Highly structured composite material and process for the manufacture of protective coatings for corroding substrates

Abstract

A highly structured composite material, which can be applied and cured as a protective layer on corroding metal substrates, particularly on steel is provided. Due to its highly structured composition it is a particularly effective barrier to protect metals against attack by corrosive substances such as hydrogen sulfide, carbon dioxide and sea water, if necessary under hydrothermal conditions. At the same time it is also abrasion stable, for example against a grinding effect by sand, as well as resistant to the impact of mechanical load e.g. by tools. This is achieved by a coating composition comprising a binder comprising at least one cross-linkable resin, wherein the resin comprises at least one of polar group; at least one type of hydrophilic flakes with an aspect ratio of more than 10, wherein the surface of the flakes at least partially comprises a metal oxide; and an organic solvent.

Claims

1. Coating composition, comprising: a mixture of: a) 50 to 98 wt. % of a binder comprising at least one cross-linkable resin, wherein the resin is selected from the group consisting of epoxy resin, phenol resin, phenoxy resin and mixtures thereof, and wherein the resin comprises at least one polar group selected from the group consisting of hydroxyl, alkoxysilyl, epoxy, carboxyl, ester, carbonyl, oxycarbonyl, sulfide, disulfide, sulfonyl, sulfinyl, thiol, thiocarbonyl, imino, amino, nitrile, ammonium, imide, amide, hydrazo, azo, diazo, cyanide, guanidine, oxygen-containing heterocyclic, nitrogen-containing heterocyclic and sulfur-containing heterocyclic groups; b) 2 to 25 wt. % of a plurality of at least one type of hydrophilic flake with an aspect ratio of more than 10, said flakes comprising a glass, silicon dioxide, or alumina substrate coated with a transition metal oxide layer of TiO.sub.2, Fe.sub.2O.sub.3, V.sub.2O.sub.5, CeO.sub.2, MnO.sub.2, CuO, ZrO.sub.2, or mixtures thereof; c) 0.1 to 2 wt. % of a perfluoropolyether; and d) an organic solvent, wherein the binder is dissolved in the organic solvent, and a ratio of the organic solvent to the binder is 2:1 to 1:5.

2. Coating composition according to claim 1, further comprising inorganic particles selected from the group consisting oxides, nitrides, carbides, carbonitrides, silicides, borides and mixtures thereof.

3. Coating composition according to claim 2, wherein the inorganic particles are selected from the group consisting of at least one of boron carbide, silicon carbide silicon nitride, and mixtures thereof.

4. Coating composition according to claim 1, wherein the coating composition further comprises a rheology additive selected from the group consisting of synthetic waxes, polyethylene waxes, polytetrafluoroethylene waxes, high-density polyethylene waxes, polypropylene waxes, ethylene copolymers, ethylene acrylic acid copolymers and ethylene vinyl acetate copolymers.

5. Coating composition according to claim 1, wherein the binder comprises a mixture of epoxy resins and phenoxy resins.

6. Coating composition according to claim 5, wherein a ratio of epoxy resins and phenoxy resins is between 10:1 to 1:1.

7. Coating composition according to claim 1, wherein the polar group is selected from the group consisting of alkoxysilyl, carboxyl, sulfide, disulfide, sulfonyl, sulfinyl, thiol, cyanide, and nitrogen-containing heterocyclic groups.

8. Coating composition according to claim 1, wherein the organic solvent is selected from the group consisting of halogenated hydrocarbons, ethers, ketones, alcohols, (cyclo)aliphatic or aromatic solvents in a boiling range from about 150° C. to 180° C., esters, and a mixture thereof.

9. Coating composition according to claim 1, wherein the flakes have an average diameter between 1 and 500 μm and an average thickness between 0.1 of 5 μm.

10. Coating composition according to claim 1, wherein the flakes have an average diameter in a range of 1-15 μm and an average thickness of between 0.1 of 1 μm.

11. Coating composition according to claim 1, wherein the transition metal oxide layer has a closed grain structure.

12. Coating composition according to claim 1, wherein the binder is an epoxide compound comprising a polyglycidyl ether of a dihydric phenol.

13. A coated substrate, comprising a glass, ceramic, or plastic substrate coated with the coating composition according to claim 1.

14. A coated substrate comprising a substrate comprising a semiconductor, wherein the semiconductor is coated with the coating composition according to claim 1.

15. A composition, comprising: a cured coating for a gaseous corrosive environment comprising: 50 to 96 wt. % of a binder comprises a mixture of epoxy resin and phenoxy resin; 5 to 27.4 wt. % of at least one type of hydrophilic flakes comprising a silicon dioxide or alumina substrate with an aspect ratio of more than 10 coated with TiO.sub.2; and 2 to 20 wt. % cyanoguanidine crosslinking comonomer 1 to 3 wt. % ethylene vinyl acetate copolymer; and 0.28 to 0.5 wt. % perfluoropolyether.

16. Coating composition according to claim 15, wherein the at least one type of hydrophilic flakes has a tile-like arrangement configured to elongate a diffusion path of gas molecules.

17. A composition, comprising: a cured coating composition for a liquid corrosive environment comprising: 50 to 93 wt. % of a binder comprising a mixture of epoxy resin and phenoxy resin; 5 to 20 wt. % of at least one type of hydrophilic flake comprising a silicon dioxide or alumina substrate with an aspect ratio of more than 10 coated with TiO.sub.2; and 10 to 25 wt. % boron carbide particles; 0.28 to 0.5 wt. % perfluoropolyether.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1: The figure shows the rating for the Cross Cutt—Tape Test (CC/TT) according to DIN ISO 2409

(2) FIG. 2A: The figure shows results from the Fatigue test for sample G055.

(3) FIG. 2B: The figure shows results from the Fatigue test for different sample G089.

(4) FIG. 3: SEM images from a cross section from different samples. From the top: a) G035 20 wt.-% Lapis Sunlight; b) G049 20 wt.-% Lapis Sunlight+2.0% Ceratix 8461; c) G048 20 wt.-% Lapis Sunlight+2.3% Cerafak 100.

(5) TABLE-US-00001 Flake 1 Boron Co- Lapis Flake 2 car- Rheo. H.sub.2S mono- Sun- Crystal bide Add- thick- auto- Taber mer 2 Sam- light Silver HD 20 itive ness clave CC/TT CC/TT SST Δm EP307 PR722 FL ple wt.- % wt.- % wt.- % wt.- % [μm] test liquid gas. [h] [mg] wt.- % wt.- % wt.- % H193 — — — — 30.40 720 h 2/3 5/5 6.8 79.60 19.90 0.50 H139 — — 25% HD20 — 7.00 720 h 0/0 0/0 — 1.9 59.70 14.93 0.38 H226  5% LS — 15% HD20 — 7.81 720 h 0/0 0/0.5 408 2.0 63.68 15.92 0.40 H144 10% LS — — — 15.46 720 h 0/1 0/2 672 7.3 71.64 17.91 0.45 H228 10% LS — 10% HD20 — 7.88 720 h 0/0 0/0 408 1.5 63.68 15.92 0.40 H229 10% LS — 15% HD20 — 8.37 720 h 0/0 0/0 576 1.8 59.70 14.93 0.38 H246 10% LS — 15% HD20   1% CTX 11.08 720 h 0/0 0/0 1008 3.2 58.90 14.73 0.38 H247 10% LS — 15% HD20   2% CTX 16.60 720 h 0/0 0/0 1008 3.1 58.10 14.53 0.38 H248 10% LS — 15% HD20   3% CTX 14.85 720 h 0/0 0/0 1008 3.0 57.30 14.33 0.38 H230 10% LS — 25% HD20 — 9.96 720 h 0/0 0/0 576 2.5 51.74 12.94 0.33 H232 20% LS — 15% HD20 — 11.68 720 h 0/0 0/0 1080 4.3 51.74 12.94 0.33 H235 —  5% CS 15% HD20 — 16.90 720 h 0/0.5 1/3.5 408 2.8 63.68 15.92 0.40 H237 — 10% CS 10% HD20 — 21.91 720 h 0/1.5 0/2.5 408 3.3 63.68 15.92 0.40 H238 — 10% CS 15% HD20 — 17.35 720 h 0/0 0/1.5 1080 2.8 59.70 14.93 0.38 H252 — 10% CS 15% HD20   1% CTX 22.91 720 h 0/0 0/0 504 3.2 58.90 14.73 0.38 H253 — 10% CS 15% HD20   2% CTX 26.21 720 h 0/0 0/1 1008 3.6 58.10 14.53 0.38 H254 — 10% CS 15% HD20   3% CTX 28.30 720 h 0/0 0/1 840 3.4 57.30 14.33 0.38 H239 — 10% CS 25% HD20 — 58.36 720 h 0/1 0/1.5 1080 3.4 51.74 12.94 0.33 H240 — 20% CS 10% HD20 — 16.09 720 h 0/0 0/0 1080 4.0 55.72 13.93 0.35 H241 — 20% CS 15% HD20 — 19.12 720 h 0/1.5 0/0.5 1080 3.9 51.74 12.94 0.33 H242 — 20% CS 25% HD20 — 23.39 720 h 0/2.5 0/1.5 1080 5.4 43.78 10.95 0.28 H168  5% LS — 10% HD15   2% CF 25.8 720 h 0/1 0/1 480 4.2 66.06 16.52 0.43 H169  5% LS — 10% HD15 0.25% PS 19.5 720 h 1/2 0/0 984 3.4 67.46 16.87 0.43 H170  5% LS — 10% HD15  0.5% PS 17.7 720 h 0/0 0/1 1032 3.7 67.26 16.81 0.43

(6) TABLE-US-00002 TABLE 2 Flake 1 Co- Co- Lapis Flake 2 Flake 3 monomer Rheo. Rheo. H.sub.2S- mono- Sun- Crystal Glass 1 cyano- additive additive thick- auto- mer 2 Sam- light Silver flakes guanidine 1 CFX 2 CFX ness clave CC/TT Fatigue EP307 PR722 FL ple wt.- % wt.- % wt.- % wt.- % wt.- % wt.- % [μm] test gas. test wt.- % wt.- % wt.- % G046 — — — — — — 11.96 720 h 2/4 79.60 19.90 0.50 G014 — — 10.00 — — — 23.82 720 h 5/5 71.64 19.90 0.45 G099 — — — 10.54 2.24 — 19 720 h 1/2 69.43 17.63 0.43 G095  5.00 — — 2.93 2.31 — 29 720 h 0/0 71.45 17.86 0.45 G096  5.00 — — 5.29 2.25 — 28 720 h 0/0 69.62 17.41 0.44 G094  5.00 — — 10.01 2.13 — 23 720 h 0/0 65.96 16.49 0.41 G097  5.00 — — 14.73 2.01 — 24 720 h 0/0 62.29 15.57 0.39 G098  5.00 — — 19.45 1.89 — 20 720 h 0/1 58.63 14.66 0.37 G090 10.00 — — 2.77 2.19 — 27 720 h 0/0 67.69 16.92 0.42 G091 10.00 — — 5.01 2.13 — 22 720 h 0/0 65.96 16.49 0.41 G089 10.00 — — 9.48 2.02 — 27 720 h 0/0 ok 62.49 15.62 0.39 D092 10.00 — — 13.95 1.91 — 26 720 h 0/0 59.02 14.75 0.37 G093 10.00 — — 18.43 1.79 — 28 720 h 0/1 55.54 13.89 0.35 G035 20.00 — — — — — 15.67 720 h 0/1 63.68 15.92 0.45 G049 20.00 — — — 2.00 — 24.25 720 h 1/1 62.09 15.52 0.39 G048 20.00 — — — — 2.30 26.58 720 h 1/1 61.85 15.46 0.39 G085 20.00 — — 2.46 1.96 — 33 720 h 0/0 60.17 15.04 0.38 G086 20.00 — — 4.45 1.89 — 34 720 h 0/0 58.63 14.66 0.37 G051 20.00 — — 10.40 — — 23.19 720 h 0/0 55.40 13.85 0.35 G055 20.00 — — 10.16 1.75 — 29.72 720 h 0/0 ok 54.21 13.55 0.34 G053 20.00 — — 10.12 — 2.02 35.40 720 h 0/0 53.97 13.49 0.34 G039 27.40 — — — 1.83 — 25.66 720 h 0/0 56.33 14.08 0.35 G037 23.99 — — — — 2.22 29.69 720 h 0/0 58.74 14.69 0.37 G060 20.00 10.40 24.42 720 h 0/0 55.40 13.85 0.35 G064 20.00 10.16 1.75 34.49 720 h 0/0 54.21 13.55 0.34 G062 20.00 10.12 2.02 30.73 720 h 0/0 53.97 13.49 0.34

REFERENCES CITED

(7) WO 2004/022806 A1 JP S54-011938 A WO 2006/079643 A1 US 2009/0277625 A1 JP S62-050368 A DE 10 2006 062 500 A1 WO 2005/044551 A1 DE 10 2009 037 323 A1 DE 102 009 031 266 A1 DE 603 19 674 T2 WO 2006/007385 A1 EP 1 718 690 A1 EP 0 387 692 A2 DE 42 12 633 A1 WO 93/21127 A1 WO 96/31572 A1 U.S. Pat. No. 3,705,109 RU 2083621 G. Buxbaum and G. Pfaff Industrial inorganic pigments, 3.sup.rd ed. Wiley-VCH pages 243-248 F. J. Maile et al. Progress in Organic Coating 2005, 54, 150-163