely from the introduction of the components into the coating composition container. In other embodiments, mixing is achieved by mixing means such as sonication, a flow redirection barrier (FRB), a vortex flow path (CFP), stirring, etc. In some embodiments, sonication may cause excessive reaction and / or precipitation; therefore, in these embodiments, a FRB, a CFP, and / or stirring are preferred.

[0058] In some embodiments, the coating composition in the container is exposed to an external activator, such as UV-visible light, ultrasound, plasma, laser, heat, or sonication, to promote a reaction. For example, sonication can break the C=C bonds in the carbon nanotubes, thus promoting reaction with the Si-H and NH functional units in the polysilazane or hydroxyl functional groups in another component. Heat can cause a dehydrogenation crosslinking reaction.

[0059] In some embodiments, the coating composition includes additional components in addition to the polysilazane, catalyst, and active nanomaterial and / or reactive molecules that can spontaneously react with the polysilazane polymer backbone to cause fragmentation. In some embodiments, the additional components are additives, such as to introduce or adjust specific properties of the coating composition and / or coating.

[0060] In certain embodiments, such additional components are introduced and mixed into the coating composition in additional substeps of step i), such as before, after, and between steps ia), ib), and ic). In certain embodiments, such additional components are introduced and mixed into the coating composition simultaneously with one or more of steps ia), ib), and ic). The additional components may or may not be contacted and / or mixed with components A, B, and / or C prior to introduction into the coating composition container.

[0061] In some embodiments, one or more of the components, such as one or more of the polysilazanes, catalysts, reactive nanomaterials, or reactive molecules, are introduced in multiple substeps of step i). In certain embodiments, one or more polysilazanes are introduced in multiple substeps of step i).

[0062] The time between the sub-steps of step i), i.e., t cand any time t from a sub-step of step i) to the introduction of an additional component in an additional sub-step ix) of step i) immediately following said sub-step of step i). x , the group selected for components A, B, and C, and any additional components, and the time t between step i) and step ii). ii are all selected based on the known reactivities of the components of the coating composition with one another in order to control the extent of any reaction that occurs between the components of the coating composition.

[0063] The method of the present invention, through its controlled in-situ introduction of the components of the coating composition, allows for the use of reactive additives that would otherwise not be usable, while obviating fragmentation.

[0064] Some benefits of the in situ introduction of a crosslinking catalyst according to the method of the present invention are as follows: Eliminates the need to prepare and store unstable polysilazane formulations. The problems associated with the fragmentation of polysilazanes are solved by reversing the fragmentation. Interestingly, the molecular weight of the polymer also increases beyond its original value. Thus, the mechanical, optical, and possibly other properties of the polymer can be enhanced with the crosslinking catalyst alone. · Furthermore, the environmental footprint of the coating process is reduced compared to traditional coating methods as the utilization of coating materials is maximized - less energy and material resources are required for the safe disposal of waste. This method allows for shorter processing times after coating, as functional groups already crosslinked in solution are excluded from the calculation. The same is true for tack-free time, which is beneficial for faster roll-to-roll operations. The method can deliver targeted mechanical and optical properties at a given processing time compared to formulations without prior solution crosslinking. For example, the hardness and scratch resistance of the coating can be increased due to the higher molecular weight, while gloss is reduced due to the greater surface roughness caused by the incorporation of nanoparticles and / or microparticles containing crosslinked polysilazanes. Porosity for a given application can be controlled using the degree of solution crosslinking and / or the amount of catalyst. The amount of catalyst for dehydrogenation crosslinking is directly related to the amount of hydrogen released. The method of the present invention represents a practical and cost-effective way to achieve the desired level of crosslinking while avoiding extreme or costly conditions.

[0065] Furthermore, controlled in-situ mixing allows the use of reactive additives, such as reactive nanomaterials, to enhance coating properties. For example, porosity can also be controlled by using specific additives and by fine-tuning the time between their introduction into the coating mixture and application. Reactive additives can be introduced in a substep towards the end of step i), thereby limiting their contact time with the polysilazane.

[0066] For the methods and assemblies of the present invention, the components of the coating can be obtained in any manner known to those skilled in the art, such as by being obtained from natural sources, commercially obtained, or synthesized using any route and starting materials.

[0067] The polysilazanes used in the methods or assemblies of the present invention may be selected from the list including PHPS, OPSZ, polyborosilazanes, polysiloxazanes, and any combination thereof. The polysilazanes may be copolymers. The polysilazanes may be crosspolymers. In some embodiments, the number average molecular weight of the polysilazanes is in the range of 100 to 150,000 g / mol, such as 600 to 100,000 g / mol. The polysilazanes may be oligomers, such as oligomers whose number average molecular weight is in the range of 500 to 1300 g / mol.

[0068] In some embodiments, the polysilazane is PHPS. In some embodiments, the polysilazane is one or more OPSZ. In some embodiments, the polysilazane is Durazane 1800.

[0069] In some embodiments, the polysilazane has the formula [R 1 R 2 Si-NR 3 ] n The formula includes OPSZ of the formula: 1 , R 2 , and R 3 At least one of R is an organic substituent. 1 , R 2 , and R 3 At least one of R is an organic substituent having one or more carbon atoms directly bonded to a silicon or nitrogen atom of the backbone. 1 , R 2 , and R 3 At least one of R is an organic substituent having at least one heteroatom directly bonded to a silicon or nitrogen atom of the backbone. Such heteroatoms can be selected from the group including, but not limited to, silicon, nitrogen, oxygen, and sulfur. In some embodiments, R 1 , R 2 , and R 3At least one of R is an organic substituent having 1 to 18 carbon atoms, e.g., 1 to 12 carbon atoms, e.g., 1 to 8 carbon atoms. 1 , R 2 , and R 3 At least one of R is an organic substituent selected from the group including, but not limited to, alkyl, alkenyl, cycloalkyl, aryl, aralkyl, alkyl, silyl, alkylamino, alkoxy, and nitrile. 1 , R 2 , and R 3 At least one of may contain a substituent selected from the group including, but not limited to, an alkoxy group, a cyano group.

[0070] In a preferred embodiment, R 1 , R 2 , and R 3 At least one of is an organic substituent selected from the group including, but not limited to, alkyl, alkenyl, alkynyl, alkoxyalkyl, organofluorine groups such as fluorocarbons, hydrofluorocarbons, fluorocarbenes, and the like.

[0071] In some embodiments, the polysilazanes include OPSZ, which contain pendant groups with carbon-carbon double bonds. In such embodiments, the use of platinum complexes and / or DCP can result in hydrosilylation reactions (free radicals of DCP), cleaving the double bond to react with Si-H. These reactions represent another form of solution crosslinking or can be used to bond nanomaterials with unsaturated bonds. As known to those skilled in the art, catalysts and / or reactants may be used to open unsaturated bonds to facilitate these reactions.

[0072] Reactive nanomaterials that can be used in the methods or assemblies of the present invention are nanomaterials that contain functional units that can react directly or indirectly with Si-H and / or NH and / or Si-NH-Si motifs in organic or inorganic polysilazanes and / or with vinyl groups in organic polysilazanes. Such functional groups include hydroxyl, carbonyl, carboxyl, amine / amino, epoxy, thiol, carbon-carbon double bonds such as in graphene and graphene oxide, and BN triple bonds in hexagonal boron nitride.

[0073] In some embodiments, the reactive nanomaterials can spontaneously react with the polysilazane polymer backbone, causing fragmentation. In some embodiments, the coating composition comprises a plurality of reactive nanomaterials.

[0074] Reactive nanomaterials have various morphologies, such as particles, wires, rods, and platelets. In some embodiments, the nanomaterial is a nanoparticle. In some embodiments, the nanomaterial is selected from the list including, but not limited to, SiO2; carbon-based materials such as graphene, graphene oxide, and carbon nanotubes; TiO2; ZnO; SnO; WS2; MoS2; boron nitride; silver; and other inorganic nanomaterials. Other non-limiting examples are organic nanomaterials such as nanocellulose, e.g., cellulose nanofibers and cellulose crystals, and hybrids such as polyhedral oligomeric silsesquioxanes (POSS).

[0075] The reactive nanomaterials can be selected from a list including, but not limited to, inorganic nanomaterials such as silica, titanium dioxide, graphene, and boron nitride; magnetic nanomaterials; antibacterial nanomaterials such as graphene oxide and silver; and hybrid nanomaterials such as polyhedral oligomeric silsesquioxanes (POSS). The nanomaterials may also be organic nanomaterials. In some embodiments, at least two types of nanomaterials are included in the coating composition. The reactive nanomaterials are selected based on the desired properties of the coating.

[0076] Inorganic nanomaterials can react with polysilazanes through their naturally occurring functional groups, such as hydroxyl groups in oxide nanomaterials and carbon-carbon double bonds in carbon-based materials, or can be functionalized to enhance or control these reactions and / or to impart additional properties, such as flexibility, through bonding with organic materials. Such functionalization can be achieved by several means, with a common method being direct or indirect reaction with silanes. For example, amine functional groups are imparted through the use of APTES, while vinyl functional groups are imparted through the use of triethoxyvinylsilane. To improve their dispersion and stability in solution, inorganic nanomaterials can be surface-modified by immobilizing short-, medium-, or long-chain alkyl groups or organofluorine groups thereon, such as with silanes. The alkyl groups or organofluorine groups can be or contain reactive functional groups, such as butyronitrile (which has a carbon-nitrogen triple bond) and propyl methacrylate (which has a vinyl unit). The use of silane coupling agents to achieve dispersion and stability and to promote reactivity of inorganic particles with polymers is well known in the art. The modifying group may be a completely inert group, such as a perfluorooctyl or propyl group from a suitable silane.

[0077] In the methods of the present invention, the reactive nanomaterial may be replaced by or combined with a reactive molecule capable of spontaneously reacting with the polysilazane polymer backbone to cause fragmentation. The molecule must contain a functional group known to those skilled in the art to be capable of spontaneously reacting with the polysilazane to cleave the Si-N bond. In some embodiments, the reactive molecule is a monomer, such as 1,2-benzenedimethanol or hexane-1,6 diol diacrylate. In some embodiments, the reactive molecule is an oligomer, such as a urethane acrylate. In some embodiments, the reactive molecule is a short-, medium-, or long-chain organic compound, such as 2-fluoroethanol, 2,2,2-trifluoroethanol, triethoxyvinylsilane, 1,8-octanediol, 1H,1H,2H,2H-perfluorooctyltriethoxysilane, erucamide, or behenamide. In some embodiments, the reactive molecule is a polymer, such as polyethylene glycol, a polyethylene glycol derivative, a polyethylene glycol copolymer, or cellulose. For example, if the goal is a coating with a very low coefficient of friction, inorganic nanomaterials that can increase surface roughness may be substituted for or combined with 2-fluoroethanol to take advantage of the low surface energy of C—F bonds.

[0078] In some embodiments, the coating composition comprises a plurality of reactive molecules capable of spontaneously reacting with the polysilazane polymer backbone to cause fragmentation. In some embodiments, the coating composition comprises at least one reactive molecule capable of spontaneously reacting with the polysilazane polymer backbone to cause fragmentation and at least one reactive nanomaterial.

[0079] Catalysts that can be used in the method or for assembly of the present invention can be selected from a list including, but not limited to, crosslinking catalysts and curing catalysts known to those skilled in the art.

[0080] In some embodiments, the method comprises the use of one or more catalysts selected from the following group: Other catalysts that can promote the crosslinking reaction between the Si-H and NH of polysilazanes to form nucleophiles and stable Si-N bonds, such as, but not limited to, catalysts selected from the group including tetrabutylammonium fluoride (TBAF), tetrabutylammonium bromide (TBAB), and tetrabutylammonium iodide (TBAI), can also enhance the reactivity of Si-H with nucleophiles. Metal complexes, such as platinum complex Karlstedt catalysts, that can promote hydrosilation or other reactions between unsaturated centers and the Si-H and / or NH of polysilazanes. Such unsaturated centers include C=C, nitriles (carbon-nitrogen triple bonds), C=O, C=N, N=O, etc. Non-limiting examples of additives with unsaturated bonds include diphenylacetylene, 4-ethyl-1-pentene, vinyl-functionalized POSS, pentafluoropropionic anhydride, and ethyleneimine. These may or may not react spontaneously, and the reaction may occur in solution or after coating, depending on the type of catalyst. External activators may be applied during mixing, during coating application, or after coating.

[0081] In some embodiments, a catalyst is used that is a nucleophile capable of activating Si atoms for nucleophilic attack while simultaneously promoting crosslinking of Si-H and NH centers to avoid fragmentation of the polymer backbone. In some embodiments, an organic nucleophile is used. Organic nucleophiles facilitate use in polar aprotic or nonpolar solvents. In some embodiments, a metal complex, such as a platinum complex, e.g., Karlstedt's catalyst, is used as the catalyst, such as to promote solution crosslinking. In a specific embodiment, 4,5-dicyanopyridazine (DCP) is used as the catalyst. In a specific embodiment, TBAF is used as the catalyst.

[0082] It may be necessary to control the degree of solution crosslinking by quenching the catalyst with a quenching agent, which must be selected from among compounds known by those skilled in the art not to stabilize precipitates.

[0083] In some embodiments, the method includes including one or more additional components, such as additives, in the coating composition. The additional components may be premixed with one or more of components A, B, and / or C, or may be added simultaneously. The additional components may be added in one or more separate substeps ix) of step i), for example, before substep ia), between substep ia) and substep ib), between substep ib) and substep ic), after substep ic), etc. The time from the preceding substep to substep ix) is referred to as t x In some embodiments, the method includes further including one or more components already added, such as components A, B, and / or C.

[0084] In some embodiments, such additives are included to enhance the properties of the polysilazanes, coating compositions, and / or coatings and / or to affect new properties. In some embodiments, the additives are selected from a list including small molecules such as 2,2,3,3,3-pentafluoro-1-propanol, butanol, and triethoxyvinylsilane. Functional groups such as hydroxyl and alkoxy groups in these additives react with polysilazanes. Such additives can be used to reduce friction and improve anti-stick properties due to the (fluoro)alkyl groups, especially for coatings containing PHPS as the only polysilazane. The vinyl groups can participate in UV or thermal radical curing after coating and further improve crosslinking, such as with Durazane 1800. In some embodiments, the additives are selected from a list including medium- and long-chain molecules such as octanol, urethane acrylates, methacrylates, and erucamide. Such additives can function as described for small molecules above. The long chains can enhance the slip properties of the coating, as well as polymerization properties such as flexibility of PHPS-dominated coatings. The hydroxyl groups of butanol, the amino and carbonyl groups of erucamide, and the alkoxyester and NH groups of urethane acrylate react with polysilazane. In some embodiments, the additive is selected from a list including polymers such as cellulose or nanocellulose fibers with activated hydroxyl groups. These additives can be used, for example, in biocomposites as reinforcing agents (fillers) to improve mechanical properties. Other additives known to those skilled in the art, such as thickeners, emulsifiers, dispersants, pigments, defoamers, leveling agents, light stabilizers, driers, drying accelerators, surfactants, flow improvers, and thixotropic agents, can also be included in the coating composition. If such additives can react with polysilazane to fragment it, they are called or treated as reactive additives.

[0085] Reactive additives generally react spontaneously with polysilazanes (primarily Si-H, but in some cases, to some extent NH) due to the presence of certain functional groups. Non-limiting examples of such functional groups include hydroxyl, carbonyl, amine, and carboxylic acid groups. Of particular note are hydroxyl groups, which are often present in commonly used additives. Non-reactive additives require an activator to react; such activators can be chemical accelerators or catalysts, or external activators. When an activator is used, a crosslinker may be necessary to avoid fragmentation. Due to the difference in reactivity of PHPS compared to OPSZ, an additive may be a reactive additive in a coating composition containing PHPS, but a non-reactive additive in a coating composition containing OPSZ but not PHPS.

[0086] Examples of reactive additives that can be used in the method of the present invention are compounds that, due to their inherent properties—for example, ATPE must first hydrolyze in atmospheric moisture—promote crosslinking only after coating, or in the presence of an activator that requires heat and a photoinitiator such as hydroxycyclohexyl phenyl ketone (HCPK), e.g., a radical initiator such as dicumyl peroxide (DPC).

[0087] The coating composition further comprises one or more solvents. The concentrations of the various components can be varied to control the properties of the coating composition and / or coating. In some embodiments, the concentration of the components in the coating composition container does not exceed 50 wt %. In some embodiments, the concentration of the components in the coating composition is between 2 wt % and 20 wt %. The solvent may be a polar aprotic solvent and / or a nonpolar solvent. The solvent may be an anhydrous solvent. In some embodiments, all components are completely dissolved or suspended as a stable suspension prior to their introduction into the coating composition container. In other embodiments, one or more liquid components are introduced into the coating composition container neat, i.e., without the presence of a solvent, while all other components are completely dissolved or suspended as a stable suspension prior to their introduction into the coating composition container. In some embodiments, all components are dissolved or suspended in the same solvent. In other embodiments, different solvents are used for two or more components. In some embodiments, the solvent is selected from the list including, but not limited to, dimethyl sulfoxide (DMSO), butyl acetate, tetrahydrofuran (THF), dimethylformamide (DMF), dibutyl ether, and xylene. In preferred embodiments, coating compositions containing only OPSZ with small amounts (5 wt%, 2 wt%, 1 wt%, etc.) of PHPS or no PHPS contain a solvent selected from the list of polar aprotic solvents such as DMSO, butyl acetate, tetrahydrofuran, and DMF. In preferred embodiments, coating compositions containing a significant amount of PHPS contain only non-polar solvents such as dibutyl ether and xylene.

[0088] In some embodiments, particular embodiments where one skilled in the art will recognize the need for this benefit, anhydrous conditions are used.

[0089] In some embodiments, the components are introduced gradually, slowly, non-batchwise.

[0090] The time between the sub-steps of step i), i.e., t c and any time t from a sub-step of step i) to the introduction of an additional component in an additional sub-step ix) of step i) immediately following said sub-step of step i). x , the group selected for components A, B, and C, and any additional components, and the time t between step i) and step ii). iiare all selected based on the known reactivities of the coating composition components with each other to control the extent of any reactions occurring between them. The above times and the order of the groups selected for the components are predetermined to allow any desired reactions to occur in the coating composition, and / or to avoid any precipitation and / or undesired reactions, and / or to limit the extent of reactions between the components occurring in the coating composition container. For example, a component known by those skilled in the art to cause fragmentation of the polysilazane can be introduced after the introduction of the polysilazane. The time from the introduction of such a component to step ii) can be as short as can be tolerated by the coating equipment, or can be selected to be shorter than the time it takes to reach a particular degree of fragmentation. A component known to stabilize the polysilazane, such as by preventing or reversing fragmentation, can also be introduced before the introduction of the polysilazane. To allow the desired reaction of the nanomaterials to occur without interference from the other components, a component known to cause a desired reaction between the nanomaterials can be introduced before or together with the nanomaterials and before the introduction of the polysilazane and catalyst. The time before the introduction of the latter component can be selected to allow sufficient time for the desired reaction to occur. To reduce the tack-free time of the coating, the crosslinking catalyst can be introduced at a certain time before application of the coating to allow the desired degree of solution crosslinking to occur in the coating composition container, but the time should be limited to avoid excessive crosslinking, which can affect the desired properties of the coating or cause precipitation.

[0091] Excessive reaction is a relative term in this context. For example, too much solution cross-linking can cause the formation, aggregation, or hybridization of nano- or microparticles, which can result in high surface roughness. For certain applications, a high surface roughness is desired, such as for camouflaged coatings that do not need to be glossy, or porous coatings for use in filtration. For other specific applications, such as high-gloss, stain-resistant, superhydrophobic coatings, the surface roughness should be kept low, for example, less than 400 nm, less than 200 nm, and preferably less than 100 nm.

[0092] In some embodiments, the group selection for each of the components, as well as t c and t ii The prior determination of is made based on the known reactivities of the components of the coating composition with one another so that any desired reactions, such as solution crosslinking, occur to the desired extent in the coating composition. In some embodiments, the selection of groups for each of the components, as well as the c and t ii The prior determination of is made based on the known reactivities of the components of the coating composition with one another to avoid any precipitation in the coating composition, such as any precipitation known by those skilled in the art to occur in such coating compositions. In some embodiments, the selection of groups for each of the components, as well as the c and t ii The prior determination of is made based on the known reactivities of the components of the coating composition with one another to avoid or limit undesirable reactions, such as fragmentation, known by those skilled in the art to occur in coating compositions. In some embodiments, the selection of groups for each of the components, as well as the c and t ii A prior determination of is made based on the known reactivities of the components of the coating composition with one another to limit the extent of reaction between the components that occurs in the coating composition container, such as solution crosslinking.

[0093] Time t c and t ii and any time t from a sub-step of step i) to the introduction of an additional component in an additional sub-step ix) of step i) immediately following that sub-step of step i). x The groups selected for components A, B, and C, and any additional components, may be the same or different. c and / or t x is 0 seconds, meaning that the components of these steps are introduced into the coating composition container simultaneously. When the components are to be introduced simultaneously, they may be contacted and / or mixed with each other prior to introduction into the coating composition container, or they may first come into contact with each other upon entering the coating composition container.

[0094] In some embodiments, 0 <t c < 1200 seconds, and / or 1 <t ii <1200 seconds. In some embodiments, 0 <t c < 900 seconds, and / or 1 <t ii <900 seconds. <t c < 600 seconds, and / or 1 <t ii <600 seconds. <t c < 400 seconds, and / or 1 <t ii <400 seconds. <t c <300 seconds, and / or 1 <t ii <300 seconds. <t c < 180 seconds, and / or 1 <t ii <180 seconds. <t c <120 seconds, and / or 1 <t ii <120 seconds. <t c <60 seconds, and / or 1 <t ii<60 seconds. <t c <30 seconds, and / or 1 <t ii In some embodiments, the time is <30 seconds. <t c <60 seconds, and / or 5 <t ii <60 seconds. <t x <900 seconds. <t x <300 seconds. <t x In some embodiments, the time is <120 seconds. <t x <60 seconds.

[0095] In some embodiments, t c controls the level of polysilazane fragmentation, and t ii controls the level of solution crosslinking.

[0096] In some embodiments, component A is selected from the group of polysilazanes, component B is selected from the group of catalysts, and component C is selected from the group of reactive nanomaterials or reactive molecules that can spontaneously react with reactive nanomaterials and polysilazane polymer backbones to cause fragmentation.

[0097] In some embodiments, component A is selected from the group of polysilazanes, component B is selected from the group of reactive nanomaterials or reactive molecules that can spontaneously react with reactive nanomaterials and polysilazane polymer backbones to cause fragmentation, and component C is selected from the group of catalysts.

[0098] In some embodiments, component A is selected from the group of polysilazanes, component B is selected from the group of reactive nanomaterials or reactive molecules that can spontaneously react with reactive nanomaterials and polysilazane polymer backbones to cause fragmentation, and component C is selected from the group of catalysts.

[0099] In some embodiments, component A is selected from the group of reactive nanomaterials and / or reactive molecules that can spontaneously react with reactive nanomaterials and polysilazane polymer backbones to cause fragmentation, component B is selected from the group of polysilazanes, and component C is selected from the group of catalysts.

[0100] In some embodiments, component A is selected from the group of reactive nanomaterials and / or reactive molecules that can spontaneously react with reactive nanomaterials and polysilazane polymer backbones to cause fragmentation, component B is selected from the group of catalysts, and component C is selected from the group of polysilazanes.

[0101] In some embodiments, component A is selected from the group of catalysts, component B is selected from the group of reactive nanomaterials and / or reactive molecules that can spontaneously react with reactive nanomaterials and polysilazane polymer backbones to cause fragmentation, and component C is selected from the group of polysilazanes.

[0102] In some embodiments, component A is selected from the group of catalysts, component B is selected from the group of polysilazanes, and component C is selected from the group of reactive nanomaterials and / or reactive molecules that can spontaneously react with reactive nanomaterials and polysilazane polymer backbones to cause fragmentation.

[0103] FIG. 2 shows an embodiment of the method of the present invention, in which the additional component X is added after substep ib) at time t x and is introduced in sub-step ix) and further comprises a curing step iii).

[0104] In some embodiments, the sub-steps of step i) are selected as follows: Each sub-step is performed separated in time from each other. Sub-step ia) Component A is a nanomaterial containing functional units that can fragment or bond to polysilazane, for example through π-π interactions, such as boron nitride, graphene, carbon nanotubes, WS2, MOS2, etc. The following may be premixed with component A and introduced simultaneously: catalysts that prevent or reverse fragmentation, such as nucleophiles, metal complexes, DPC, etc.; and / or · Small amounts of OPSZ, such as Durazane 1800. Such catalysts can also cause solution crosslinking of polysilazanes, so their concentrations may need to be minimized initially. The catalysts are present because 1) the nanomaterials and / or their functional groups are not sensitive to the catalyst, and 2) the functional groups present on the nanoparticles are sensitive to each other. The catalyst, e.g., Karlstedt's catalyst, can aggregate nanomaterials with nitrile and / or vinyl groups through either covalent interactions or weak unsaturated bond coupling, thus inducing some self-assembly. The presence of small amounts of OPSZ can stabilize certain nanomaterials, such as graphene oxide, carbon nanotubes, hexagonal boron nitride, and WS2, which are known to be stabilized in solution through covalent or non-covalent functionalization with organic molecules, including those with unsaturated bonds. Sub-step ix) Additional steps The following are introduced in this step: a catalyst for solution crosslinking, such as TBAF, TBAB, and / or TBAI; and / or Additives, such as those for maintaining colloidal stability during further processing, which are not sensitive to the components of step ia) but may interfere with any reaction and / or premixing between these components. Sub-step ib) Component B is one or more polysilazanes. The following may be premixed with component B and introduced simultaneously: Non-reactive additives, such as traditional additives used to improve coating properties, e.g., thickeners, emulsifiers, dispersants, pigments, defoamers, leveling agents, light stabilizers, drying agents, drying accelerators, surfactants, flow improvers, thixotropic agents, etc.; and / or Reactive additives that require an external trigger, such as UV light, to react after the coating is applied. Sub-step ic) Component C is a crosslinking catalyst. The following may be premixed with component C and introduced simultaneously: reactive additives; and / or Non-reactive additives

[0105] In certain embodiments, the catalyst in ia) is the same as the catalyst in ib). In certain embodiments, the catalyst in ia) is different from the catalyst in ib). In certain embodiments, the catalyst in ia) primarily promotes nanomaterial self-assembly / aggregation, while the catalyst in ib) primarily promotes nanomaterial-polysilazane reaction and solution crosslinking.

[0106] When the method is carried out using a continuous flow, it is possible to dilute the flow before substep ib), for example, to reduce the concentration of another component, for example, to reduce the concentration of the catalyst to reduce solution crosslinking. As used herein, the terms "dilute" and "dilution" refer to adding more solvent to the coating composition. It is also possible to dilute the flow before step ii), for example, to improve application. In some embodiments, a diluent is added in an additional substep iy) just before or just after substep ix), or in substep ix). The diluent may be a polar aprotic solvent or a nonpolar solvent. The diluent may or may not be the same as the solvent already present in the coating composition. For coating compositions containing a significant amount of PHPS, a preferred diluent is dibutyl ether.

[0107] In some embodiments, the degree of solution crosslinking is controlled by quenching the catalyst. The quenching may be carried out by introducing a quenching agent into the coating composition container that is known by those skilled in the art to quench the catalyst and not promote precipitation. Such a quenching agent may be introduced in a separate substep iz) after substep ic). In some embodiments, the quenching agent is calcium borohydride bis(tetrahydrofuran), which is added in an amount that does not cause significant precipitation and can quench TBAF.

[0108] In some embodiments, the components are selected as follows: Sub-step ia) Component A is PHPS. Non-reactive additives may be premixed with component A and introduced simultaneously. Sub-step ib) Component B is the catalyst TBAF or TBAB. Sub-step ic) Component C is a reactive molecule that can spontaneously react with the polysilazane polymer backbone to cause fragmentation. Sub-step ic) is carried out simultaneously with sub-step ib), and components B and C may be premixed.

[0109] In some embodiments, the coating may be an optical coating that has high gloss and / or anti-stick properties, such as being scratch resistant or anti-fingerprint. ii must be long enough to allow the desired level of solution crosslinking and / or further reaction with component C, but not so long that precipitation and / or undesirable surface roughness results.

[0110] An added benefit of these embodiments is that the surface roughness of the resulting coating can be adjusted to some extent by varying the degree of solution cross-linking.

[0111] In similar embodiments, some or all of the PHPS is replaced with OPSZ. In these embodiments, the resulting coating has lower hardness, is more hydrophobic and softer, and has enhanced anti-stick properties.

[0112] In a similar embodiment, the components are selected as follows: Sub-step ia) Component A is the catalyst DCP. TBAF is premixed with component A and introduced simultaneously. Sub-step ib) Component B is a reactive molecule that can spontaneously react with the polysilazane polymer backbone to cause fragmentation. Sub-step ic) is carried out simultaneously with sub-step ib), and components B and C may be premixed. Sub-step ic) Component C is PHPS and Durazane 1800. Non-reactive additives may be premixed with Component A and introduced simultaneously.

[0113] In some embodiments, the selection of components for the sub-steps of step i) is as follows: Each sub-step is performed separated in time from each other. Sub-step ia) Component A is a nanomaterial comprising functional units capable of fragmenting polysilazanes. Reactive or non-reactive additives such as Karstedt catalysts, stabilizers, etc. may be premixed with component A and introduced simultaneously. Sub-step ix) Additional steps: The following are introduced in this step: TBAF or TBAB; and / or Non-reactive additives Sub-step ib) Component B is PHPS and OPSZ. The following may be premixed with component B and introduced simultaneously: Non-reactive additives such as non-ionic surfactants Sub-step ic) Component C comprises the catalysts TBAF and DCP.

[0114] In these embodiments, a Karstedt catalyst may be added in step ia) to induce changes, such as aggregation, between the nanomaterials before they encounter the polysilazane in step ib). While TBAF or TBAB helps incorporate the nanomaterial into the polysilazane via covalent bonds, it also promotes solution crosslinking in the polysilazane, likely faster than reaction with the nanomaterial. The stepwise introduction and the order in which the components are selected in these embodiments give the nanomaterials a "head start" prior to crosslinking. After coating, DCP can induce crosslinking / reaction of vinyl groups and / or any other unsaturated bonds representing Si-H on the Durazane 1800 (e.g., by application of heat). The addition of DCP in step ix) may be useful if it is necessary to limit its amount in step ia).

[0115] The reactive additive in ia) may be a polysilazane, such as OPSZ, in a substantially lesser amount than in ib). If a polysilazane is added in i), TBAF may not be necessary in ia) because intentional fragmentation of the polysilazane would require the production of more fragments to react with the nanomaterial. These fragments can later be brought back into the polymer backbone with TBAF, TBAB, or other suitable nucleophilic catalyst.

[0116] An added benefit of these embodiments is that the surface roughness of the resulting coating can be enhanced with nanomaterials. For example, nanomaterials such as silica, titanium dioxide, POSS, etc. can be used to approach or achieve superhydrophobicity. The combination of surface roughness and hydrophobicity is crucial to achieving superhydrophobicity.

[0117] The method of the present invention can be employed even without reactive nanomaterials, using only polysilazanes and solution crosslinking catalysts, or even optionally with non-reactive additives. The method functions to promote solution crosslinking to optimize coating properties and reduce post-coating processing time. The coating composition is then applied at a predetermined time after mixing the polysilazanes with the catalyst. For example, solution crosslinking of OPSZ can result in the formation of stable nano / microparticles (SiO2-organic hybrids) that affect the surface roughness of the coating. A greater amount of this crosslinking results in greater surface roughness, which may be desirable for certain coating applications. Solution crosslinking also reduces post-coating cure time, because functional groups crosslinked in solution do not need to be crosslinked after coating. Therefore, for a given time and set of cure conditions, solution crosslinking can also result in higher coating hardness and abrasion resistance.

[0118] The method of the present invention can be carried out at any temperature that is compatible with the components of the coating, hi some embodiments, the method is carried out at room temperature.

[0119] Applying the coating composition to the substrate can be done by any technique known to those skilled in the art for applying solution-processed materials, such as, but not limited to, a method selected from the list including: spraying, such as ultrasonic spray coating, spray painting, pneumatic spraying; spin coating; inkjet printing; doctor blading, electrospinning, and other processes known in the art for converting solution-processed chemical compositions into coatings or films at low temperatures. Applying the coating composition in a continuous flow process can particularly benefit from roll-to-roll processing, involving processes such as spraying, inkjet printing, electrospinning, etc.

[0120] In some embodiments, application is performed by spraying, such as ultrasonic spray coating. Ultrasonic spray coating offers unique advantages in minimizing material loss, achieving uniform coating over large areas in a short time through atomization of the coating formulation, uniformly distributing the coating components, compatibility with in-line processing (e.g., roll-to-roll), and optimizing the surface roughness of the coating. Furthermore, the intensity of the ultrasonic waves at the nozzle can be used to accelerate the rate of solution reactions, such as crosslinking, immediately prior to spraying.

[0121] In some embodiments, the substrate is activated prior to application of a coating composition provided in accordance with the present invention, such as to improve adhesion of the coating to the substrate, such as on polymeric and / or plastic substrates. Such activation can be performed using any method known to those skilled in the art, such as UV treatment, plasma treatment, chemical activation, etc.

[0122] In some embodiments, coatings provided using methods or assemblies of the present invention adhere to a substrate by covalent bonds. In other embodiments, coatings provided using methods or assemblies of the present invention are free-standing films. In some embodiments, coatings provided using methods or assemblies of the present invention are monolayer coatings. In other embodiments, coatings provided using methods or assemblies of the present invention form part of a multilayer coating, e.g., a multilayer coating including multiple coating layers provided using methods and assemblies of the present invention, or a multilayer coating including one coating layer provided using methods and assemblies of the present invention.

[0123] In another aspect, the present invention provides an assembly for carrying out the method of the present invention.

[0124] In some embodiments, as shown in FIG. 3, the present invention provides an assembly 100 for performing the method of the present invention, comprising: an elongated coating composition container (110) having a first end (121) and a second end (122), wherein the first end and the second end are disposed opposite each other, the elongated coating composition container comprising: a first injection port (131); a second injection port (132) located closer to the second end than the first injection port; a third injection port (133) located a distance (D) from the second injection port and closer to the second end than the second injection port; an applicator port (141) located a distance (D') from the third injection port and closer to the second end than the third injection port; an elongated coating composition container (110) comprising: an applicator (150) connected to the applicator port to provide a fluid connection between the applicator and the elongated coating composition container; a pressure generating unit (161) configured to generate a pressure, the pressure generating unit (161) being directly or indirectly connected to the first injection port to generate a pressure differential between the first injection port and the applicator port; An assembly 100 is provided, comprising:

[0125] Figure 4 shows an example of an assembly 100 according to the present invention. Features of the example of Figure 4 are presented below.

[0126] In some embodiments, the coating composition container further comprises a fourth injection port 134. In some embodiments, the coating composition container comprises further additional injection ports, such as a fifth injection port, a sixth injection port, etc.

[0127] Each of the injection ports (131, 132, 133, 134) is attachable to a container (161, 162, 163, 164) for one or more components of the coating composition such that a fluid connection is provided between the container and the coating composition container. In some embodiments, each of the injection ports is attached to a container. The injection ports may be attachable directly to the container and / or via a connector (171, 172, 173, 174). In some embodiments, the connector is a tube or pipe. In some embodiments, the assembly further comprises such a container (161, 162, 163, 164) and / or such a connector (171, 172, 173, 174), such as one for each injection port. In some embodiments, one or more injection ports comprise a valve for sealing and opening the injection port to control the presence of a fluid connection between the coating composition container and the container. In some embodiments, one or more injection ports comprise a means for gradually and / or slowly introducing components into the coating composition container, such as to avoid concentration spikes that may cause excessive reaction, e.g., precipitation.

[0128] In use, each of the containers (161, 162, 163, 164) can contain components for a coating composition. In some embodiments, each of the containers may contain all of the components to be introduced in one specific substep (ia), ib), ic), ix)) of step i) of the method of the present invention, or all of the components to be introduced at one specific time. When the substeps of step i) of the method are to be performed simultaneously, the components of the substeps performed simultaneously may be contained in the same container. The containers are easily interchangeable.

[0129] The number of injection ports and containers may be selected based on the number of components to be introduced into the coating composition container at different times.

[0130] In some embodiments, at least one container is divided into multiple sub-containers connected to the container via pipes or other similar means. The sub-containers may be easily interchangeable. In some embodiments, sub-containers are used to control pre-mixing of two or more components in a container prior to introduction into the coating composition container. This may be because, for example, mixing the components takes too long to fit into the total time the coating composition spends in the container, or an external activator is required to mix the components.

[0131] The pressure generating unit (161) is configured to generate pressure and is connected to the first inlet port (131). It may be directly connected to the first inlet port or indirectly connected to the inlet port, such as by being connected to a container (161) connected to the inlet port or to a connector (171) connecting the container and the inlet port. In some embodiments, the assembly further includes an additional pressure generating unit (162) configured to generate pressure, the second pressure generating unit being directly or indirectly connected to the second inlet port (132) or the third inlet port (133). In some embodiments, a pressure generating unit is directly or indirectly connected to each of the inlet ports of the coating composition container.

[0132] In some embodiments, each pressure generating unit is selected from the list including a pump, a piston, and a gas container. In some embodiments, each pressure generating unit is a pump, such as a peristaltic pump. Each pressure generating unit is arranged to generate a pressure difference between the injection port and the applicator port (141) to which it is directly or indirectly connected. Thus, in use, the pressure generating unit causes components present in a container connected to said injection port to be introduced into the coating composition container. The pressure generator further generates a flow (F) of coating composition through the coating composition container from said injection port to the applicator port.

[0133] In some embodiments, the assembly further comprises a controller (170). In certain embodiments, the controller is for controlling an injection port, such as for controlling a valve on the injection port. In certain embodiments, the controller is for controlling one or more pressure generating units, such as for controlling a pressure differential generated by a pressure generating unit. The controller can ensure a desired introduction rate of components and / or a flow rate of the coating composition through the coating composition container to the applicator port and applicator. The length and diameter of the coating composition container and the flow rate of the coating composition can be determined by the t c , t x , t ii etc., selected to obtain the desired length of time for the methods of the present invention. In some embodiments, distance D and / or distance D' are adjustable.

[0134] The relative proportions of the components in the coating composition container may be controlled by their concentrations or their relative flow rates.

[0135] In some embodiments, the controller controls the intake of coating composition components from different containers via injection ports, such as via connectors, into the coating composition vessel, thus ensuring a step-by-step, time-controlled, gradual and / or slow introduction and mixing of the coating composition components, which is then subsequently applied to a substrate using an applicator.

[0136] The applicator is suitable for applying a coating composition, such as the coating composition contained in assembly (100), to a substrate. In some embodiments, the applicator is a spray nozzle, such as a spray nozzle for ultrasonic spray coating. In other embodiments, the applicator is selected from a list including, but not limited to, an inkjet printer, an electrospinner, a doctor blade, or any suitable film applicator.

[0137] In some embodiments, the assemblies are specifically adapted for use with components known to those skilled in the art to be reactive to air and / or moisture.

[0138] In some embodiments, the assembly further comprises a pressure relief device (180), such as a gas release device, pressure relief valve, etc., connected to the coating composition container, such as through a pressure relief port on the coating composition container. Such a pressure relief device can be used to release generated gas when a gas-generating reaction occurs in the coating composition.

[0139] In some embodiments, the assembly further comprises one or more sensors (190), e.g., in or on the coating composition vessel, in or on the container, etc. The sensors may be sensors for monitoring process conditions and / or the extent of reactions such as cross-linking, fragmentation, etc. The sensors may be selected from a list including, but not limited to, optical sensors, pressure sensors, temperature sensors.

[0140] In some embodiments, the assembly further comprises one or more mixing means (200), such as in or on the coating composition container, in or on a container, etc. Non-limiting examples of mixing means include an ultrasonicator, an agitator, a flow redirecting barrier (FRB) in the coating composition container, a spiral flow path (CFP) in the coating composition container, or an abrupt increase in the diameter of the coating composition container. Examples of a flow redirecting barrier (FRB), a spiral flow path (CFP), and an abrupt increase in the diameter of the coating composition container are shown in Figures 5a, 5b, and 5c, respectively. In some embodiments, ultrasonication may cause excessive reaction and / or precipitation; therefore, an FBR, a CFP, and / or agitation are preferred in this embodiment.

[0141] In some embodiments, the assembly further comprises one or more activators (210) in or on the coating composition vessel, in or on the container, etc. Non-limiting examples of activators include devices for applying electromagnetic radiation (e.g., UV-visible light, ultrasound), plasma, laser, heat, sonication, ultrasonic treatment to the coating composition.

[0142] In some embodiments, the present invention provides an assembly for carrying out the method of the present invention, comprising: an elongated coating composition container (110) having a first end (121) and a second end (122), the first end and the second end being positioned opposite each other; a first injection port (131); a second injection port (132) located closer to the second end than the first injection port; an applicator port (141) located a distance (D') from the second injection port and closer to the second end than the second injection port; the elongated coating composition container (110) comprising: a container containing the components of the coating composition; an applicator (150) connected to the applicator port to provide a fluid connection between the applicator and the elongated coating composition container; a pressure generating unit (161) configured to generate a pressure, the pressure generating unit (161) being directly or indirectly connected to the first injection port to generate a pressure differential between the first injection port and the applicator port; An assembly is provided comprising:

[0143] Embodiments and features in the context of one aspect, for example, for an aspect directed to a method, also apply to all other aspects of the invention, for example, assemblies.

[0144] The present invention should not be limited to the embodiments and examples shown. While various embodiments of the present disclosure are described herein, it will be apparent to those skilled in the art that such embodiments are provided by way of example only. Numerous modifications and variations, as well as various changes and substitutions of the embodiments described herein, will be apparent to those skilled in the art without departing from the scope of the present invention. It is understood that various alternatives to the embodiments described herein can be used in carrying out the present disclosure. Furthermore, it is intended that the appended claims cover such modifications and variations that fall within the true scope of the present invention.

[0145] It should be understood that all embodiments of the present disclosure may be optionally combined with one or more of the other embodiments described herein.

[0146] It should be understood that each component, compound, or parameter disclosed herein is to be construed as being disclosed for use alone or in combination with one or more of each and every other component, compound, or parameter disclosed herein. Each amount / value or amount / value range for each component, compound, or parameter disclosed herein is also to be construed as being disclosed in combination with each amount / value or amount or value range disclosed for any other component(s), compound(s), or parameter(s) disclosed herein; thus, it should be further understood that any combination of amount / values ​​or amount / value ranges for two or more components, two or more compounds, or two or more parameters disclosed herein is also disclosed in combination with each other for purposes of this description. Any and all features described herein, as well as combinations of such features, are included within the scope of the present invention, provided that these features are not mutually inconsistent.

[0147] It should be understood that each lower limit of each range disclosed herein is to be interpreted as being disclosed in combination with each upper limit of each range disclosed herein for the same component, compound, or parameter. Thus, the disclosure of two ranges is to be interpreted as disclosing four ranges obtained by combining each lower limit with each upper limit of each range. The disclosure of three ranges is to be interpreted as disclosing nine ranges obtained by combining each lower limit with each upper limit of each range, and so on. Furthermore, a specific amount / value of a component, compound, or parameter disclosed in the description or examples is to be interpreted as describing either a lower or upper limit of a range, and therefore can be combined with any other lower or upper limit or range or specific amount / value for the same component, compound, or parameter disclosed elsewhere in this application to form a range for the component, compound, or parameter. [Example]

[0148] Experiments 1a, 1b, and 1c Coating composition: 10wt% PHPS 5wt% TBAB 45wt% acetone 40% dibutyl ether (solvent)

[0149] Selection of groups of components and specific components: Sub-step ia) Component A: A reactive molecule that can spontaneously react with the polysilazane polymer backbone to cause fragmentation; acetone. Sub-step ib) Component B: Catalyst TBAB (dissolved in acetone). Sub-step ic) Component C: Polysilazane PHPS (dissolved in dibutyl ether).

[0150] The components were mixed in stages in a beaker.

[0151] Application methods, step ii): Drop casting and spreading.

[0152] time: T c =60 seconds Experiment 1a:T ii = 300 seconds, Experiment 1b: T ii = 600 seconds, Experiment 1c:T ii =1200 seconds.

[0153] result: Experiments 1a, 1b, and 1c were ii For each of Experiments 1a, 1b, and 1c, a corresponding control experiment without TBAB was also performed.

[0154] The resulting coatings from the above experiments were evaluated by visual inspection and, for hardness evaluation, by manual scratch testing using a glass cutter and copper tip.

[0155] Acetone was used as both the solvent and the reactant, and since TBAB was dissolved in acetone, the acetone was in excess and therefore the concentration of TBAB was kept high.

[0156] t ii Experiment 1a, with the shortest time of 300 seconds, produced a thicker coating than the corresponding control experiment without TBAB. Surface roughness was much greater when too much coating solution was applied. The coating composition was much less viscous when TBAB was not used, and as a result, the coating thickness could not be increased and its viscosity decreased over time.

[0157] t ii Experiment 1b, where the time is 600 s, resulted in coatings with increased surface roughness and hardness compared to experiment 1c.

[0158] t iiExperiment 1c, with a T = 1200 seconds, resulted in very high coating hardness (scratch resistance). Although it was difficult to obtain thin films due to the high crosslinking, which resulted in a more viscous composition over time, thinner portions of the coating showed very high scratch resistance. The corresponding control experiment without TBAB did not result in a film.

[0159] The very large difference in yield, i.e., coating thickness, between the catalyzed and uncatalyzed reactions indicates that solution cross-linking, leading to higher yields, works in the presence of fragmentation. In Experiment 1c, the control composition did not form a film. In the presence of a large amount of reactive component (acetone), the drop-cast formulation likely consisted primarily of solvent, volatile fragments, uncross-linked fragments, and acetone-PHPS reaction products.

[0160] In a further set of experiments, acetone was replaced with isopropanol, mirroring experiments 1a-c. In these experiments, scratch resistance decreased, indicating a stronger effect on hydroxyl fragmentation.

[0161] Experiments 2a, 2b, and 2c Coating composition: 9.5wt% PHPS 9wt% Durazane 1800 4.5wt% TBAB 40wt% acetone 37% dibutyl ether (solvent)

[0162] Selection of groups of components and specific components: Sub-step ia) Component A: A reactive molecule that can spontaneously react with the polysilazane polymer backbone to cause fragmentation; acetone. Sub-step ib) Component B: Catalyst TBAB (dissolved in acetone). Sub-step ic) Component C: Polysilazane PHPS and Durazane 1800 (dissolved in dibutyl ether).

[0163] The components were mixed stepwise in a beaker.

[0164] Application method, step ii): Drop casting method and spreading method.

[0165] time: T c =60 seconds Experiment 2a:T ii = 300 seconds, Experiment 2b: T ii = 600 seconds, Experiment 2c:T ii =1200 seconds.

[0166] result: Experiments 2a, 2b, and 2c were ii These experiments differed from one another in that the amount of TBAB in the control group was changed. For each of these experiments, a control experiment without TBAB was also performed. For each of experiments 2a, 2b, and 2c, a corresponding control experiment without TBAB was also performed.

[0167] The resulting coatings from the above experiments were evaluated by visual inspection and, for hardness evaluation, by manual scratch testing using a glass cutter and copper tip.

[0168] These experiments showed the same effects on yield and hardness as a function of time as in Experiments 1a-c. However, all t c For Experiments 2a-c, the coatings were less hard and smoother (less surface roughness) than the corresponding coatings in Experiments 1a-c. The lower hardness and lower surface roughness are likely due to the presence of the organopolysilazane Durazane 1800, which limits the degree of cross-linking and / or formation of the hard (inflexible) inorganic components of the coatings.

[0169] conclusion The results of Experiments 1 and 2 emphasize the importance of the time between mixing and application of the coating composition: hardness is determined by the time ii The surface roughness also increased significantly with increasing crosslinking time, i.e., tii The film thickness increased with increasing SiO2, but this effect was counteracted by the addition of organopolysilazane. It is also noteworthy that, as far as visual inspection could tell, no film formed after 1200 seconds without the catalyst.

[0170] Designed Experiment I - Coatings to Improve Scratch and Stain Resistance Coating composition (minus solvent): 60-80wt% Durazane 1033 (OPSZ that does not contain only methyl as a pendant group) 5-10wt% Durazane 1800 3~10wt% APTES

[0171] wt% based on the total weight of polysilazane and APTES: 1 to 4 wt% acrylic resin (e.g., PARALOID (registered trademark) B-44) 0.5-4 wt% surfactant TEGO (registered trademark) Phobe 1505 2~10wt% 2,2,2-trifluoroethanol 0.5~5wt% TBAB

[0172] Ratio of coating components to solvent (n-butyl acetate): 2 to 20 wt%

[0173] Selection of groups of components and specific components: Sub-step ia) Component A: Catalyst TBAB. Sub-step ib) Component B: reactive molecules that can react spontaneously with the polysilazane polymer backbone to cause fragmentation; APTES and 2,2,2-trifluoroethanol. Sub-step ic) Component C: the polysilazane described above. Further components that are premixed with component C and introduced simultaneously: acrylic resin, surfactant.

[0174] Application method, step ii): ultrasonic spray coating.

[0175] time: T c =5~60 seconds. T ii =5~300 seconds.

[0176] Additional curing step iii): In-line UV curing with H2O2 vapor.

[0177] Designed Experiment II - Coatings to Improve Scratch Resistance and Hydrophobicity Coating composition (minus solvent): 20-30wt% Durazane 1800 50~65wt% OPSZ other than Durazane1800 5-30wt% OH, nitrile and / or vinyl functionalized silica and / or TiO2

[0178] wt% of the total weight of the above ingredients: 0.0025~1wt% TBAF or TBAB 0.5~15wt% Hexane-1,6-diol diacrylate (HDC) 1~10wt% HCPK 2~10ppm Karlstedt catalyst

[0179] Ratio of coating composition to solvent (DMSO): 5 to 40 wt%

[0180] Selection of groups of components and specific components: Sub-step ia) Component A: Catalyst TBAF or TBAB. Further components that are premixed with component A and introduced simultaneously: HCPK, HDC. Sub-step ib) Component B: nanomaterials SiO2 and / or TiO2. A further component that is premixed with component B and introduced simultaneously: Karstedt catalyst. Sub-step ic) Component C: the polysilazane described above.

[0181] Application method, step ii): ultrasonic spray coating.

[0182] time: T c =5~60 seconds. T ii =5~300 seconds.

[0183] Additional curing step iii): In-line UV curing with H2O2 vapor.

[0184] Designed Experiment III - Coatings for Low Friction and Wear Applications Coating composition (minus solvent): 20~80wt% PHPS 10-40wt% Durazane 1800 10~40wt% OPSZ other than Durazane1800

[0185] wt% of the total weight of the above ingredients: Graphene oxide with 0.5-10 wt% OH, carbonyl and / or epoxy functional groups 0.5~5wt% 2-fluoroethanol 0.005~0.5wt% TBAF or TBAB

[0186] Ratio of coating composition to solvent (dibutyl ether): 2 to 40 wt%

[0187] Selection of groups of components and specific components: Sub-step ia) Component A: Nanomaterial. Graphene oxide mentioned above; ·One or more of the above WS2, MoS2, hexagonal boron nitride. A further component that is premixed with component A and introduced simultaneously: PEGD. Sub-step ib) Component B: Catalyst TBAF or TBAB. Further components that are premixed with component B and introduced simultaneously: HDC and / or DCP; 2-fluoroethanol; erucamide. Sub-step ix) Durazane1800. Sub-step ic) Component C: the above PHPS and OPSZ.

[0188] Application method, step ii): ultrasonic spray coating.

[0189] time T x Between (ib) and (ix): 5 to 60 seconds T c =5~60 seconds T ii =5~100 seconds

[0190] Additional curing step iii): cure with UV light; inert or ambient environment; 80-600°C.

Claims

1. 1. A polysilazane coating method for limiting fragmentation of the polysilazane, the method comprising: i) preparing a coating composition, the preparation of the coating composition comprising mixing components A, B, and C in a coating composition container; wherein components A, B, and C are each selected from the group of polysilazanes, the group of nucleophilic catalysts, or the group of reactive molecules that can spontaneously react with the reactive nanomaterial and / or polysilazane polymer backbone to cause fragmentation; said components A, B, and C are all selected from different groups; The selection of groups for each of the components A, B, and C is predetermined based on the known reactivities of the components with respect to one another. preparing a coating composition; ii) applying the coating composition to a substrate; Including, Step ii) is performed for a predetermined time t that is predetermined based on the known reactivities of the components with each other. ii It starts with Polysilazane coating method.

2. The step i) a. introducing component A into the coating composition container; b. introducing component B into said coating composition container and mixing component B with component A; c. introducing component C into said coating composition container and mixing component C with components A and B; The method of claim 1 , comprising:

3. 3. The method of claim 2, wherein the introduction of component C in substep ic) begins a predetermined time tc after the introduction of component B in substep ib); and tc is selected such that 0≦tc<900 seconds.

4. 4. The method of claim 3, wherein tc is selected such that 0<tc<900 seconds.

5. The predetermined time t ii is 1≦t ii 5. The method of any one of claims 1 to 4, wherein the time period is selected to be ≦1200 seconds.

6. The predetermined time t c and t ii 4. The method of claim 3, wherein the time period is not more than 300 seconds.

7. The method according to any one of claims 1 to 6, wherein the group of nucleophilic catalysts comprises a catalyst for crosslinking polysilazanes.

8. The method according to any one of claims 1 to 7, wherein the method is carried out using a continuous flow.

9. The method according to any one of claims 1 to 8, wherein step ii) is carried out by ultrasonic spray coating or by roller coating.

10. The method of any one of claims 1 to 9, wherein the coating composition is diluted prior to application in step ii).

11. 11. The method of any one of claims 1 to 10, wherein component A is selected from the group of reactive molecules that can react spontaneously with reactive nanomaterials and / or polysilazane polymer backbones to cause fragmentation, component B is selected from the group of polysilazanes, and component C is selected from the group of nucleophilic catalysts.

12. 11. The method of any one of claims 1 to 10, wherein component A is selected from the group of reactive molecules that can react spontaneously with reactive nanomaterials and / or polysilazane polymer backbones to cause fragmentation, component B is selected from the group of nucleophilic catalysts, and component C is selected from the group of polysilazanes.

13. 13. The method of claim 12, wherein components A and B are premixed before being introduced into the coating composition container.

14. 3. The method of claim 2, further comprising an additional substep ix) before or after any one of said substeps ia), ib), or ic).

15. An assembly (100) for carrying out the method according to any one of claims 1 to 14, comprising: an elongated coating composition container (110) having a first end (121) and a second end (122), the first end and the second end being positioned opposite one another; a first injection port (131); a second injection port (132) located closer to the second end than the first injection port; a third injection port (133) located a distance (D) from the second injection port and closer to the second end than the second injection port; an applicator port (141) located a distance (D') from the third injection port and closer to the second end than the third injection port; an elongated coating composition container (110) comprising: an applicator (150) connected to the applicator port so as to provide a fluid connection between the applicator and the elongated coating composition container; a pressure generating unit (161) connected directly or indirectly to the first injection port and configured to generate a pressure to generate a pressure difference between the first injection port and the applicator port; An assembly (100) comprising:

16. 16. The assembly of claim 15, further comprising an additional pressure generating unit (162) configured to generate a pressure, the additional pressure generating unit being directly or indirectly connected to the second injection port (132) or the third injection port (133) to generate a pressure differential between the second or third injection port and the applicator port (141).

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