Patent Publication Number: US-2017349825-A1

Title: Nanocomposite coatings for oxidation protection of composites

Description:
FIELD 
     The present disclosure relates generally to carbon-carbon composites and, more specifically, to oxidation protection systems for carbon-carbon composite structures. 
     BACKGROUND 
     Oxidation protection systems for carbon-carbon composites are typically designed to minimize loss of carbon material due to oxidation at operating conditions, which include temperatures as high as 900° C. (1652° F.). Phosphate-based oxidation protection systems may reduce infiltration of oxygen and oxidation catalysts into the composite structure. However, despite the use of such oxidation protection systems, significant oxidation of the carbon-carbon composites may still occur during operation of components such as, for example, aircraft braking systems. 
     SUMMARY 
     A method for coating a composite structure is provided comprising applying a first slurry of a first phosphate glass composition on an outer surface of the composite structure. The first slurry comprises a first additive including at least one of molybdenum disulfide or tungsten disulfide. The method may further include heating the composite structure to a temperature sufficient to form a base layer adhered to the composite structure. 
     In various embodiments, the method may further comprise forming a first pre-slurry composition by combining the first additive with a first glass frit comprising the first phosphate glass composition. The method may further comprise forming the first slurry by combining the first pre-slurry composition with a first carrier fluid. The first carrier fluid may comprise an acid aluminum phosphate. The first slurry may further comprise a second additive including boron nitride. A ratio of the first additive and the second additive may be between 1:10 and 17:1. A ratio of the first additive and the second additive may be between 1:1 and 1:9. In various embodiments, the method may further comprise applying a second slurry of a second phosphate glass composition to the base layer, and heating the composite structure to a temperature sufficient to form sealing layer adhered to the base layer. In various embodiments, the second slurry may be substantially free of molybdenum disulfide, tungsten disulfide and boron nitride. 
     In various embodiments, the first phosphate glass composition may be represented by the formula a(A′ 2 O) x (P 2 O 5 ) y1 b(G f O) y2 c(A″O) z : 
     A′ is selected from: lithium, sodium, potassium, rubidium, cesium, and mixtures thereof; 
     G f  is selected from: boron, silicon, sulfur, germanium, arsenic, antimony, and mixtures thereof; 
     A″ is selected from: vanadium, aluminum, tin, titanium, chromium, manganese, iron, cobalt, nickel, copper, mercury, zinc, thulium, lead, zirconium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, actinium, thorium, uranium, yttrium, gallium, magnesium, calcium, strontium, barium, tin, bismuth, cadmium, and mixtures thereof; 
     a is a number in the range from 1 to about 5; 
     b is a number in the range from 0 to about 10; 
     c is a number in the range from 0 to about 30; 
     x is a number in the range from about 0.050 to about 0.500; 
     y 1  is a number in the range from about 0.100 to about 0.950; 
     y 2  is a number in the range from 0 to about 0.20; and 
     z is a number in the range from about 0.01 to about 0.5; 
     (x+y 1 +y 2 +z)=1; and 
     x&lt;(y 1 +y 2 ). 
     An article is also provided comprising a composite structure and an oxidation protection composition including a base layer disposed on an outer surface of the composite structure. The base layer may comprise a first phosphate glass composition having a first additive dispersed throughout the base layer. The first additive may include at least one of molybdenum disulfide or tungsten disulfide. 
     In various embodiments, the base layer may further comprise a boron nitride additive. A ratio of the first additive and the second additive may be between 1:10 and 17:1. A ratio of the first additive and the second additive may be between 1:1 and 1:9. In various embodiments, a sealing layer may be disposed on an outer surface of the base layer. The sealing layer may comprise a second phosphate glass composition. The sealing layer may be substantially free of boron nitride, molybdenum disulfide and tungsten disulfide. 
     An oxidation protection composition is also provided comprising a first phosphate glass composition having a first additive. The first additive may include at least one of molybdenum disulfide or tungsten disulfide. The oxidation protection composition may also comprise a first carrier fluid. 
     In various embodiments, a second additive may include boron nitride. A ratio of the first additive and the second additive may be between 1:10 and 17:1. A ratio of the first additive and the second additive may be between 1:1 and 1:9. The first carrier fluid may comprise an acid aluminum phosphate. 
     In various embodiments, the first phosphate glass composition is represented by the formula a(A′ 2 O) x (P 2 O 5 ) y1 b(G f O) y2 c(A″O) z : 
     A′ is selected from: lithium, sodium, potassium, rubidium, cesium, and mixtures thereof; 
     G f  is selected from: boron, silicon, sulfur, germanium, arsenic, antimony, and mixtures thereof; 
     A″ is selected from: vanadium, aluminum, tin, titanium, chromium, manganese, iron, cobalt, nickel, copper, mercury, zinc, thulium, lead, zirconium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, actinium, thorium, uranium, yttrium, gallium, magnesium, calcium, strontium, barium, tin, bismuth, cadmium, and mixtures thereof; 
     a is a number in the range from 1 to about 5; 
     b is a number in the range from 0 to about 10; 
     c is a number in the range from 0 to about 30; 
     x is a number in the range from about 0.050 to about 0.500; 
     y 1  is a number in the range from about 0.100 to about 0.950; 
     y 2  is a number in the range from 0 to about 0.20; and 
     z is a number in the range from about 0.01 to about 0.5; 
     (x+y 1 +y 2 +z)=1; and 
     x&lt;(y 1 +y 2 ). 
    
    
     
       BRIEF DESCRIPTION OF THE DRAWINGS 
       The subject matter of the present disclosure is particularly pointed out and distinctly claimed in the concluding portion of the specification. A more complete understanding of the present disclosure, however, may best be obtained by referring to the detailed description and claims when considered in connection with the drawing figures, wherein like numerals denote like elements. 
         FIG. 1A  illustrates a cross sectional view of an aircraft wheel braking assembly, in accordance with various embodiments; 
         FIG. 1B  illustrates a partial side view of an aircraft wheel braking assembly, in accordance with various embodiments; 
         FIGS. 2A, 2B, and 2C  illustrate a method for coating a composite structure in accordance with various embodiments; 
         FIG. 3  illustrates experimental data obtained from testing various glass compositions in accordance with various embodiments; 
         FIG. 4  illustrates further experimental data obtained from testing various glass compositions in accordance with various embodiments at 760° C. (1400° F.); and 
         FIG. 5  illustrates further experimental data obtained from testing various oxidation protection slurries in accordance with various embodiments at 760° C. (1400° F.). 
     
    
    
     DETAILED DESCRIPTION 
     The detailed description of embodiments herein makes reference to the accompanying drawings, which show embodiments by way of illustration. While these embodiments are described in sufficient detail to enable those skilled in the art to practice the disclosure, it should be understood that other embodiments may be realized and that logical and mechanical changes may be made without departing from the spirit and scope of the disclosure. Thus, the detailed description herein is presented for purposes of illustration only and not for limitation. For example, any reference to singular includes plural embodiments, and any reference to more than one component or step may include a singular embodiment or step. Also, any reference to attached, fixed, connected or the like may include permanent, removable, temporary, partial, full and/or any other possible attachment option. 
     With initial reference to  FIGS. 1A and 1B , aircraft wheel braking assembly  10  such as may be found on an aircraft, in accordance with various embodiments is illustrated. Aircraft wheel braking assembly may, for example, comprise a bogie axle  12 , a wheel  14  including a hub  16  and a wheel well  18 , a web  20 , a torque take-out assembly  22 , one or more torque bars  24 , a wheel rotational axis  26 , a wheel well recess  28 , an actuator  30 , multiple brake rotors  32 , multiple brake stators  34 , a pressure plate  36 , an end plate  38 , a heat shield  40 , multiple heat shield sections  42 , multiple heat shield carriers  44 , an air gap  46 , multiple torque bar bolts  48 , a torque bar pin  50 , a wheel web hole  52 , multiple heat shield fasteners  53 , multiple rotor lugs  54 , and multiple stator slots  56 .  FIG. 1B  illustrates a portion of aircraft wheel braking assembly  10  as viewed into wheel well  18  and wheel well recess  28 . 
     In various embodiments, the various components of aircraft wheel braking assembly  10  may be subjected to the application of compositions and methods for protecting the components from oxidation. 
     Brake disks (e.g., interleaved rotors  32  and stators  34 ) are disposed in wheel well recess  28  of wheel well  18 . Rotors  32  are secured to torque bars  24  for rotation with wheel  14 , while stators  34  are engaged with torque take-out assembly  22 . At least one actuator  30  is operable to compress interleaved rotors  32  and stators  34  for stopping the aircraft. In this example, actuator  30  is shown as a hydraulically actuated piston, but many types of actuators are suitable, such as an electromechanical actuator. Pressure plate  36  and end plate  38  are disposed at opposite ends of the interleaved rotors  32  and stators  34 . Rotors  32  and stators  34  can comprise any material suitable for friction disks, including ceramics or carbon materials, such as a carbon/carbon composite. 
     Through compression of interleaved rotors  32  and stators  34  between pressure plates  36  and end plate  38 , the resulting frictional contact slows rotation of wheel  14 . Torque take-out assembly  22  is secured to a stationary portion of the landing gear truck such as a bogie beam or other landing gear strut, such that torque take-out assembly  22  and stators  34  are prevented from rotating during braking of the aircraft. 
     Carbon-carbon composites (also referred to herein as composite structures, composite substrates, and carbon-carbon composite structures, interchangeably) in the friction disks may operate as a heat sink to absorb large amounts of kinetic energy converted to heat during slowing of the aircraft. Heat shield  40  may reflect thermal energy away from wheel well  18  and back toward rotors  32  and stators  34 . With reference to  FIG. 1A , a portion of wheel well  18  and torque bar  24  is removed to better illustrate heat shield  40  and heat shield segments  42 . With reference to  FIG. 1B , heat shield  40  is attached to wheel  14  and is concentric with wheel well  18 . Individual heat shield sections  42  may be secured in place between wheel well  18  and rotors  32  by respective heat shield carriers  44  fixed to wheel well  18 . Air gap  46  is defined annularly between heat shield segments  42  and wheel well  18 . 
     Torque bars  24  and heat shield carriers  44  can be secured to wheel  14  using bolts or other fasteners. Torque bar bolts  48  can extend through a hole formed in a flange or other mounting surface on wheel  14 . Each torque bar  24  can optionally include at least one torque bar pin  50  at an end opposite torque bar bolts  48 , such that torque bar pin  50  can be received through wheel web hole  52  in web  20 . Heat shield sections  42  and respective heat shield carriers  44  can then be fastened to wheel well  18  by heat shield fasteners  53 . 
     Under the operating conditions (e.g., high temperature) of aircraft wheel braking assembly  10 , carbon-carbon composites may be prone to material loss from oxidation of the carbon. For example, various carbon-carbon composite components of aircraft wheel braking assembly  10  may experience both catalytic oxidation and inherent thermal oxidation caused by heating the composite during operation. In various embodiments, composite rotors  32  and stators  34  may be heated to sufficiently high temperatures that may oxidize the carbon surfaces exposed to air. At elevated temperatures, infiltration of air and contaminants may cause internal oxidation and weakening, especially in and around brake rotor lugs  54  or stator slots  56  securing the friction disks to the respective torque bar  24  and torque take-out assembly  22 . Because carbon-carbon composite components of aircraft wheel braking assembly  10  may retain heat for a substantial time period after slowing the aircraft, oxygen from the ambient atmosphere may react with the carbon matrix and/or carbon fibers to accelerate material loss. Further, damage to brake components may be caused by the oxidation enlargement of cracks around fibers or enlargement of cracks in a reaction-formed porous barrier coating (e.g., a silicon-based barrier coating) applied to the carbon-carbon composite. 
     Elements identified in severely oxidized regions of carbon-carbon composite brake components include potassium (K) and sodium (Na). These alkali contaminants may come into contact with aircraft brakes as part of cleaning or de-icing materials. Other sources include salt deposits left from seawater or sea spray. These and other contaminants (e.g. Ca, Fe, etc.) can penetrate and leave deposits in pores of carbon-carbon composite aircraft brakes, including the substrate and any reaction-formed porous barrier coating. When such contamination occurs, the rate of carbon loss by oxidation can be increased by one to two orders of magnitude. 
     In various embodiments, components of aircraft wheel braking assembly  10  may reach operating temperatures in the range from about 100° C. up to about 900° C. However, it will be recognized that the oxidation protection compositions and methods of the present disclosure may be readily adapted to many parts in this and other braking assemblies, as well as to other carbon-carbon composite structures susceptible to oxidation losses from infiltration of atmospheric oxygen and/or catalytic contaminants. 
     In various embodiments, a method for limiting an oxidation reaction in a composite structure may comprise forming a slurry, which may be an oxidation protection composition, by combining a pre-slurry composition comprising a first phosphate glass composition in the form of a glass frit, powder, or other suitable pulverized form with a first carrier fluid (such as, for example, water), applying the slurry to a composite structure, and heating the composite structure to a temperature sufficient to dry the carrier fluid and form an oxidation protection composition or coating (or oxidation inhibiting composition) on the composite structure, which in various embodiments may be referred to as a base layer. The slurry, which may be an oxidation protection composition, may comprise additives to increase temperature resistance, to change chemical reactivity, to improve hydrolytic stability, and/or to increase the composite structure&#39;s resistance to oxidation, thereby tending to reduce mass loss of composite structure. In various embodiments, the pre-slurry composition of the slurry may comprise one or more additives to increase temperature resistance of the oxidation protection coating. The one or more additives may include carbide, nitride, boron nitride, silicon carbide, titanium carbide, boron carbide, silicon oxycarbide, molybdenum disulfide, tungsten disulfide and/or silicon nitride. In various embodiments, an additive may include molybdenum disulfide (MoS 2 ), tungsten disulfide (WS 2 ), and/or boron nitride (BN). For example, the pre-slurry composition of the slurry may comprise a first additive, such as molybdenum disulfide, tungsten disulfide, and/or boron nitride. The pre-slurry composition of the slurry may further comprise a second additive, such as molybdenum disulfide, tungsten disulfide, and/or boron nitride. 
     In various embodiments, the pre-slurry composition of the slurry may further comprise additives, such as, for example, ammonium hydroxide, ammonium dihydrogen phosphate, nanoplatelets (such as graphene-based nanoplatelets), among others to improve hydrolytic stability and/or to increase the composite structure&#39;s resistance to oxidation. In various embodiments, a slurry may comprise acid aluminum phosphates having an aluminum (Al) to phosphoric acid (H 3 PO 4 ) ratio of 1 to 5 or less by weight. In various embodiments, a slurry comprising acid aluminum phosphates having an aluminum (Al) to phosphoric acid (H 3 PO 4 ) ratio of 1 to 3 or less by weight, such as an Al:H 3 PO 4  ratio of between 1 to 2 and 1 to 3 by weight, tends to provide increased hydrolytic stability without substantially increasing composite structure mass loss. In various embodiments, a slurry comprising acid aluminum phosphates having an Al:H 3 PO 4  ratio between 1:2 to 1:3 produces an increase in hydrolytic protection and an unexpected reduction in composite structure mass loss. 
     With initial reference to  FIG. 2A , a method  200  for coating a composite structure in accordance with various embodiments is illustrated. Method  200  may, for example, comprise applying an oxidation inhibiting composition, or oxidation protection composition, to non-wearing surfaces of carbon-carbon composite brake components. In various embodiments, method  200  may be used on the back face of pressure plate  36  and/or end plate  38 , an inner diameter (ID) surface of stators  34  including slots  56 , as well as outer diameter (OD) surfaces of rotors  32  including lugs  54 . The oxidation protection composition or oxidation inhibiting composition of method  200  may be applied to preselected regions of a carbon-carbon composite structure that may be otherwise susceptible to oxidation. For example, aircraft brake disks may have the oxidation inhibiting composition applied on or proximate stator slots  56  and/or rotor lugs  54 . 
     In various embodiments, method  200  may comprise forming a first slurry  210 , which may be an oxidation protection composition, by combining a first phosphate glass composition in the form of a glass frit, powder, or other suitable pulverized and/or ground form with a first carrier fluid (such as, for example, water). In various embodiments, the first phosphate glass composition may be combined with one or more additives to form a first pre-slurry composition. An additive may include carbide, nitride, boron nitride, silicon carbide, titanium carbide, boron carbide, silicon oxycarbide, molybdenum disulfide, tungsten disulfide and/or silicon nitride. For example, the first pre-slurry composition may include a first additive, a second additive and/or a third additive. A first pre-slurry composition comprising a first additive may include molybdenum disulfide, tungsten disulfide or boron nitride. A first pre-slurry composition comprising a first additive and a second additive may include molybdenum disulfide and tungsten disulfide, molybdenum disulfide and boron nitride, or tungsten disulfide and boron nitride. A first pre-slurry composition comprising a first additive, a second additive and a third additive may include molybdenum disulfide, tungsten disulfide and boron nitride. 
     In various embodiments, the first phosphate glass composition of the first slurry may be combined with a first additive, which may include a molybdenum disulfide (MoS 2 ) additive and/or a tungsten disulfide (WS 2 ) additive. For example, molybdenum disulfide, such as hexagonal molybdenum disulfide (h-MoS 2 ), may be added to the first phosphate glass composition to form a resulting pre-slurry composition comprising between about 1.0 and 9.0 percent molybdenum disulfide by mass, wherein the term “about” in this context only means+/−1 percent. The pre-slurry composition may comprise between about 4.0 and 9.0 percent molybdenum disulfide by mass, wherein the term “about” in this context only means+/−1 percent by mass. Further, the pre-slurry composition may comprise between about 7.0 and 9.0 percent molybdenum disulfide by mass, wherein the term “about” in this context only means+/−1 percent by mass. Molybdenum disulfide may be prepared for addition to the first phosphate glass composition by, for example, ultrasonically exfoliating molybdenum disulfide in dimethylformamide (DMF), a solution of DMF and water, or 2-propanol solution. In various embodiments, the molybdenum disulfide additive may comprise a molybdenum disulfide that has been prepared for addition to the first phosphate glass composition by crushing or milling (e.g., ball milling) the molybdenum disulfide. The resulting molybdenum disulfide may be combined with the first phosphate glass composition glass frit to form the pre-slurry composition. 
     The first additive of the pre-slurry composition may comprise a tungsten disulfide additive. For example, tungsten disulfide may be added to the first phosphate glass composition to form a resulting pre-slurry composition comprising between about 0.1 and 9.0 percent tungsten disulfide by mass, wherein the term “about” in this context only means+/−0.1 percent by mass. The pre-slurry composition may comprise between about 0.25 and 7.5 percent tungsten disulfide by mass, wherein the term “about” in this context only means+/−0.25 percent by mass. The pre-slurry composition may comprise between about 4.0 and 9.0 percent tungsten disulfide by mass, wherein the term “about” in this context only means+/−1 percent by mass. Tungsten disulfide may be prepared for addition to the first phosphate glass composition by, for example, ultrasonically exfoliating tungsten disulfide in DMF, a solution of DMF and water, or 2-propanol solution. In various embodiments, the tungsten disulfide additive may comprise a tungsten disulfide that has been prepared for addition to the first phosphate glass composition by crushing or milling (e.g., ball milling) the tungsten disulfide. The resulting tungsten disulfide may be combined with the first phosphate glass composition glass frit to form the pre-slurry composition. 
     In various embodiments, the first phosphate glass composition of the first pre-slurry composition may further be combined with a second additive, which may include a molybdenum disulfide additive, a tungsten disulfide additive and/or a boron nitride additive. For example, a boron nitride (such as hexagonal boron nitride) may be added to the pre-slurry composition such that the pre-slurry composition comprises between about 0.1 and 8.0 percent boron nitride by mass, wherein the term “about” in this context only means+/−0.1 percent by mass. The pre-slurry composition may comprise between about 0.25 and 7.5 percent boron nitride by mass, wherein the term “about” in this context only means+/−0.25 percent by mass. Further, the pre-slurry composition may comprise between about 0.25 and 4.5 percent boron nitride by mass, wherein the term “about” in this context only means+/−0.25 percent by mass. In various embodiments, the pre-slurry composition may comprise between about 10 weight percent and about 30 weight percent of boron nitride, wherein the term “about” in this context only means+/−2 weight percent. Further, the pre-slurry composition may comprise between about 15 weight percent and 25 weight percent of boron nitride, wherein the term “about” in this context only means+/−2% weight percent. Further, the pre-slurry composition may comprise between about 17 weight percent and 29 weight percent of boron nitride, wherein the term “about” in this context only means+/−2 weight percent. Boron nitride may be prepared for addition to the first phosphate glass composition by, for example, ultrasonically exfoliating boron nitride in DMF, a solution of DMF and water, or 2-propanol solution. In various embodiments, the boron nitride additive may comprise a boron nitride that has been prepared for addition to the first phosphate glass composition by crushing or milling (e.g., ball milling) the boron nitride. The resulting boron nitride may be combined with the first phosphate glass composition glass frit to form the pre-slurry composition. 
     In various embodiments, the pre-slurry composition may comprise a first additive and a second additive. The first additive may include molybdenum disulfide and the second additive may include boron nitride. The first additive may include tungsten disulfide and the second additive may include boron nitride. The ratio of the first additive to the second additive, MoS 2  or WS 2  to BN, may be 1:1, 1:2, 1:4, 1:9, 1.5:7.25, 2:1, 4:1, 9:1, 16.5:1, or 17:1, or 1.5:7.25, or between 1:1 and 34:1, or between 1:10 and 17:1, or between 17:1 and 34:1. The first additive may include molybdenum disulfide and the second additive may include tungsten disulfide. The ratio of the first additive to the second additive, MoS 2  to WS 2 , may be 1:1, 1:2, 1:4, 1:9, 1.5:7.25, 2:1, 4:1, 9:1, 16.5:1, or 17:1, or 1.5:7.25, or between 1:1 and 34:1, or between 1:10 and 17:1, or between 17:1 and 34:1. In various embodiments, the pre-slurry composition may further comprise a third additive. The first additive may include molybdenum disulfide, the second additive may include boron nitride and the third additive may include tungsten disulfide. The ratio of the first additive, second additive, and third additive may be, for example, between 1:1:1 and 1:10:1, between 1:1:1 and 10:1:1, or between 1:1:1 and 1:1:10. 
     The first phosphate glass composition may comprise one or more alkali metal glass modifiers, one or more glass network modifiers and/or one or more additional glass formers. In various embodiments, boron oxide or a precursor may optionally be combined with the P 2 O 5  mixture to form a borophosphate glass, which has improved self-healing properties at the operating temperatures typically seen in aircraft braking assemblies. In various embodiments, the phosphate glass and/or borophosphate glass may be characterized by the absence of an oxide of silicon. Further, the ratio of P 2 O 5  to metal oxide in the fused glass may be in the range from about 0.25 to about 5 by weight. 
     Potential alkali metal glass modifiers may be selected from oxides of lithium, sodium, potassium, rubidium, cesium, and mixtures thereof. In various embodiments, the glass modifier may be an oxide of lithium, sodium, potassium, or mixtures thereof. These or other glass modifiers may function as fluxing agents. Additional glass formers can include oxides of boron, silicon, sulfur, germanium, arsenic, antimony, and mixtures thereof. 
     Suitable glass network modifiers include oxides of vanadium, aluminum, tin, titanium, chromium, manganese, iron, cobalt, nickel, copper, mercury, zinc, thulium, lead, zirconium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, actinium, thorium, uranium, yttrium, gallium, magnesium, calcium, strontium, barium, tin, bismuth, cadmium, and mixtures thereof. 
     The first phosphate glass composition may be prepared by combining the above alkali metal glass modifiers, glass network modifiers, glass formers and/or P 2 O 5  and heating them to a fusion temperature. In various embodiments, depending on the particular combination of elements, the fusion temperature may be in the range from about 700° C. (1292° F.) to about 1500° C. (2732° F.). The resultant melt may then be cooled and pulverized and/or ground to form a glass frit or powder. In various embodiments, the first phosphate glass composition may be annealed to a rigid, friable state prior to being pulverized. Glass transition temperature (T g ), glass softening temperature (T s ) and glass melting temperature (T m ) may be increased by increasing refinement time and/or temperature. Before fusion, the first phosphate glass composition comprises from about 20 mol % to about 80 mol % of P 2 O 5 . In various embodiments, the first phosphate glass composition comprises from about 30 mol % to about 70 mol % P 2 O 5 , or precursor thereof. In various embodiments, the first phosphate glass composition comprises from about 40 to about 60 mol % of P 2 O 5 . 
     The first phosphate glass composition may comprise from about 5 mol % to about 50 mol % of the alkali metal oxide. In various embodiments, the first phosphate glass composition comprises from about 10 mol % to about 40 mol % of the alkali metal oxide. Further, the first phosphate glass composition comprises from about 15 to about 30 mol % of the alkali metal oxide or one or more precursors thereof. In various embodiments, the first phosphate glass composition may comprise from about 0.5 mol % to about 50 mol % of one or more of the above-indicated glass formers. The first phosphate glass composition may comprise about 5 to about 20 mol % by weight of one or more of the above-indicated glass formers. As used herein, mol % is defined as the number of moles of a constituent per the total moles of the solution. 
     In various embodiments, the first phosphate glass composition can comprise from about 0.5 mol % to about 40 mol % of one or more of the above-indicated glass network modifiers. The first phosphate glass composition may comprise from about 2.0 mol % to about 25 mol % of one or more of the above-indicated glass network modifiers. 
     In various embodiments, the first phosphate glass composition may represented by the formula: 
         a (A′ 2 O) x (P 2 O 5 ) y1   b (G f O) y2   c (A″O) z   [1]
 
     In Formula 1, A′ is selected from: lithium, sodium, potassium, rubidium, cesium, and mixtures thereof; G f  is selected from: boron, silicon, sulfur, germanium, arsenic, antimony, and mixtures thereof; A″ is selected from: vanadium, aluminum, tin, titanium, chromium, manganese, iron, cobalt, nickel, copper, mercury, zinc, thulium, lead, zirconium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, actinium, thorium, uranium, yttrium, gallium, magnesium, calcium, strontium, barium, tin, bismuth, cadmium, and mixtures thereof; a is a number in the range from 1 to about 5; b is a number in the range from 0 to about 10; c is a number in the range from 0 to about 30; x is a number in the range from about 0.050 to about 0.500; y 1  is a number in the range from about 0.100 to about 0.950; y 2  is a number in the range from 0 to about 0.20; and z is a number in the range from about 0.01 to about 0.5; (x+y 1 +y 2 +z)=1; and x&lt;(y 1 +y 2 ). The first phosphate glass composition may be formulated to balance the reactivity, durability and flow of the resulting glass barrier layer for optimal performance. 
     In various embodiments, the first phosphate glass composition in glass frit form may be combined with additional components to form the first pre-slurry composition. For example, crushed first phosphate glass composition in glass frit form may be combined with ammonium hydroxide, ammonium dihydrogen phosphate, nanoplatelets (such as graphene-based nanoplatelets), among others. For example, graphene nanoplatelets could be added to the first phosphate glass composition in glass frit form. In various embodiments, the additional components may be combined and preprocessed before combining them with first phosphate glass composition in glass frit form. Other suitable additional components include, for example, surfactants such as, for example, an ethoxylated low-foam wetting agent and flow modifiers, such as, for example, polyvinyl alcohol, polyacrylate, or similar polymers. In various embodiments, other suitable additional components may include additives to enhance impact resistance and/or to toughen the oxidation protection coating, such as, for example, at least one of whiskers, nanofibers or nanotubes consisting of nitrides, carbides, carbon, graphite, quartz, silicates, aluminosilicates, phosphates, and the like. In various embodiments, additives to increase temperature resistance, to change chemical reactivity, enhance impact resistance and/or to toughen the oxidation protection coating may include silicon carbide whiskers, carbon nanofibers, molybdenum disulfide nanoplatelets, tungsten disulfide, boron nitride nanotubes and similar materials. 
     In various embodiments, the first pre-slurry composition may be combined with a first carrier fluid to form the first slurry. The first carrier fluid of the first slurry may comprise an acid aluminum phosphate wherein the ratio of Al:H 3 PO 4  may be between 1:2 to 1:5, between 1:2 to 1:3, between 1:3 to 1:5, between 1:2.2 to 1:3, between 1:2.5 to 1:3, between 1:2.7 to 1:3 or between 1:29 to 1:3, as measured by weight. 
     In various embodiments, method  200  further comprises applying the first slurry to a composite structure  220 . Applying the first slurry may comprise, for example, spraying or brushing the first slurry of the first phosphate glass composition on to an outer surface of the composite structure. Any suitable manner of applying the base layer to the composite structure is within the scope of the present disclosure. As referenced herein, the composite structure may refer to a carbon-carbon composite structure. 
     In various embodiments, method  200  further comprises a step  230  of heating the composite structure to form a base layer of phosphate glass. The composite structure may be heated (e.g., dried or baked) at a temperature in the range from about 150° C. (302° F.) to about 1000° C. (1832° F.). In various embodiments, the composite structure is heated to a temperature in a range from about 600° C. (1112° F.) to about 1000° C. (1832° F.), or between about 150° C. (302° F.) to about 900° C. (1652° F.), or further, between about 400° C. (752° F.) to about 850° C. (1562° F.). Step  230  may, for example, comprise heating the composite structure for a period between about 0.5 hour and about 8 hours, wherein the term “about” in this context only means+/−0.25 hours. The base layer may also be referred to as a coating. 
     In various embodiments, the composite structure may be heated to a first, lower temperature (for example, about 30° C. (86° F.) to about 400° C. (752° F.)) to bake or dry the base layer at a controlled depth. A second, higher temperature (for example, about 300° C. (572° F.) to about 1000° C. (1832° F.)) may then be used to form a deposit from the base layer within the pores of the composite structure. The duration of each heating step can be determined as a fraction of the overall heating time and can range from about 10% to about 50%, wherein the term “about” in this context only means+/−5%. In various embodiments, the duration of the lower temperature heating step(s) can range from about 20% to about 40% of the overall heating time, wherein the term “about” in this context only means+/−5%. The lower temperature step(s) may occupy a larger fraction of the overall heating time, for example, to provide relatively slow heating up to and through the first lower temperature. The exact heating profile will depend on a combination of the first temperature and desired depth of the drying portion. 
     Step  230  may be performed in an inert environment, such as under a blanket of inert gas or less reactive gas (e.g., nitrogen, argon, other noble gases and the like). For example, a composite structure may be pretreated or warmed prior to application of the base layer to aid in the penetration of the base layer. Step  230  may be for a period of about 2 hours at a temperature of about 600° C. (1112° F.) to about 800° C. (1472° F.), wherein the term “about” in this context only means+/−10° C. The composite structure and base layer may then be dried or baked in a non-oxidizing, inert or less reactive atmosphere, e.g., noble gasses and/or nitrogen (N 2 ), to optimize the retention of the first pre-slurry composition of the base layer in the pores of the composite structure. This retention may, for example, be improved by heating the composite structure to about 200° C. (392° F.) and maintaining the temperature for about 1 hour before heating the carbon-carbon composite to a temperature in the range described above. The temperature rise may be controlled at a rate that removes water without boiling, and provides temperature uniformity throughout the composite structure. 
     With reference now to  FIG. 2B , a method  300  for coating a composite structure in accordance with various embodiments is illustrated. Method  300  may, for example, comprise applying an oxidation inhibiting composition or oxidation protection composition to non-wearing surfaces of carbon-carbon composite brake components. Method  300 , which comprises steps also found in method  200 , may further comprise a step  240 , similar to step  210 , of forming a second slurry by combining a second pre-slurry composition, which may comprise a second phosphate glass composition in glass frit or powder form with a second carrier fluid (such as, for example, water). In various embodiments, the second slurry may comprise an acid aluminum phosphate wherein the ratio of aluminum (Al) to phosphoric acid (H 3 PO 4 ) may be between 1:2 to 1:5, between 1:2 to 1:3, between 1:3 to 1:5, between 1:2.2 to 1:3, between 1:2.5 to 1:3, between 1:2.7 to 1:3 or between 1:29 to 1:3. Step  240  may further comprise, similar to step  220 , applying the second slurry to the base layer. Step  240  may comprise spraying or brushing the second slurry of the second phosphate glass composition on to an outer surface of the base layer. Any suitable manner of applying the sealing layer to the base layer is within the scope of the present disclosure. 
     In various embodiments, the second slurry may be substantially free of molybdenum disulfide, tungsten disulfide and boron nitride. The second slurry may be substantially free of carbide, nitride, boron nitride, silicon carbide, titanium carbide, boron carbide, silicon oxycarbide, molybdenum disulfide, tungsten disulfide, and silicon nitride. In this case, “substantially free” means less than 0.01 percent by weight. For example, the second pre-slurry composition may comprise any of the glass compositions described in connection with the first phosphate glass composition, without the addition of a molybdenum disulfide additive, without the addition of a tungsten disulfide additive and without the addition of a boron nitride additive. In various embodiments, the second pre-slurry composition may comprise the same pre-slurry composition and/or phosphate glass composition used to prepare the first pre-slurry composition and/or first phosphate glass composition. In various embodiments, the second pre-slurry composition may comprise a different pre-slurry composition and/or phosphate glass composition than the first pre-slurry composition and/or first phosphate glass composition. 
     In various embodiments, the first slurry and the second slurry may be formulated to balance the durability, temperature resistance, chemical resistance, impact resistance, and self-healing properties of the oxidation protection coating on the composite structure. The first pre-slurry composition or first slurry may comprise additives to increase temperature resistance, while the second pre-slurry composition or second slurry may be formulated to improve the impact resistance and self-healing properties of the oxidation protection coating. The oxidation protection coating comprising the first and second pre-slurry compositions or slurries may have both increased temperature resistance and self-healing properties, thereby increasing the oxidation protection capability of the coating and reducing mass loss of composite structures at higher temperatures. 
     Method  300  may further comprise a step  250  of heating the composite structure to form a sealing layer of phosphate glass over the base layer. Similar to step  230 , the composite structure may be heated at a temperature sufficient to adhere the sealing layer to the base layer by, for example, drying or baking the carbon-carbon composite structure at a temperature in the range from about 200° C. (392° F.) to about 1000° C. (1832° F.). In various embodiments, the composite structure is heated to a temperature in a range from about 650° C. (1202° F.) to about 900° C. (1652° F.), or between about 200° C. (392° F.) to about 900° C. (1652° F.), or further, between about 400° C. (752° F.) to about 850° C. (1562° F.), wherein in this context only, the term “about” means+/−10° C. Further, step  250  may, for example, comprise heating the composite structure for a period between about 0.5 hour and about 8 hours, where the term “about” in this context only means+/−0.25 hours. 
     In various embodiments, step  250  may comprise heating the composite structure to a first, lower temperature (for example, about 30° C. (86° F.) to about 300° C. (572° F.)) followed by heating at a second, higher temperature (for example, about 300° C. (572° F.) to about 1000° C. (1832° F.)). Further, step  250  may be performed in an inert environment, such as under a blanket of inert or less reactive gas (e.g., nitrogen, argon, other noble gases, and the like). 
     In various embodiments and with reference now to  FIG. 2C , method  400 , which comprises steps also found in method  300 , may further comprise applying at least one of a pretreating composition or a barrier coating  215  prior to applying the first slurry. Pretreatment step  215  may, for example, comprise applying a first pretreating composition to an outer surface of a composite structure, such as a component of aircraft wheel braking assembly  10 . In various embodiments, the first pretreating composition comprises an aluminum oxide in water. For example, the aluminum oxide may comprise an additive, such as a nanoparticle dispersion of aluminum oxide (for example, NanoBYK-3600®, sold by BYK Additives &amp; Instruments). The first pretreating composition may further comprise a surfactant or a wetting agent. The composite structure may be porous, allowing the pretreating composition to penetrate at least a portion of the pores of the composite structure. 
     In various embodiments, after applying the first pretreating composition, the component is heated to remove water and fix the aluminum oxide in place. For example, the component may be heated between about 100° C. (212° F.) and 200° C., and further, between 100° C. (212° F.) and 150° C. (392° F.). 
     Pretreatment step  215  may further comprise applying a second pretreating composition. In various embodiments, the second pretreating composition comprises a phosphoric acid and an aluminum phosphate, aluminum hydroxide, or aluminum oxide. The second pretreating composition may further comprise, for example, a second metal salt such as a magnesium salt. In various embodiments, the aluminum to phosphorus ratio of the aluminum phosphate is 1 to 5 or less by weight. Further, the second pretreating composition may also comprise a surfactant or a wetting agent. In various embodiments, the second pretreating composition is applied to the composite structure atop the first pretreating composition. The composite structure may then, for example, be heated. In various embodiments, the composite structure may be heated between about 600° C. (1112° F.) and about 800° C. (1472° F.), and further, between about 650° C. (1202° F.) and 750° C. (1382° F.). 
     Pretreatment step  215  may further comprise applying a barrier coating to an outer surface of a composite structure, such as a component of aircraft wheel braking assembly  10 . In various embodiments the barrier coating composition may comprise carbides or nitrides, including at least one of a molybdenum disulfide, tungsten disulfide, boron nitride, silicon carbide, titanium carbide, boron carbide, silicon oxycarbide, and silicon nitride. In various embodiments, the barrier coating may be formed by treating the composite structure with molten silicon. The molten silicon is reactive and may form a silicon carbide barrier on the composite structure. Step  215  may comprise, for example, application of the barrier coating by spraying, chemical vapor deposition (CVD), molten application, or brushing the barrier coating composition on to the outer surface of the carbon-carbon composite structure. Any suitable manner of applying the base layer to composite structure is within the scope of the present disclosure. 
     TABLES 1 and 2 illustrates a variety of pre-slurry compositions, including phosphate glass compositions, in accordance with various embodiments. 
     
       
         
           
               
               
             
               
                   
                 TABLE 1 
               
             
            
               
                   
                   
               
               
                   
                 Pre-slurry Composition 
               
            
           
           
               
               
               
               
               
               
               
            
               
                   
                 A 
                 B 
                 C 
                 D 
                 E 
                 F 
               
               
                   
                   
               
            
           
           
               
               
               
               
               
               
               
            
               
                 Wt % Glass 
                 75.01 
                 75.01 
                 76.71 
                 69.74 
                 80.20 
                 73.22 
               
               
                 Wt % Boron Nitride 
                 0 
                 0 
                 21.07 
                 28.09 
                 17.53 
                 24.54 
               
               
                 Wt % o-AlPO4 
                 0 
                 2.27 
                 0 
                 0 
                 0 
                 0 
               
               
                   
               
            
           
         
       
     
     
       
         
           
               
               
             
               
                   
                 TABLE 2 
               
             
            
               
                   
                   
               
               
                   
                 Pre-slurry Composition 
               
            
           
           
               
               
               
               
               
               
               
               
               
            
               
                   
                 H 
                 J 
                 K 
                 L 
                 M 
                 N 
                 P 
                 Q 
               
               
                   
                   
               
            
           
           
               
               
               
               
               
               
               
               
               
            
               
                 % Glass 
                 35.21 
                 35.21 
                 35.21 
                 35.21 
                 35.21 
                 35.21 
                 35.21 
                 35.21 
               
               
                 % Boron Nitride 
                 0.49 
                 4.33 
                 7.17 
                 0 
                 0 
                 4.33 
                 0 
                 % X BN   
               
               
                 % Molybdenum Disulfide 
                 8.16 
                 4.33 
                 1.48 
                 8.65 
                 0 
                 0 
                 4.33 
                 % Y MoS   
               
               
                 % Tungsten Disulfide 
                 0 
                 0 
                 0 
                 0 
                 8.65 
                 4.33 
                 4.33 
                 % Z WS   
               
               
                   
               
            
           
         
       
     
     Pre-slurry compositions A and B comprise phosphate glass compositions free of molybdenum disulfide, tungsten disulfide, and boron nitride. For example, compositions A and B may be suitable sealing layers, such as the sealing layer applied in step  240  of methods  300  and  400 . Pre-slurry compositions C, D, E, F, H, J, K, L, M, N, P and Q comprise phosphate glass and boron nitride and/or molybdenum disulfide additives. For example, pre-slurry compositions C, D, E, F, H, J, K, L, M, N, P and Q may illustrate suitable base layers, such as base layers applied in step  220  of methods  200 ,  300 , and  400 . As illustrated in TABLE 1, the boron nitride content of pre-slurry compositions C, D, E, and F varies between about 17.53 and 28.09 weight percent boron nitride. Molybdenum disulfide or tungsten disulfide may be substituted for boron nitride in pre-slurry compositions C, D, E, and F. As illustrated in TABLE 2, the boron nitride content of pre-slurry compositions H, J, K, L, and N varies between about 0 and 7.17 percent boron nitride by mass. As illustrated in TABLE 2, the molybdenum disulfide content of pre-slurry compositions H, J, K, L and P varies between about 1.48 and 8.65 percent molybdenum disulfide by mass. As illustrated in TABLE 2, the tungsten disulfide content of pre-slurry compositions M, N and P varies between about 4.33 and 8.65 percent tungsten disulfide by mass. However, any suitable phosphate glass pre-slurry containing molybdenum disulfide, tungsten disulfide and/or boron nitride (as described above) is in accordance with the present disclosure. Pre-slurry composition Q represents a pre-slurry composition which may include one or more additives, such as of molybdenum disulfide, tungsten disulfide and/or boron nitride. In various embodiments, a mass percent of additives in the first pre-slurry composition may represented by the formula: 
       % Y MoS +% Z WS +% X BN   [2]
 
     In Formula [2], a mass percent of molybdenum disulfide, shown by % Y MoS , may range from 0 to 8.65. A mass percent of tungsten disulfide, shown by % Z WS , may range from 0 to 8.65. A mass percent of boron nitride, shown by % X BN , may range from 0 to 8.65. 
     With reference to  FIG. 3  and TABLE 3 (below), experimental data obtained from testing various glass compositions in accordance with various embodiments is illustrated. 
     
       
         
           
               
               
             
               
                   
                 TABLE 3 
               
             
            
               
                   
                   
               
               
                   
                 Base Layer 
               
            
           
           
               
               
               
               
               
               
            
               
                   
                 (none) 
                 E 
                 D 
                 C 
                 F 
               
            
           
           
               
               
            
               
                   
                 Sealing Layer 
               
            
           
           
               
               
               
               
               
               
               
            
               
                 Oxidation 
                 Exposure 
                 A 
                 A 
                 A 
                 A 
                 A 
               
            
           
           
               
               
               
            
               
                 Temp 
                 Time (Hours) 
                 Percentage Weight Loss 
               
               
                   
               
            
           
           
               
               
               
               
               
               
               
            
               
                 675 
                 0 
                 0.00 
                 0.00 
                 0.00 
                 0.00 
                 0.00 
               
               
                 Degrees C. 
                 4 
                 0.90 
                 0.32 
                 0.41 
                 0.44 
                 0.18 
               
               
                   
                 8 
                 1.98 
                 0.70 
                 1.01 
                 1.07 
                 0.39 
               
               
                   
                 12 
                 3.13 
                 1.19 
                 1.76 
                 1.95 
                 0.64 
               
               
                   
                 16 
                 4.41 
                 1.80 
                 2.56 
                 2.98 
                 0.95 
               
               
                   
                 20 
                 5.94 
                 2.52 
                 3.56 
                 4.65 
                 1.31 
               
               
                   
                 24 
                 7.48 
                 3.41 
                 4.73 
                 6.29 
                 1.76 
               
               
                 760 
                 26 
                 10.63 
                 4.31 
                 6.43 
                 8.47 
                 2.11 
               
               
                 Degrees C. 
                 28 
                 14.28 
                 5.40 
                 8.37 
                 11.13 
                 2.54 
               
               
                 870 
                 30 
                 24.43 
                 7.18 
                 11.96 
                 15.95 
                 3.50 
               
               
                 Degrees C. 
                 32 
                 36.45 
                 12.76 
                 17.27 
                 23.43 
                 6.89 
               
               
                   
               
            
           
         
       
     
     The base layers and sealing layers shown in TABLE 3 are the same as shown in TABLE 1, with like labeling A, B, C, D, E and F. A base layer of formed of phosphate glass in compositions C, D, E, F, H, J, K, L, M, N, P and/or Q comprising molybdenum disulfide, tungsten disulfide and/or boron nitride are applied as slurry (i.e. a first slurry of a first phosphate glass composition) to a composite structure. Compositions A, B, C, D, E, F, H, J, K, L, M, N, P and/or Q may be oxidation protection compositions. A sealing layer formed of composition A and/or B is applied over the base layer (i.e. a second slurry of a second phosphate glass composition). As illustrated in TABLE 3, a sealing layer formed of composition A is applied over a base layer of phosphate glass formed of compositions C, D, E and F. As shown, the composite structure having the base layer exhibited a lower weight loss to oxidation at temperatures at and above 675° C. (1250° F.) than composite structures having layer A by itself.  FIG. 3  illustrates the data from TABLE 3, with percent weight loss on the y axis and exposure time in hours on the x axis. 
     With reference to  FIG. 4 , a number of combinations are illustrated, including various combinations of pre-treatment (such as, for example, as may be performed by pretreatment step  215 ), base layers, and sealing layers. The base layer and sealing layers are shown in  FIG. 4  with the same labeling as shown in TABLE 1, A through F. For example,  FIG. 4  illustrates that the performance of a composition comprising a base layer of glass composition F and a sealing layer B provides improved oxidation protection over a pretreated composite structure having only sealing layer B. Other combinations include a base layer of glass composition F and a sealing layer A (without pre-treatment), a pretreatment with sealing layer A only, a base layer of F with a sealing layer of A (with pre-treatment). 
     TABLES 4 and 5 illustrate a variety of slurries comprising pre-slurry compositions, including phosphate glass compositions, prepared in accordance with various embodiments. 
     
       
         
           
               
               
               
               
               
               
               
               
               
             
               
                 TABLE 4 
               
               
                   
               
               
                 Example &gt;&gt; 
                 A 
                 B1 
                 B2 
                 C 
                 D 
                 E 
                 F 
                 G 
               
               
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
               
               
               
               
               
            
               
                 h-Boron nitride (h-BN) powder A 
                 0 
                 0 
                 0 
                 8.75 
                 8.75 
                 8.25 
                 8.25 
                 8.25 
               
               
                 h-Boron nitride (h-BN) powder B 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0.50 
                 0.50 
                 0.50 
               
               
                 h-molybdenum disulfide (h-MoS 2 ) 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
               
               
                 Graphene nanoplatelets 
                 0 
                 0 
                 0 
                 0.15 
                 0.15 
                 0.15 
                 0.15 
                 0.15 
               
               
                 H 2 O 
                 52.40 
                 52.40 
                 52.40 
                 50.00 
                 50.00 
                 45.00 
                 45.00 
                 60.00 
               
               
                 Surfynol 465 surfactant 
                 0 
                 0 
                 0 
                 0.20 
                 0.20 
                 0.20 
                 0.20 
                 0.20 
               
               
                 Ammonium dihydrogen phosphate (ADHP) 
                 11.33 
                 11.33 
                 1.00 
                 0 
                 0 
                 0 
                 0 
                 0.50 
               
               
                 NH 4 OH 
                 0 
                 0 
                 0 
                 0.50 
                 0 
                 0.50 
                 0.50 
                 0 
               
               
                 Glass frit 
                 34.00 
                 34.00 
                 34.00 
                 26.50 
                 26.50 
                 26.50 
                 26.50 
                 26.50 
               
               
                 Acid aluminum phosphate (1:3 Al-P) 
                 0 
                 0 
                 0 
                 0 
                 0 
                 10.00 
                 0 
                 0 
               
               
                 Acid aluminum phosphate (1:2.5 Al-P) 
                 0 
                 0 
                 10.00 
                 0 
                 0 
                 0 
                 0 
                 5.00 
               
               
                 Acid aluminum phosphate (1:2 Al-P) 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 10.00 
                 0 
               
               
                 Ammonium dihydrogen phosphate (ADHP) 
                 0 
                 0 
                 0 
                 0 
                 0.50 
                 0 
                 0 
                 0 
               
               
                 Aluminum orthophosphate (o-AlPO 4 ) 
                 0 
                 2.270 
                 2.270 
                 0 
                 0 
                 0 
                 0 
                 0 
               
               
                   
               
            
           
         
       
     
     
       
         
           
               
               
               
               
               
               
               
               
               
             
               
                 TABLE 5 
               
               
                   
               
               
                 Example &gt;&gt; 
                 H 
                 J 
                 K 
                 L 
                 M 
                 N 
                 P 
                 Q 
               
               
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
               
               
               
               
               
            
               
                 h-Boron nitride (h-BN) powder 
                 0.50 
                 4.375 
                 7.25 
                 0 
                 0 
                 4.375 
                 0 
                 X BN   
               
               
                 h-Molybdenum disulfide (h-MoS 2 ) 
                 8.25 
                 4.375 
                 1.50 
                 8.75 
                 0 
                 0 
                 4.375 
                 Y MoS   
               
               
                 Tungsten disulfide (WS 2 ) 
                 0 
                 0 
                 0 
                 0 
                 8.75 
                 4.375 
                 4.375 
                 Z WS   
               
               
                 Graphene nanoplatelets 
                 0.15 
                 0.15 
                 0.15 
                 0.15 
                 0.15 
                 0.15 
                 0.15 
                 0.15 
               
               
                 H 2 O 
                 60.00 
                 60.00 
                 60.00 
                 60.00 
                 60.00 
                 60.00 
                 60.00 
                 60.00 
               
               
                 Surfynol 465 surfactant 
                 0.20 
                 0.20 
                 0.20 
                 0.20 
                 0.20 
                 0.20 
                 0.20 
                 0.20 
               
               
                 Ammonium dihydrogen phosphate (ADHP) 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
               
               
                 NH 4 OH 
                 0.50 
                 0.50 
                 0.50 
                 0.50 
                 0.50 
                 0.50 
                 0.50 
                 0.50 
               
               
                 Glass frit 
                 26.50 
                 26.50 
                 26.50 
                 26.50 
                 26.50 
                 26.50 
                 26.50 
                 26.50 
               
               
                 Acid aluminum phosphate (1:3 Al-P) 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
               
               
                 Acid aluminum phosphate (1:2.5 Al-P) 
                 5.00 
                 5.00 
                 5.00 
                 5.00 
                 5.00 
                 5.00 
                 5.00 
                 5.00 
               
               
                 Acid aluminum phosphate (1:2 Al-P) 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
               
               
                 Ammonium dihydrogen phosphate (ADHP) 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
               
               
                 Aluminum orthophosphate (o-AlPO 4 ) 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
               
               
                   
               
            
           
         
       
     
     TABLE 6 illustrates a variety of aluminum phosphate solutions in accordance with various embodiments. 
     
       
         
           
               
             
               
                 TABLE 6 
               
               
                   
               
               
                 Acid aluminum phosphate solutions 
               
               
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
               
               
            
               
                   
                 AlPO 1:4 
                 AlPO 1:3.5 
                 AlPO 1:3 
                 AlPO 1:2.5 
                 AlPO 1:2 
               
            
           
           
               
               
               
            
               
                 Component 
                 MW 
                 Amount (grams) 
               
               
                   
               
            
           
           
               
               
               
               
               
               
               
            
               
                 H 2 O 
                 18.01 
                 60.10 
                 60.65 
                 61.42 
                 62.50 
                 64.08 
               
               
                 H 3 PO 4  (85%) 
                 98.00 
                 100.00 
                 100.00 
                 100.00 
                 100.00 
                 100.00 
               
               
                 Al(OH) 3   
                 78.00 
                 19.90 
                 22.74 
                 26.53 
                 31.85 
                 39.80 
               
               
                   
               
            
           
           
               
               
            
               
                   
                 Al:P 
               
               
                   
                   
               
            
           
           
               
               
               
               
               
               
            
               
                   
                 0.250 
                 0.286 
                 0.333 
                 0.400 
                 0.500 
               
               
                   
                   
               
            
           
         
       
     
     As illustrated in TABLES 4, 5, and 6, oxidation protection system slurries comprising a phosphate glass composition glass frit in a carrier fluid (i.e., water) and various additives including h-molybdenum disulfide, h-boron nitride, graphene nanoplatelets, a surfactant, a flow modifier such as, for example, polyvinyl alcohol, polyacrylate or similar polymer, ammonium dihydrogen phosphate, ammonium hydroxide, and acid aluminum phosphates with Al:H 3 PO 4  ratios of between 1 to 2 and 1 to 5 by weight were prepared. Such as, for example, slurry example G contained h-boron nitride, graphene nanoplatelets, and an acid aluminum phosphate solution with an aluminum to phosphorus ratio of 1:2.5 (see TABLE 4). As a further example, slurry example H contained h-molybdenum disulfide, h-boron nitride, graphene nanoplatelets, and an acid aluminum phosphate solution with an aluminum to phosphorus ratio of 1:2.5. As a further example, slurry example L contained h-molybdenum disulfide, graphene nanoplatelets, and an acid aluminum phosphate solution with an aluminum to phosphorus ratio of 1:2.5. As a further example, slurry example Q represents a composition which may include one or more additives, such as of molybdenum disulfide, tungsten disulfide and/or boron nitride. In various embodiments, a quantity or mass (in grams) of the one or more additives in the first pre-slurry composition may represented by the formula: 
       Y MoS +Z WS +X BN   [3]
 
     In Formula [3], a mass of molybdenum disulfide, shown by Y MoS , may range from 0 to 8.75. A mass of tungsten disulfide, shown by Z WS , may range from 0 to 8.75. A mass of boron nitride, shown by X BN , may range from 0 to 8.75. 
     The slurries (examples C, D, E, F, G, H, J, K, L, M, N, and P) were applied to 50 gram carbon-carbon composite structure coupons and cured in inert atmosphere under heat at 899° C. (1650° F.). After cooling, glazes (examples A, B1 or B2) were applied atop the cured layer and the coupons were fired again in an inert atmosphere. A control coupon was pretreated with an alumina nanoparticle and given an acid aluminum phosphate base layer with a Al:H 3 PO 4  ratio of about 1 to 3.0, as described in various embodiments, and cured under an inert atmosphere. A control glaze was prepared as a slurry comprising a phosphate glass composition, water, ammonium dihydrogen phosphate, and aluminum orthophosphate. The control glaze (example B1) was applied atop the cured pretreated control and then fired again under an inert atmosphere forming, for example, a base layer. After cooling, the coupons were subjected to isothermal oxidation testing a 760° C. (1400° F.) over a period of 24 hours while monitoring mass loss. 
     With reference to TABLE 4 and  FIG. 5 , the performance of the coatings applied according to various embodiments is illustrated in comparison with a control. The control includes a pretreated composite structure having only base layer B. Percent weight loss is shown in the y axis and exposure time is shown in the x axis. Against the control, the addition of an acid aluminum phosphate with ratio of Al:H 3 PO 4  of between 1:2 and 1:3 reduces mass losses due to oxidation by between two times to over ten times (i.e., an order of magnitude). After 24 hours at 760° C. (1400° F.) the control had lost 24.1% of its mass in comparison the best performing test sample which had lost only 0.7% of its mass. The combined effect of adding acid aluminum phosphate into the slurry wherein the ratio of Al:H 3 PO 4  is between about 1:2 and 1:3 provides an unexpected increase in protection over standalone pretreatment of the carbon-carbon composite structure followed by application of a base layer or a base layer and sealing layer. Without being bound by theory, it is thought that the addition of acid aluminum phosphate wherein the ratio of Al:H 3 PO 4  is between about 1:2 and 1:3 produces a base layer which is both cohesive and adhesive. 
     With reference to TABLE 5, the performance of the coatings applied according to various embodiments H, J, and K was tested as described above. After 24 hours at 760° C. (1400° F.) the test sample including base layer H had lost 2.84% of its mass, the test sample including base layer J had lost greater than 50% of its mass, and the test sample including base layer K had lost greater than 50% of its mass. 
     Benefits and other advantages have been described herein with regard to specific embodiments. Furthermore, the connecting lines shown in the various figures contained herein are intended to represent exemplary functional relationships and/or physical couplings between the various elements. It should be noted that many alternative or additional functional relationships or physical connections may be present in a practical system. However, the benefits, advantages, solutions to problems, and any elements that may cause any benefit, advantage, or solution to occur or become more pronounced are not to be construed as critical, required, or essential features or elements of the disclosure. The scope of the disclosure is accordingly to be limited by nothing other than the appended claims, in which reference to an element in the singular is not intended to mean “one and only one” unless explicitly so stated, but rather “one or more.” Moreover, where a phrase similar to “at least one of A, B, or C” is used in the claims, it is intended that the phrase be interpreted to mean that A alone may be present in an embodiment, B alone may be present in an embodiment, C alone may be present in an embodiment, or that any combination of the elements A, B and C may be present in a single embodiment; for example, A and B, A and C, B and C, or A and B and C. 
     Systems, methods and apparatus are provided herein. In the detailed description herein, references to “one embodiment,” “an embodiment,” “an example embodiment,” etc., indicate that the embodiment described may include a particular feature, structure, or characteristic, but every embodiment may not necessarily include the particular feature, structure, or characteristic. Moreover, such phrases are not necessarily referring to the same embodiment. Further, when a particular feature, structure, or characteristic is described in connection with an embodiment, it is submitted that it is within the knowledge of one skilled in the art to affect such feature, structure, or characteristic in connection with other embodiments whether or not explicitly described. After reading the description, it will be apparent to one skilled in the relevant art(s) how to implement the disclosure in alternative embodiments. 
     Furthermore, no element, component, or method step in the present disclosure is intended to be dedicated to the public regardless of whether the element, component, or method step is explicitly recited in the claims. No claim element herein is to be construed under the provisions of 35 U.S.C. 112(f), unless the element is expressly recited using the phrase “means for.” As used herein, the terms “comprises,” “comprising,” or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.