Pigmented, Fine-Structured, Tribological Composite Material

Abstract

A composition for producing a tribological composite material includes at least one platelet-shaped solid-state lubricant, at least one type of inorganic, platelet-shaped pigment particles, at least one surface-active compound which possesses at least one hydrophilic group and at least one hydrophobic group, and a curable binder system comprising at least one organic polymer or oligomer having one or more functional groups, or a precursor thereof.

Claims

1. A composition for producing a tribological composite material, comprising: a) at least one platelet-shaped, solid-state lubricant; b) at least one type of inorganic, platelet-shaped pigment particles; c) at least one surface-active compound possessing at least one hydrophilic group and at least one hydrophobic group; and d) a curable binder system comprising at least one organic polymer or oligomer having one or more functional groups, or a precursor thereof, wherein the pigment particles comprise transition metal oxides and form bonds to the at least one hydrophilic group of the at least one surface-active compound, resulting in a quasi-transfer film in interlayers between the solid-state lubricant and the pigment particles.

2. The composition as claimed in claim 1, wherein the solid-state lubricant has a thickness of between 100 nm and 1000 nm and an aspect ratio of greater than 5.

3. The composition as claimed in claim 1, wherein the pigment particles have a thickness of from 0.5 m to 2 m and an average aspect ratio of greater than or equal to 10.

4. The composition as claimed in claim 1, wherein the composition further comprises inorganic particles.

5. The composition as claimed in claim 4, wherein the inorganic particles have a hardness of from 1000 MPa to 3500 MPa.

6. The composition as claimed in claim 4, wherein the inorganic particles comprise Si.sub.3N.sub.4, SiC, B.sub.4C, Al.sub.2O.sub.3 and/or SiO.sub.2.

7. The composition as claimed in claim 4, wherein the inorganic particles comprise Si.sub.3N.sub.4.

8. The composition as claimed in claim 1, wherein the solid-state lubricant is selected from the group consisting of natural graphite, synthetic graphite, graphene, hexagonal boron nitride, turbostratic boron nitride, molybdenum disulfide and/or tungsten disulfide.

9. The composition as claimed in claim 1, further comprising an organic, solid-state lubricant selected from the group consisting of perfluoropolymers, polytetrafluoroethylene and/or polyethylene.

10. The composition as claimed in claim 1, wherein the surface of the pigment particles comprises at least partly of a transition metal oxide.

11. The composition as claimed in claim 10, wherein the transition metal oxide is selected from the group consisting of TiO.sub.2, ZrO.sub.2, ZnO, and FeO.sub.x.

12. The composition as claimed in claim 1, wherein the surface-active compound is selected from the group consisting of ammonioalkyl compounds, phosphonioalkyl compounds, sulfonioalkyl compounds, imidazolinium compounds, pyridinium compounds, pyrrolidinium compounds, ionic liquids, functionalized, fluorine-containing polymers, polyethers, and functionalized polysiloxanes.

13. The composition as claimed in claim 1, wherein the binder system comprises an epoxy resin, phenolic resin, phenoxy resin, polyol, a blocked or nonblocked polyisocyanate, a polyimide, a polyamideimide, polyamide, polybenzimidazole, a polyester, polyurea, polyurethane, a polyepoxide, a polyamine and/or a polyacrylate, or precursors thereof.

14. The composition as claimed in claim 1, wherein the binder system comprises a dicarboxylic or tetracarboxylic acid, the anhydride thereof, or another derivative thereof, as carboxylic acid component, and comprises a diamine, triamine, or tetraamine as amine component, at least one component being aromatic.

15. A substrate with a tribological composite coating composed of a cured composition as claimed in claim 1.

16. The composition as claimed in claim 1, wherein: the surface of the pigment particles comprises at least partly of a transition metal oxide; and the surface-active compound is selected from the group consisting of ammonioalkyl compounds, phosphonioalkyl compounds, sulfonioalkyl compounds, imidazolinium compounds, pyridinium compounds, pyrrolidinium compounds, ionic liquids, functionalized, fluorine-containing polymers, polyethers, and functionalized polysiloxanes.

17. The composition as claimed in claim 1, wherein the solid-state lubricant comprises hexagonal boron nitride or turbostratic boron nitride.

18. The composition as claimed in claim 1, further comprising an organic, solid-state lubricant comprising a perfluoropolymer.

19. The composition as claimed in claim 1, wherein surface-active compounds adopt an orientation to a hydrophobic air side.

20. The composition as claimed in claim 1, wherein solid-state lubricants are arranged in a layer format between platelet-shaped pigment particles.

21. A method for producing a tribological composite material, comprising: applying a composition as claimed in claim 1 to a substrate; and thermally and/or photochemically curing the composition.

22. The method as claimed in claim 21, wherein said composition is obtained by: preparing a mixture of at least one platelet-shaped, solid-state lubricant and a surface-active compound in a solvent suitable for the binder system; adding the curable binder system and at least one type of inorganic, platelet-shaped pigment particles; and applying the resulting mixture to a substrate.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 comparison of different pigment particles in terms of their influence on the friction coefficient for a pigment concentration of 5 wt % (BN 110: 30 wt %, SiC: 5 wt %; A 65: comparative sample without pigment;

(2) FIG. 2 comparison of selected pigment particles in terms of their influence on the friction coefficient for a pigment concentration of 5 wt % (BN 110: 30 wt %, SiC: 5 wt %); AM: Autumn Mystery, LS: Lapis Sunlight); A 65: comparative sample without pigment;

(3) FIG. 3 variation of SiC UF-10 for 5% Lapis 5 and 10% FL;

(4) FIG. 4 variation of Lapis S in the SiC system;

(5) FIG. 5 systematic construction of SiC system; A193=inventive composition; A113, A119, A274, and A65=comparative examples;

(6) FIG. 6 variation of Si.sub.3N.sub.4 nano70 content;

(7) FIG. 7 variation of Si.sub.3N.sub.4 E05;

(8) FIG. 8 variation of Si.sub.3N.sub.4 E03;

(9) FIG. 9 variation of Si.sub.3N.sub.4 M11-A (broad distribution) content;

(10) FIG. 10 variation of Si.sub.3N.sub.4 B7 (3.0 m) content;

(11) FIG. 11 variation of FL D10H content in the system without hard material;

(12) FIG. 12 variation of FL D10H content in the Si.sub.3N.sub.4 B7 (3.0 m) system;

(13) FIG. 13 systematic construction of Si.sub.3N.sub.4 M11-A system without BN;

(14) FIG. 14 systematic construction of Si.sub.3N.sub.4 M11-A system with BN;

(15) FIG. 15 SEM micrograph of Hebofil BN 110;

(16) FIG. 16 SEM micrograph of SiC;

(17) FIG. 17 SEM micrograph of hard material particles Si.sub.3N.sub.4 E05;

(18) FIG. 18 SEM micrograph of hard material particles Si.sub.3N.sub.4 E03;

(19) FIG. 19 SEM micrograph of hard material particles Si.sub.3N.sub.4 M11-A;

(20) FIG. 20 SEM micrograph of Autumn Mystery pigment particles with FeO.sub.x surface;

(21) FIG. 21 SEM micrograph of Lapis Sunlight pigment particles with TiO.sub.2 surface;

(22) FIG. 22 SEM micrograph of A219, plan view;

(23) FIG. 23 SEM micrograph of A219, cross section;

(24) FIG. 24 neutral salt spray test after 312 h.

DETAILED DESCRIPTION OF INVENTION

(25) It is possible for numerous modifications and developments of the working examples described to be actualized.

Working Examples

(26) General Synthesis Procedure:

(27) In a Dispermat, 10-40% of the solvent used, glass dispersing beads, the solid lubricant and the surface-active compound having at least one hydrophilic and at least one hydrophobic group are dispersed at 50 C. and 2000 rpm. After 15 minutes the matrix components and, optionally, the hard material particles are added, and dispersion is continued for 90 minutes more at 50 C. and 2000 rpm. The glass beads are removed from the crude product by filtration. Subsequent dispersing of the pigment particles in the overall mixture is done using a dissolver disk over 30 minutes at 25 C. and 1000 rpm.

(28) Application:

(29) The reactive mixture obtained can be applied by application methods customary in the art, such as dip application or spray application, for example. Curing takes place at 150 C.-250 C. for 1 h-2 h.

(30) Inventive Compositions

Example 1: Base System without Hard Material (A200)

(31) 5.94 g of boron nitride BN 110 (Henze) are mixed with 35 ml of N-methyl-2-pyrrolidone (NMP) and 1.98 g of Fluorolink D10H (Solvay) in a Dispermat at 50 C. and 2000 rpm over 15 minutes. Then 3.37 g of pyromellitic dianhydride (PMDA) and 7.51 g of bis[4-(3-aminophenoxy)phenyl]sulfone (BAPPS) are added, followed by dispersion for 90 minutes more at 50 C. and 2000 rpm. Following removal of the glass beads, 0.99 g of Lapis Sunlight T20-04-WNT (Merck) is added, and the resulting overall mixture is mixed using a dissolver disk for 30 minutes at 25 C. and 1000 rpm. A homogeneous, liquid reactive mixture is obtained, which has a pale brownish coloring.

Example 2: Analogous to Example 1 with 1.25% SiC (A201)

(32) 6.08 g of boron nitride BN 110 (Henze) are mixed with 35 ml of NMP and 2.03 g of Fluorolink D10H (Solvay) in a Dispermat at 50 C. and 2000 rpm over 15 minutes. Then 3.37 g of PMDA, 7.51 g of BAPPS, and 0.25 g of SiC UF10 (HC Starck) are added, followed by dispersion for 90 minutes more at 50 C. and 2000 rpm. Following removal of the glass beads, 1.01 g of Lapis Sunlight T20-04-WNT (Merck) are added, and the resulting overall mixture is mixed using a dissolver disk for 30 minutes at 25 C. and 1000 rpm. A homogeneous, liquid reactive mixture is obtained, which has a pale brownish coloring.

Example 3: Analogous to Example 1 with 2.5% SiC (A202)

(33) 6.22 g of boron nitride BN 110 (Henze) are mixed with 35 ml of NMP and 2.07 g of Fluorolink D10H (Solvay) in a Dispermat at 50 C. and 2000 rpm over 15 minutes. Then 3.37 g of PMDA, 7.51 g of BAPPS, and 0.52 g of SiC UF10 (HC Starck) are added, followed by dispersion for 90 minutes more at 50 C. and 2000 rpm. Following removal of the glass beads, 1.04 g of Lapis Sunlight T20-04-WNT (Merck) are added, and the resulting overall mixture is mixed using a dissolver disk for 30 minutes at 25 C. and 1000 rpm. A homogeneous, liquid reactive mixture is obtained, which has a pale brownish coloring.

Example 4: Analogous to Example 1 with 5% SiC (A169/A193)

(34) 6.53 g of boron nitride BN 110 (Henze) are mixed with 35 ml of NMP and 2.18 g of Fluorolink D10H (Solvay) in a Dispermat at 50 C. and 2000 rpm over 15 minutes. Then 3.37 g of PMDA, 7.51 g of BAPPS, and 1.09 g of SiC UF10 (HC Starck) are added, followed by dispersion for 90 minutes more at 50 C. and 2000 rpm. Following removal of the glass beads, 1.09 g of Lapis Sunlight T20-04-WNT (Merck) are added, and the resulting overall mixture is mixed using a dissolver disk for 30 minutes at 25 C. and 1000 rpm. A homogeneous, liquid reactive mixture is obtained, which has a pale brownish coloring.

Example 5: Analogous to Example 1 with 10% SiC (A204)

(35) 7.26 g of boron nitride BN 110 (Henze) are mixed with 35 ml of NMP and 2.42 g of Fluorolink D10H (Solvay) in a Dispermat at 50 C. and 2000 rpm over 15 minutes. Then 3.37 g of PMDA, 7.51 g of BAPPS, and 2.42 g of SiC UF10 (HC Starck) are added, followed by dispersion for 90 minutes more at 50 C. and 2000 rpm. Following removal of the glass beads, 1.21 g of Lapis Sunlight T20-04-WNT (Merck) are added, and the resulting overall mixture is mixed using a dissolver disk for 30 minutes at 25 C. and 1000 rpm. A homogeneous, liquid reactive mixture is obtained, which has a pale brownish coloring.

Example 6: Analogous to Example 1 with 15% SiC (A205)

(36) 8.16 g of boron nitride BN 110 (Henze) are mixed with 35 ml of NMP and 2.72 g of Fluorolink D10H (Solvay) in a Dispermat at 50 C. and 2000 rpm over 15 minutes. Then 3.37 g of PMDA, 7.51 g of BAPPS, and 4.08 g of SiC UF10 (HC Starck) are added, followed by dispersion for 90 minutes more at 50 C. and 2000 rpm. Following removal of the glass beads, 1.36 g of Lapis Sunlight T20-04-WNT (Merck) are added, and the resulting overall mixture is mixed using a dissolver disk for 30 minutes at 25 C. and 1000 rpm. A homogeneous, liquid reactive mixture is obtained, which has a pale brownish coloring.

Example 7: Analogous to Example 1 with 20% SiC (A206)

(37) 9.33 g of boron nitride BN 110 (Henze) are mixed with 35 ml of NMP and 3.11 g of Fluorolink D10H (Solvay) in a Dispermat at 50 C. and 2000 rpm over 15 minutes. Then 3.37 g of PMDA, 7.51 g of BAPPS, and 6.22 g of SiC UF10 (HC Starck) are added, followed by dispersion for 90 minutes more at 50 C. and 2000 rpm. Following removal of the glass beads, 1.55 g of Lapis Sunlight T20-04-WNT (Merck) are added, and the resulting overall mixture is mixed using a dissolver disk for 30 minutes at 25 C. and 1000 rpm. A homogeneous, liquid reactive mixture is obtained, which has a pale brownish coloring.

Example 8: Analogous to Example 2 with 1.25% Si3N4 E05 (A233)

(38) 6.08 g boron nitride BN 110 (Henze), 35 ml NMP, 2.03 g Fluorolink D10H (Solvay), 3.37 g PMDA, 7.51 g BAPPS, 0.25 g Si.sub.3N.sub.4 E05 (UBE), 1.01 g Lapis Sunlight T20-04-WNT (Merck)

Example 9: Analogous to Example 3 with 2.5% Si3N4 E05 (A234)

(39) 6.22 g boron nitride BN 110 (Henze), 35 ml NMP, 2.07 g Fluorolink D10H (Solvay), 3.37 g PMDA, 7.51 g BAPPS, 0.52 g Si.sub.3N.sub.4 E05 (UBE), 1.04 g Lapis Sunlight T20-04-WNT (Merck)

Example 10: Analogous to Example 4 with 5% Si3N4 E05 (A235)

(40) 6.53 g boron nitride BN 110 (Henze), 35 ml NMP, 2.18 g Fluorolink D10H (Solvay), 3.37 g PMDA, 7.51 g BAPPS, 1.09 g Si.sub.3N.sub.4 E05 (UBE), 1.09 g Lapis Sunlight T20-04-WNT (Merck)

Example 11: Analogous to Example 5 with 10% Si3N4 E05 (A236)

(41) 7.26 g boron nitride BN 110 (Henze), 35 ml NMP, 2.42 g Fluorolink D10H (Solvay), 3.37 g PMDA, 7.51 g BAPPS, 2.42 g Si.sub.3N.sub.4 E05 (UBE), 1.21 g Lapis Sunlight T20-04-WNT (Merck)

Example 12: Analogous to Example 6 with 15% Si3N4 E05 (A237)

(42) 8.16 g boron nitride BN 110 (Henze), 35 ml NMP, 2.72 g Fluorolink D10H (Solvay), 3.37 g PMDA, 7.51 g BAPPS, 4.08 g Si.sub.3N.sub.4 E05 (UBE), 1.36 g Lapis Sunlight T20-04-WNT (Merck)

Example 13: Analogous to Example 2 with 1.25% Si3N4 E03 (A238)

(43) 6.08 g boron nitride BN 110 (Henze), 35 ml NMP, 2.03 g Fluorolink D10H (Solvay), 3.37 g PMDA, 7.51 g BAPPS, 0.25 g Si.sub.3N.sub.4 E03 (UBE), 1.01 g Lapis Sunlight T20-04-WNT (Merck)

Example 14: Analogous to Example 3 with 2.5% Si3N4 E03 (A239)

(44) 6.22 g boron nitride BN 110 (Henze), 35 ml NMP, 2.07 g Fluorolink D10H (Solvay), 3.37 g PMDA, 7.51 g BAPPS, 0.52 g Si.sub.3N.sub.4 E03 (UBE), 1.04 g Lapis Sunlight T20-04-WNT (Merck)

Example 15: Analogous to Example 4 with 5% Si3N4 E03 (A240)

(45) 6.53 g boron nitride BN 110 (Henze), 35 ml NMP, 2.18 g Fluorolink D10H (Solvay), 3.37 g PMDA, 7.51 g BAPPS, 1.09 g Si.sub.3N.sub.4 E03 (UBE), 1.09 g Lapis Sunlight T20-04-WNT (Merck)

Example 16: Analogous to Example 5 with 10% Si3N4 E03 (A241)

(46) 7.26 g boron nitride BN 110 (Henze), 35 ml NMP, 2.42 g Fluorolink D10H (Solvay), 3.37 g PMDA, 7.51 g BAPPS, 2.42 g Si.sub.3N.sub.4 E03 (UBE), 1.21 g Lapis Sunlight T20-04-WNT (Merck)

Example 17: Analogous to Example 6 with 15% Si3N4 E03 (A242)

(47) 8.16 g boron nitride BN 110 (Henze), 35 ml NMP, 2.72 g Fluorolink D10H (Solvay), 3.37 g PMDA, 7.51 g BAPPS, 4.08 g Si.sub.3N.sub.4 E03 (UBE), 1.36 g Lapis Sunlight T20-04-WNT (Merck)

Example 18: Analogous to Example 2 with 1.25% Si3N4 M11-A (A218)

(48) 6.08 g boron nitride BN 110 (Henze), 35 ml NMP, 2.03 g Fluorolink D10H (Solvay), 3.37 g PMDA, 7.51 g BAPPS, 0.25 g Si.sub.3N.sub.4 M11-A (HC Starck), 1.01 g Lapis Sunlight T20-04-WNT (Merck)

Example 19: Analogous to Example 3 with 2.5% Si3N4 M11-A (A219)

(49) 6.22 g boron nitride BN 110 (Henze), 35 ml NMP, 2.07 g Fluorolink D10H (Solvay), 3.37 g PMDA, 7.51 g BAPPS, 0.52 g Si.sub.3N.sub.4 M11-A (HC Starck), 1.04 g Lapis Sunlight T20-04-WNT (Merck)

Example 20: Analogous to Example 4 with 5% Si3N4 M11-A (A220)

(50) 6.53 g boron nitride BN 110 (Henze), 35 ml NMP, 2.18 g Fluorolink D10H (Solvay), 3.37 g PMDA, 7.51 g BAPPS, 1.09 g Si.sub.3N.sub.4 M11-A (HC Starck), 1.09 g Lapis Sunlight T20-04-WNT (Merck)

Example 21: Analogous to Example 5 with 10% Si3N4 M11-A (A221)

(51) 7.26 g boron nitride BN 110 (Henze), 35 ml NMP, 2.42 g Fluorolink D10H (Solvay), 3.37 g PMDA, 7.51 g BAPPS, 2.42 g Si.sub.3N.sub.4 M11-A (HC Starck), 1.21 g Lapis Sunlight T20-04-WNT (Merck)

Example 22: Analogous to Example 6 with 15% Si3N4 M11-A (A222)

(52) 8.16 g boron nitride BN 110 (Henze), 35 ml NMP, 2.72 g Fluorolink D10H (Solvay), 3.37 g PMDA, 7.51 g BAPPS, 4.08 g Si.sub.3N.sub.4 M11-A (HC Starck), 1.36 g Lapis Sunlight T20-04-WNT (Merck)

Example 23: Analogous to Example 2 with 1.25% Si3N4 B7 (A223)

(53) 6.08 g boron nitride BN 110 (Henze), 35 ml NMP, 2.03 g Fluorolink D10H (Solvay), 3.37 g PMDA, 7.51 g BAPPS, 0.25 g Si.sub.3N.sub.4 B7 (HC Starck), 1.01 g Lapis Sunlight T20-04-WNT (Merck)

Example 24: Analogous to Example 3 with 2.5% Si3N4 B7 (A224)

(54) 6.22 g boron nitride BN 110 (Henze), 35 ml NMP, 2.07 g Fluorolink D10H (Solvay), 3.37 g PMDA, 7.51 g BAPPS, 0.52 g Si.sub.3N.sub.4 B7 (HC Starck), 1.04 g Lapis Sunlight T20-04-WNT (Merck)

Example 25: Analogous to Example 4 with 5% Si3N4 B7 (A225)

(55) 6.53 g boron nitride BN 110 (Henze), 35 ml NMP, 2.18 g Fluorolink D10H (Solvay), 3.37 g PMDA, 7.51 g BAPPS, 1.09 g Si.sub.3N.sub.4 B7 (HC Starck), 1.09 g Lapis Sunlight T20-04-WNT (Merck)

Example 26: Analogous to Example 5 with 10% Si3N4 B7 (A226)

(56) 7.26 g boron nitride BN 110 (Henze), 35 ml NMP, 2.42 g Fluorolink D10H (Solvay), 3.37 g PMDA, 7.51 g BAPPS, 2.42 g Si.sub.3N.sub.4 B7 (HC Starck), 1.21 g Lapis Sunlight T20-04-WNT (Merck)

Example 27: Analogous to Example 6 with 15% Si3N4 B7 (A227)

(57) 8.16 g boron nitride BN 110 (Henze), 35 ml NMP, 2.72 g Fluorolink D10H (Solvay), 3.37 g PMDA, 7.51 g BAPPS, 4.08 g Si.sub.3N.sub.4 B7 (HC Starck), 1.36 g Lapis Sunlight T20-04-WNT (Merck)

Example 28: Analogous to Example 2 with 1.25% Si3N4 Nano70 (A228)

(58) 6.08 g boron nitride BN 110 (Henze), 35 ml NMP, 2.03 g Fluorolink D10H (Solvay), 3.37 g PMDA, 7.51 g BAPPS, 0.25 g Si.sub.3N.sub.4 nano70 (Aldrich), 1.01 g Lapis Sunlight T20-04-WNT (Merck)

Example 29: Analogous to Example 3 with 2.5% Si3N4 Nano70 (A229)

(59) 6.22 g boron nitride BN 110 (Henze), 35 ml NMP, 2.07 g Fluorolink D10H (Solvay), 3.37 g PMDA, 7.51 g BAPPS, 0.52 g Si.sub.3N.sub.4 nano70 (Aldrich), 1.04 g Lapis Sunlight T20-04-WNT (Merck)

Example 30: Analogous to Example 4 with 5% Si3N4 Nano70 (A230)

(60) 6.53 g boron nitride BN 110 (Henze), 35 ml NMP, 2.18 g Fluorolink D10H (Solvay), 3.37 g PMDA, 7.51 g BAPPS, 1.09 g Si.sub.3N.sub.4 nano70 (Aldrich), 1.09 g Lapis Sunlight T20-04-WNT (Merck)

Example 31: Analogous to Example 5 with 10% Si3N4 Nano70 (A231)

(61) 7.26 g boron nitride BN 110 (Henze), 35 ml NMP, 2.42 g Fluorolink D10H (Solvay), 3.37 g PMDA, 7.51 g BAPPS, 2.42 g Si.sub.3N.sub.4 nano70 (Aldrich), 1.21 g Lapis Sunlight T20-04-WNT (Merck)

Example 32: Analogous to Example 6 with 15% Si3N4 Nano70 (A232)

(62) 8.16 g boron nitride BN 110 (Henze), 35 ml NMP, 2.72 g Fluorolink D10H (Solvay), 3.37 g PMDA, 7.51 g BAPPS, 4.08 g Si.sub.3N.sub.4 nano70 (Aldrich), 1.36 g Lapis Sunlight T20-04-WNT (Merck)

Example 33: Analogous to Example 23 with 1.25% FL D10H (A243)

(63) 5.22 g boron nitride BN 110 (Henze), 35 ml NMP, 0.22 g Fluorolink D10H (Solvay), 3.37 g PMDA, 7.51 g BAPPS, 0.22 g Si.sub.3N.sub.4 B7 (HC Starck), 0.87 g Lapis Sunlight T20-04-WNT (Merck)

Example 34: Analogous to Example 23 with 2.5% FL D10H (A244)

(64) 5.33 g boron nitride BN 110 (Henze), 35 ml NMP, 0.44 g Fluorolink D10H (Solvay), 3.37 g PMDA, 7.51 g BAPPS, 0.22 g Si.sub.3N.sub.4 B7 (HC Starck), 0.89 g Lapis Sunlight T20-04-WNT (Merck)

Example 35: Analogous to Example 23 with 5% FL D10H (A245)

(65) 5.56 g boron nitride BN 110 (Henze), 35 ml NMP, 0.93 g Fluorolink D10H (Solvay), 3.37 g PMDA, 7.51 g BAPPS, 0.23 g Si.sub.3N.sub.4 B7 (HC Starck), 0.93 g Lapis Sunlight T20-04-WNT (Merck)

Example 36: Analogous to Example 23 with 7.5% FL D10H (A246)

(66) 5.81 g boron nitride BN 110 (Henze), 35 ml NMP, 1.45 g Fluorolink D10H (Solvay), 3.37 g PMDA, 7.51 g BAPPS, 0.24 g Si.sub.3N.sub.4 B7 (HC Starck), 0.97 g Lapis Sunlight T20-04-WNT (Merck)

Example 37: Analogous to Example 23 with 15% FL D10H (A247)

(67) 6.70 g boron nitride BN 110 (Henze), 35 ml NMP, 3.35 g Fluorolink D10H (Solvay), 3.37 g PMDA, 7.51 g BAPPS, 0.28 g Si.sub.3N.sub.4 B7 (HC Starck), 1.12 g Lapis Sunlight T20-04-WNT (Merck)

Example 38: Analogous to Example 25 with 10% PDMS Diol-700 Instead of 10% FL D10H (A225-PMDS Diol-700)

(68) 6.53 g of boron nitride BN 110 (Henze) are mixed with 35 ml of NMP and 2.18 g of PDMS diol-700 (Aldrich CAS: 70131-67-8, poly(dimethylsiloxane), hydroxy terminated, M.sub.n550, chain length, 7-8 Si units C.sub.14H.sub.44O.sub.8Si.sub.7 mol. wt.: 537.09 C.sub.16H.sub.50O.sub.9Si.sub.8 mol. wt.: 611.25) in a Dispermat at 50 C. and 2000 rpm over 15 minutes. Then 3.37 g of PMDA, 7.51 g of BAPPS and 1.09 g of Si.sub.3N.sub.4 B7 (HC Starck) are added, followed by dispersion for 90 minutes more at 50 C. and 2000 rpm. Following removal of the glass beads, 1.09 g of Lapis Sunlight T20-04-WNT (Merck) are added, and the overall mixture obtained is mixed using a dissolver disk for 30 minutes at 25 C. and 1000 rpm. A homogeneous, liquid reactive mixture is obtained, with a pale brownish coloration.

Example 39: Analogous to Example 19 with 10% PEG-Block-PPG-Block-PEG Instead of 10% FL D10H (A219-PEG-b-PPG-b-PEG)

(69) 6.22 g of boron nitride BN 110 (Henze) are mixed with 35 ml of NMP and 2.07 g of polyethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) (Aldrich 435406 CAS [9003-11-6] M.sub.n1100, HO(C.sub.2H.sub.4O).sub.m(C.sub.3H.sub.6O).sub.n(C.sub.2H.sub.4O.sub.mH) in a Dispermat at 50 C. and 2000 rpm over 15 minutes. Then 3.37 g of PMDA, 7.51 g of BAPPS and 0.52 g of Si.sub.3N.sub.4 M11-A (HC Starck) are added, followed by dispersion for 90 minutes more at 50 C. and 2000 rpm. Following removal of the glass beads, 1.04 g of Lapis Sunlight T20-04-WNT (Merck) are added, and the overall mixture obtained is mixed using a dissolver disk for 30 minutes at 25 C. and 1000 rpm. A homogeneous, liquid reactive mixture is obtained, with a pale brownish coloration.

(70) Comparative Compositions without Lubricant

Comparative Example 1: No Lubricant, No Pigment, No Hard Material, No Surface-Active Compound (A265)

(71) 3.37 g of PMDA and 7.51 g of BAPPS are mixed with 35 ml of NMP in a Dispermat at 50 C. and 2000 rpm over 115 minutes. Following removal of the glass beads, a homogeneous, liquid reactive mixture is obtained, with a brownish coloration.

Comparative Example 2: No Lubricant, No Pigment, No Hard Material, with Surface-Active Compound (A119)

(72) 3.37 g of PMDA, 7.51 g of BAPPS, and 2.07 g of Fluorolink D10H (Solvay) are mixed with 35 ml of NMP in a Dispermat at 50 C. and 2000 rpm over 115 minutes. Following removal of the glass beads, a homogeneous, liquid reactive mixture is obtained, with a brownish coloration.

Comparative Example 3: No Lubricant, with Pigment, No Hard Material, with Surface-Active Compound (A219-14)

(73) 3.37 g of PMDA, 7.51 g of BAPPS, and 2.07 g of Fluorolink D10H (Solvay) are mixed with 35 ml of NMP in a Dispermat at 50 C. and 2000 rpm over 115 minutes. Following removal of the glass beads, 1.04 g of Lapis Sunlight T20-04-WNT (Merck) are added and the overall mixture obtained is mixed using a dissolver disk over 30 minutes at 25 C. and 1000 rpm. This gives a homogeneous, liquid reactive mixture with a pale brownish coloration.

Comparative Example 4: No Lubricant, with Pigment, with Hard Material, with Surface-Active Compound (A219-12)

(74) 3.37 g of PMDA and 7.51 g of BAPPS are mixed with 35 ml of NMP and 2.07 g of Fluorolink D10H (Solvay) in a Dispermat at 50 C. and 2000 rpm over 15 minutes. Subsequently 0.52 g of Si.sub.3N.sub.4 M11-A (HC Starck) is added, and dispersion is continued for 90 minutes more at 50 C. and 2000 rpm. Following removal of the glass beads, 1.04 g of Lapis Sunlight T20-04-WNT (Merck) are added and the overall mixture obtained is mixed using a dissolver disk over 30 minutes at 25 C. and 1000 rpm. This gives a homogeneous, liquid reactive mixture with a pale brownish coloration.

(75) Comparative Compositions with Lubricant

Comparative Example 5: With Lubricant, No Pigment, No Hard Material, No Surface-Active Compound (A269)

(76) 6.22 g of boron nitride BN 110 (Henze) are mixed with 35 ml of NMP in a Dispermat at 50 C. and 2000 rpm over 15 minutes. Then 3.37 g of PMDA and 7.51 g of BAPPS are added and dispersion is continued for 90 minutes more at 50 C. and 2000 rpm. Following removal of the glass beads, a homogeneous, liquid reactive mixture is obtained which has a pale brownish coloration.

Comparative Example 6: With Lubricant, with Pigment, No Hard Material, No Surface-Active Compound (A219-16)

(77) 6.22 g of boron nitride BN 110 (Henze) are mixed with 35 ml of NMP in a Dispermat at 50 C. and 2000 rpm over 15 minutes. Then 3.37 g of PMDA and 7.51 g of BAPPS are added, followed by dispersion for 90 minutes more at 50 C. and 2000 rpm. Following removal of the glass beads, 1.04 g of Lapis Sunlight T20-04-WNT (Merck) are added, and the resulting overall mixture is mixed using a dissolver disk for 30 minutes at 25 C. and 1000 rpm. A homogeneous, liquid reactive mixture is obtained, which has a pale brownish coloring.

Comparative Example 7: With Lubricant, with Pigment, with Hard Material, No Surface-Active Compound (A219-15)

(78) 6.22 g of boron nitride BN 110 (Henze) are mixed with 35 ml of NMP in a Dispermat at 50 C. and 2000 rpm over 15 minutes. Then 3.37 g of PMDA, 7.51 g of BAPPS, and 0.52 g of Si.sub.3N.sub.4 M11-A (HC Starck) are added, followed by dispersion for 90 minutes more at 50 C. and 2000 rpm. Following removal of the glass beads, 1.04 g of Lapis Sunlight T20-04-WNT (Merck) are added, and the resulting overall mixture is mixed using a dissolver disk for 30 minutes at 25 C. and 1000 rpm. A homogeneous, liquid reactive mixture is obtained, which has a pale brownish coloring.

Comparative Example 8: With Lubricant, No Pigment, No Hard Material, with Surface-Active Compound (A274)

(79) 6.22 g of boron nitride BN 110 (Henze) are mixed with 35 ml of NMP and 2.07 g of Fluorolink D10H (Solvay) in a Dispermat at 50 C. and 2000 rpm over 15 minutes. Then 3.37 g of PMDA and 7.51 g of BAPPS are added and dispersion is continued for 90 minutes more at 50 C. and 2000 rpm. Following removal of the glass beads, a homogeneous, liquid reactive mixture is obtained which has a pale brownish coloration.

Comparative Example 9: With Lubricant, No Pigment, with Hard Material, with Surface-Active Compound (A65)

(80) 6.53 g of boron nitride BN 110 (Henze) are mixed with 35 ml of NMP and 2.18 g of Fluorolink D10H (Solvay) in a Dispermat at 50 C. and 2000 rpm over 15 minutes. Then 3.37 g of PMDA, 7.51 g of BAPPS, and 1.09 g of SiC UF10 (HC Starck) are added and dispersion is continued for 90 minutes more at 50 C. and 2000 rpm. Following removal of the glass beads, a homogeneous, liquid reactive mixture is obtained which has a dark brownish coloration.

(81) FIG. 22 and FIG. 23 show, as an example, the construction of the composite material A219.

(82) Tribology

(83) The compositions produced were applied to stainless steel plates and cured thermally as described. The film thickness was 20-25 m. The samples were subsequently subjected to measurement in a ball-on-disk tribometer.

(84) The measurements were conducted under the following collective loading:

(85) Ball-on-disk tribometer (DIN 50324), measurement under air, 100Cr6 ball with 4 mm diameter, circular radius: 16 mm, applied force: 2 N, track speed: 10 cm/s, loading distance: 1 km.

(86) FIG. 1 shows the influence of different pigment particles (5 wt %) on the coefficient of sliding friction in the system with 5 wt % SiC hard material particles and 30 wt % BN 110 particles. FIG. 16 and FIG. 15 show representative SEM micrographs of the SiC and BN 110 particles used, respectively.

(87) It is notable here that apparently a relatively large number of different types of pigment contribute to a reduction in the friction coefficient in the initial phase of the measurement, over 3000-4000 rounds, relative to the comparative composition without such pigment. Since the aspect ratio of the pigment particles to one another is relatively similar, the surface chemistry probably plays a critical part in terms of the extent of the reduction in friction. In order to show the effect even more clearly, FIG. 2 shows the composites with Lapis Sunlight and with Autumn Mystery as pigments, in comparison to the composite without pigment. SEM micrographs of the two pigments are shown in FIG. 20 and FIG. 21.

(88) Autumn Mystery reduces the friction coefficient over a path of 2000 rounds, while Lapis Sunlight shows the positive effect even over 9000 rounds.

(89) In summary, in view of particular significance, it can be stated that the addition of a platelet-shaped filler which is initially tribologically inactive, in the form of pigment particles, to a low-friction coating system consisting of a polymer matrix, a solid-state lubricant, and a hard material, leads to a further reduction in friction. This finding represents the focal point of the above invention. The effect found can be explained only by way of a new morphology, hitherto undescribed in the art, within the composite material formed. The compositions described below serve to define the relevant compositions.

(90) It can be expected that a hard material of very high hardness will be able to lead, above a defined concentration, to destruction of the comparatively soft pigment particles in the tribological experiment. For this purpose, the concentration of SiC was raised in steps in the system with SiC as hard material and with the Lapis Sunlight pigment particle with the best reduction in friction. The compositions are shown in table 1. The results of the tribometer measurements are shown in FIG. 3. FIG. 16 shows a representative SEM micrograph of the SiC. The morphology of the particles can be designated as shapeless-angular. The particle size distribution is broad, and ranges from particles with about 50 nm up to about 2 m.

(91) Accordingly, the addition of SiC as hard material, from about 10 wt %, results in an adverse effect on the coefficient of sliding friction.

(92) An additional point of interest was the influence of the concentration of Lapis Sunlight at constant SiC hard material concentration. Table 2 and FIG. 4 show the compositions of the composites and also the corresponding results of the tribometer measurements.

(93) The results of measurement show that a favorable effect is no longer obtained only at pigment concentrations of above about 10 wt %.

(94) A further matter of interest was the additional systematic construction of the system in terms of the individual components, in order to have corresponding comparative examples available. This systematic construction, in the sense of a stepwise combination of components, was carried out first of all for the system containing SiC as hard material. Table 3 shows the compositions of interest. The inventive composition is A193. It is the reproduction of A169 and is identical to the latter in its composition. All other compositions are comparative examples.

(95) The associated tribological measurements are shown in FIG. 5.

(96) The pure matrix with 35 wt % BN 110 (A113) shows a sliding coefficient which is comparatively high for a low-friction coating, with 0.22, but with a high level of constancy over the distance of 10 000 rounds. The addition of FL D10H to the pure matrix without BN 110 (A119) leads to very low initial friction coefficients of down to =0.05, which in phenomenological terms suggest a hydrodynamic lubrication. This indicates that FL D10H is possibly not being incorporated completely into the polyimide matrix. The slope of the further course of the plot indicates a relatively high rate of wear in this system. Shortly before the 10 000 rounds are reached, layer failure occurs, as evident from the sharp fluctuations in measurement values. When BN 110 and FL D10H are combined (A274), low initial friction coefficients are likewise obtained, but the layer wears even faster than with the additives individually. This indicates that the layer has become very soft overall as a result of the two additives in total. The addition of additional SiC hard material particles (A65) shows that the sliding coefficient can be harmonized over the entire measurement distance at values of between 0.15 and 0.18. This is the classic case of the effect of a hard material on the sliding behavior. By adjustment of the inventive composition with additional platelet-shaped pigment particles (A193), in addition to the harmonization, a further lowering of the sliding coefficient is achieved, particularly in the initial phase of the loading.

(97) All in all, however, the curve profile for A193 indicates that there is still marked wear occurring. The cause of this might be considered to be the particles of hard SiC material, which can have an abrasive effect on the overall system if they are removed from the layer surface by the opposing element. The wear problem can be minimized by reducing the hardness of the particles of hard material. In this respect, silicon nitride (universal hardness HU: about 1500 MPa) is a suitable substitute for silicon carbide (universal hardware HU: about 2500 MPa).

(98) The tables (table 4, table 5, table 6, table 7, table 8) and figures (FIG. 6, FIG. 7, FIG. 8, FIG. 9, FIG. 10) show in this context the dependency relationship between the sliding behavior and the concentration of hard material for various types of silicon nitride with different particle size distributions and morphologies in combination with concentrations of BN 110, Lapis S, and FL D10H that are fixed in each case. In the majority of cases, these systems display a uniform profile of sliding coefficient below 0.13 with only a small increase over the loading distance. In a number of cases, indeed, the sliding coefficient runs at below a =0.1 over the entire duration of measurement.

(99) Table 4 and FIG. 6 show the influence of the hard material Si.sub.3N.sub.4 nano70 with nanoscale particles. The particle size distribution is between 10 nm and 200 nm. In morphological terms, the particle form can be described as shapeless to spherical.

(100) The nanoscale Si.sub.3N.sub.4 particles appear to be suitable for rational use only at up to about 5 wt %. At higher concentrations, layer failure is observed.

(101) Table 5 and FIG. 7 show the effect of the hard material Si.sub.3N.sub.4 E05, with coarser nanoscale particles. Particle size distribution is between 300 nm and 800 nm. In morphological terms, the particle shape can be described as cubelike. A representative scanning electron micrograph is shown in FIG. 17.

(102) Coarse Si.sub.3N.sub.4 particles in the nanometer range produce systems with a decidedly unitary profile up to about 15 wt %, and a much smaller increase than with SiC hard material.

(103) Table 6 and FIG. 8 show the effect of the hard material Si.sub.3N.sub.4 E03, with submicroscale particles. Particle size distribution is between 400 nm and 900 nm. In morphological terms, the particle shape can be described as cubelike. A representative scanning electron micrograph is shown in FIG. 18.

(104) Si.sub.3N.sub.4 particles in the submicrometer range produce systems with a decidedly unitary profile up to about 10 wt %, and a much smaller increase than with SiC hard material.

(105) Table 7 and FIG. 9 show the effect of the hard material Si.sub.3N.sub.4 M11-A, with submicroscale to microscale particles. Particle size distribution is broad and is between 100 nm and 2 m. In morphological terms, the particle shape can be described as shapeless. A representative scanning electron micrograph is shown in FIG. 19.

(106) Systems with Si.sub.3N.sub.4 hard material with broad particle size distribution likewise produce a great harmonization of the sliding coefficient over the entire loading distance.

(107) Table 8 and FIG. 10 show the effect of the hard material Si.sub.3N.sub.4 B7 with microscale particles.

(108) Up to about 10 wt %, the system series with Si.sub.3N.sub.4 B7 behaves similar to the series with E05 and E03.

(109) In summary it can be stated that the silicon nitride hard materials, on account of their not excessively extreme hardness as compared with silicon carbide, are less abrasive for the formation of the transfer film, and as a result a low sliding coefficient is achieved consistently over a long loading distance. Moreover, as a result of the lower abrasive effect, the pigment particles are not destroyed and are able to exert their tribological action in the above-described, inventive sense.

(110) The system series with Si.sub.3N.sub.4 B7 shows a balanced behavior for constant FL D10H content of 10 wt %. In order to discover the optimum concentration of this component in relation to the tribological properties, the FL D10H content was varied on the basis of an Si.sub.3N.sub.4 B7 concentration of 1.25 wt % (table 10, FIG. 12).

(111) It is found that in this system series, from 10 wt % of FL D10H (A223) onward, the desired tribological activity ensues. In order to rule out a purely hydrodynamic lubricating effect on the part of the FL D10H, individual components were added systematically to the starting polymer matrix material for the parallel system series with Si.sub.3N.sub.4 M11-A as hard material in comparison to the A219 system (analogous composition to A223).

(112) Tables 10 and 11 and FIGS. 12 and 13 show the effect of particular individual components which are assembled systematically for the overall composite material.

(113) These comparative series show a picture analogous to that already observed for SiC as hard material. The combination of FL with Lapis S leads to a marked reduction in the initial friction coefficient, but without any particular wear resistance (A274). Additional additization with solid-state lubricant BN 110 leads to a marked reduction in wear with a low initial friction coefficient (A200). The best balance in terms of coefficient of sliding friction and wear is obtained by additional combination of Si.sub.3N.sub.4 as hard material (A219).

(114) Wetting Behavior and Abrasion

(115) Tables 13 to 16 show additional properties of the tribological composite materials, such as the wetting behavior, the abrasion resistance as a function of the hard material particles content, and the corrosion protection effect, particularly as a function of the platelet content.

(116) From the data shown it is apparent that the systems display not only hydrophobic but also oleophobic propertiesthat is, the surface-modifying components for the particles employed accumulate at the air side of the coatings. Some of the platelets are drawn to the layer surface as a result of the hydrophobic surface modification. This is demonstrated in FIG. 22.

(117) Corrosion

(118) FIG. 24 shows the results of a neutral salt spray test.

(119) The examples shown demonstrate the corrosion protection effect of the tribological layers produced. There is no observed blistering on the surface. At the edge of the scored cross, there is no undermining of the coating. The factors responsible for this may be said to be the fine-structured composition of the overall composite (barrier effect) and the excellent substrate adhesion.

(120) TABLE-US-00001 TABLE 1 Variation of SiC UF-10 for 5% Lapis S and 10% FL BN 110 Lapis S SiC FL D10H BAPPS PMDA System wt % wt % wt % wt % wt % wt % A200 30 5 0 10 37.97 17.03 A201 30 5 1.25 10 37.10 16.65 A202 30 5 2.5 10 36.25 16.25 A169 30 5 5 10 34.52 15.48 A204 30 5 10 10 31.07 13.93 A205 30 5 15 10 27.62 12.38 A206 30 5 20 10 24.15 10.85

(121) TABLE-US-00002 TABLE 2 Variation of Lapis S in the SiC system BN 110 Lapis S SiC FL D10H BAPPS PMDA System wt % wt % wt % wt % wt % wt % A65 30 0 5 10 37.97 17.03 A190 30 1.25 5 10 37.10 16.65 A191 30 2.5 5 10 36.25 16.25 A192 30 3.5 5 10 35.53 15.97 A193 30 5 5 10 34.52 15.48 A194 30 10 5 10 31.07 13.93 A195 30 15 5 10 27.62 12.38

(122) TABLE-US-00003 TABLE 3 Systematic construction of SiC systems; A193 = inventive composition; A113, A119, A274, and A65 = comparative examples BN 110 Lapis S SiC FL D10H BAPPS PMDA System wt % wt % wt % wt % wt % wt % A265 0 0 0 0 69.10 30.90 A269 30 0 0 0 48.30 27.70 A113 35 0 0 0 44.92 20.08 A119 0 0 0 12.4 60.49 27.11 A274 30 0 0 10 41.46 18.54 A65 30 0 5 10 37.97 17.03 A193 30 5 5 10 34.55 15.45

(123) TABLE-US-00004 TABLE 4 Variation of Si.sub.3N.sub.4 nano70 content BN 110 Lapis S n-Si.sub.3N.sub.4 FL D10H BAPPS PMDA System wt % wt % wt % wt % wt % wt % A200 30 5 0 10 37.97 17.03 A228 30 5 1.25 10 37.10 16.65 A229 30 5 2.5 10 36.25 16.25 A230 30 5 5 10 34.52 15.48 A231 30 5 10 10 31.07 13.93 A232 30 5 15 10 27.62 12.38

(124) TABLE-US-00005 TABLE 5 Variation of Si.sub.3N.sub.4 E05 Si.sub.3N.sub.4 BN 110 Lapis S E05 FL D10H BAPPS PMDA System wt % wt % wt % wt % wt % wt % A200 30 5 0 10 37.97 17.03 A233 30 5 1.25 10 37.10 16.65 A234 30 5 2.5 10 36.25 16.25 A235 30 5 5 10 34.52 15.48 A236 30 5 10 10 31.07 13.93 A237 30 5 15 10 27.62 12.38

(125) TABLE-US-00006 TABLE 6 Variation of Si.sub.3N.sub.4 E03 Si.sub.3N.sub.4 BN 110 Lapis S E03 FL D10H BAPPS PMDA System wt % wt % wt % wt % wt % wt % A200 30 5 0 10 37.97 17.03 A238 30 5 1.25 10 37.10 16.65 A239 30 5 2.5 10 36.25 16.25 A240 30 5 5 10 34.52 15.48 A241 30 5 10 10 31.07 13.93 A242 30 5 15 10 27.62 12.38

(126) TABLE-US-00007 TABLE 7 Variation of Si.sub.3N.sub.4 M11-A (broad distribution) content BN 110 Lapis S Si.sub.3N.sub.4-M FL D10H BAPPS PMDA System wt % wt % wt % wt % wt % wt % A200 30 5 0 10 37.97 17.03 A218 30 5 1.25 10 37.10 16.65 A219 30 5 2.5 10 36.25 16.25 A220 30 5 5 10 34.52 15.48 A221 30 5 10 10 31.07 13.93 A222 30 5 15 10 27.62 12.38

(127) TABLE-US-00008 TABLE 8 Variation of Si.sub.3N.sub.4 B7 (3.0 m) content BN 110 Lapis S Si.sub.3N.sub.4-B7 FL D10H BAPPS PMDA System wt % wt % wt % wt % wt % wt % A200 30 5 0 10 37.97 17.03 A223 30 5 1.25 10 37.10 16.65 A224 30 5 2.5 10 36.25 16.25 A225 30 5 5 10 34.52 15.48 A226 30 5 10 10 31.07 13.93 A227 30 5 15 10 27.62 12.38

(128) TABLE-US-00009 TABLE 9 Variation of FL D10H content in the system without hard material BN 110 Lapis S Si.sub.3N.sub.4 FL D10H BAPPS PMDA System wt % wt % wt % wt % wt % wt % A269 30 0 0 0 48.30 27.70 A270 30 0 0 1.25 47.44 21.31 A271 30 0 0 2.5 46.58 20.92 A272 30 0 0 5.0 44.85 20.15 A273 30 0 0 7.5 43.13 19.37 A274 30 0 0 10.0 41.40 18.60 A275 30 0 0 12.5 39.68 17.82 A276 30 0 0 15.0 37.95 17.05

(129) TABLE-US-00010 TABLE 10 Variation of FL D10H content in the Si.sub.3N.sub.4 B7 (3.0 m) system BN 110 Lapis S Si.sub.3N.sub.4-B7 FL D10H BAPPS PMDA System wt % wt % wt % wt % wt % wt % A219-16 30 5 0 0 44.92 20.08 A243 30 5 1.25 1.25 43.19 19.31 A244 30 5 1.25 2.5 42.32 18.93 A245 30 5 1.25 5.0 40.60 18.15 A246 30 5 1.25 7.5 38.87 17.38 A223 30 5 1.25 10 37.10 16.65 A247 30 5 1.25 15 33.69 15.06

(130) TABLE-US-00011 TABLE 11 Systematic construction of Si.sub.3N.sub.4 M11-A system without BN Si.sub.3N.sub.4 BN 110 Lapis S M11 FL D10H BAPPS PMDA System wt % wt % wt % wt % wt % wt % A265 0 0 0 0 69.10 30.90 A119 0 0 0 12.4 60.49 27.11 A219-14 0 5 0 10 58.74 26.26 A219-12 0 5 2.5 10 57.01 25.49

(131) TABLE-US-00012 TABLE 12 Systematic construction of Si.sub.3N.sub.4 M11-A system with BN Si.sub.3N.sub.4 BN 110 Lapis S M11 FL D10H BAPPS PMDA System wt % wt % wt % wt % wt % wt % A269 30 0 0 0 48.30 27.70 A219-16 30 5 0 0 44.92 20.08 A219-15 30 5 2.5 0 43.19 19.31 A274 30 0 0 10 41.46 18.54 A200 30 5 0 10 37.97 17.03 A219 30 5 2.5 10 36.25 16.25

(132) TABLE-US-00013 TABLE 13 5 wt % Lapis S, 30% BN 110, 10% FL D10H Weight loss after 1000 cycles CPE CPE Si.sub.3N.sub.4-M11 CPE Taber (H.sub.2O) (HD) (1.3 m)/ (H.sub.2O) CPE (HD) (CS-17)/ after after System wt % initial initial mg Taber Taber A65 0 94 62 33 99 47 A218 1.25 101 66 61 102 46 A219 2.5 100 67 77 100 51 A220 5 104 70 62 103 45 A221 10 91 65 71 93 51 A222 15 129 81 70 100 50

(133) TABLE-US-00014 TABLE 14 5 wt % Lapis S, 30% BN 110, 10% FL D10H Weight loss CPE CPE Si.sub.3N.sub.4-B7 CPE after 1000 (H.sub.2O) (HD) (3.0 m)/ (H.sub.2O) CPE (HD) cycles Taber after after System wt % initial initial (CS-17)/mg Taber Taber A65 0 94 62 33 99 47 A223 1.25 109 71 60 103 49 A224 2.5 107 71 61 95 50 A225 5 106 67 58 99 53 A226 10 106 75 43 94 61 A227 15 129 82 59 100 50

(134) TABLE-US-00015 TABLE 15 5 wt % SiC, 30% BN, 10% FL D10H Weight loss CPE CPE CPE after 1000 (H.sub.2O) (HD) Lapis (H.sub.2O) CPE (HD) cycles Taber after after System S/wt % initial initial (CS-17)/mg Taber Taber A65 0 94 62 33 99 47 A190 1.25 102 66 50 100 50 A191 2.5 103 67 36 100 46 A192 3.5 103 70 60 100 53 A193 5 108 71 44 99 50 A194 10 114 73 37 103 50 A195 15 127 80 60 104 50

(135) TABLE-US-00016 TABLE 16 Comparative systems Weight loss CPE CPE Si.sub.3N.sub.4 CPE CPE after 1000 (H.sub.2O) (HD) Lapis M11- (H.sub.2O) (HD) cycles Taber after after System BN/wt % S/wt % A/wt % FL/wt % initial initial (CS-17)/mg Taber Taber 219 30 5 2.5 10 91 63 5.1 95 49 219-12 0 5 2.5 10 92 64 1.6 93 56 200 30 5 0 10 83 61 6.8 100 50 219-14 0 5 0 10 96 63 1.5 94 57 219-15 30 5 2.5 0 87 45 5.2 97 24 219-16 30 5 0 0 88 44 4.0 99 20

CITED LITERATURE

(136) U.S. Pat. No. 4,694,038A U.S. Pat. No. 5,789,523A WO2002005293A2 US20040229759A1 U.S. Pat. No. 4,898,905A U.S. Pat. No. 3,809,442 EP1350817A1 WO2005010107A1 WO2005010107A1 EP1718690