High temperature composites and their application

Abstract

A high temperature composite includes a binder, cement or geopolymer and ceramic filler, negative coefficient of thermal expansion materials of AM.sub.2O.sub.8 or A.sub.2(MO.sub.4).sub.3 family or ZrV.sub.2O.sub.7. The material is compatible with concrete, any ceramics or metals or metal alloy. The material is heat shock resistant and stable in harsh chemical environments and is impermeable to most solvents. The new sealant materials can be used as sealants, heat shock resistant structural materials and coatings.

Claims

1. A product comprising a sealant material comprising a binder, a ceramic filler and a family of negative thermal expansion coefficient materials, wherein the family of negative thermal expansion coefficient materials is selected from the group consisting of AM.sub.2O.sub.8 or A.sub.2(MO.sub.4).sub.3 wherein (A=Zr or Hf, M=Mo or W), ZrV.sub.2O.sub.7, and combinations thereof, wherein the binder is selected from cement, geopolymer, polymer, metal, and combinations thereof, and wherein the family of negative thermal expansion coefficient materials is greater than 40% up to 59% of a combination of the binder, the ceramic filler and the family of negative thermal expansion coefficient materials.

2. The product of claim 1, wherein the sealant material is resistant to very high or very low temperature.

3. The product of claim 1, wherein the sealant material is adapted for use in fuel cell technology, transportation, defense and space structures, concrete roads or bridges, aircraft runways, missile and satellite launching pads and pads for vertical takeoff and landing.

4. The product of claim 1, wherein the sealant material is adapted for high temperature applications and uses in aircraft runway, pavement, insulation and shielding materials in nuclear power plants.

5. The product of claim 1, wherein the sealant materials is adapted for corrosive chemical application and uses in liquid gas storage or equipment facility, fuel or chemical storage facility.

6. The product of claim 1, wherein the binder and ceramic filler which further comprises materials of AM.sub.2O.sub.8 or A.sub.2(MO.sub.4).sub.3 family or ZrV.sub.2O.sub.7 is made by blending the binder and the filler in powder form, mixing the binder and the filler, homogenizing the binder and the filler, creating a paste and applying the paste between elements to be sealed.

7. The product of claim 1, wherein the binder and ceramic filler which further comprises materials of AM.sub.2O.sub.8 or A.sub.2(MO.sub.4).sub.3 family or ZrV.sub.2O.sub.7 is made by blending the binder and the filler in powder form, mixing the binder and the filler, homogenizing the binder and the filler, creating a paste and forming the paste into inserts, and drying and curing the inserts for use between articles to be sealed.

8. The product of claim 2, wherein the binder is Portland cement, silicates, polymers, siloxane, or metals.

9. The product of claim 8, wherein the Portland cement and ceramic filler which further comprises materials of AM.sub.2O.sub.8 or A.sub.2(MO.sub.4).sub.3 family or ZrV.sub.2O.sub.7 is made by blending the Portland cement and the filler in powder form, mixing the Portland cement and the filler, homogenizing the Portland cement and the filler, creating a paste and applying the paste between elements to be sealed.

10. The product of claim 8, wherein the Portland cement and ceramic filler which further comprises materials of AM.sub.2O.sub.8 or A.sub.2(MO.sub.4).sub.3 family or ZrV.sub.2O.sub.7 is made by blending the Portland cement and the filler in powder form, mixing the Portland cement and the filler, homogenizing the Portland cement and the filler and creating a paste.

11. The product of claim 1, wherein the binder and ceramic filler which further comprises materials of AM.sub.2O.sub.8 or A.sub.2(MO.sub.4).sub.3 family or ZrV.sub.2O.sub.7 is made by blending the binder and the filler in powder form, mixing the binder and the filler, homogenizing the binder and the filler, melting it to liquid and pouring the liquid between elements to be sealed.

12. The product of claim 1, wherein the binder and ceramic filler which further comprises materials of AM.sub.2O.sub.8 or A.sub.2(MO.sub.4).sub.3 family or ZrV.sub.2O.sub.7 is made by blending the binder and the filler in powder form, mixing the binder and the filler, homogenizing the binder and the filler, making a dispersing in solvent and spraying the liquid between elements to be sealed.

13. The product of claim 1, wherein the material is compatible with concrete, polymers, plastic, metal or metal alloy and ceramics and is adapted for use in sealants, heat shock resistant structural materials or coatings.

14. A process for making a sealant material, comprising mixing a powdered or liquid binder and a powdered or liquid filler material, further comprising mixing greater than 40% up to 59% of total content of a family of negative thermal expansion coefficient materials selected from the group consisting of AM.sub.2O.sub.8 or A.sub.2(MO.sub.4).sub.3 family, wherein (A=Zr or Hf, M=Mo or W), or ZrV.sub.2O.sub.7, and combinations thereof, mixing the powdered binder and filler, homogenizing the mixed powdered or liquid binder and filler into a paste, liquid or dispersion and applying the paste liquid or dispersion and wherein the binder is selected from cement, geopolymer, polymer, metal, and combinations thereof.

15. The process of claim 14, wherein the applying the paste or liquid or dispersion comprises applying the paste or liquid or dispersion between objects as a sealant material, applying the paste or liquid or dispersion to forms of structural material, applying the paste or liquid or dispersion as a heat shock resistant material to structural materials or applying the paste or liquid or dispersion to forms, or molding sealant material and applying the sealant material between objects, and further comprising curing and drying the paste or liquid or dispersion.

16. The process of claim 14, further comprising hydrating the binder, and wherein the mixing further comprises mixing the powdered filler with the hydrated binder.

17. The process of claim 14, further comprising liquid the binder, and wherein the mixing further comprises mixing the powdered or liquid filler with the binder.

18. The process of claim 14, further comprising hydrating the mixed powders.

19. The process of claim 14, further comprising hydrating the homogenized powders.

20. The process of claim 14, further comprising chemical crosslinking the homogenized powders or liquid.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIGS. 1A-1E depict the shape of the specimen in FIG. 1A, a synthesis protocol for manufacturing the sealant materials in FIG. 1B, fabrication of a cement based specimen in FIG. 1C, prefabricated specimens in FIG. 1D and cross sectional view of the specimen in FIG. 1E.

(2) FIGS. 2A-C are graphs of the thermo-gravimetric analysis (TGA) data, showing normalized weight as a function of temperature.

(3) FIGS. 3A and 3B show specimens in FIG. 3A and a graph of the change in volume as a function of thermal cycle in FIG. 3B.

(4) FIG. 4 shows a chemical resistivity test of cement-zirconium tungstate.

(5) FIG. 5 shows the thermal expansion of specimens 1 as a function of temperature.

(6) FIGS. 6A and 6B show a schematic in FIG. 6A and lab setup in FIG. 6B for a simulated exhaust test.

(7) FIG. 7A-C show lab testing at 500° F. in FIG. 7A, and a specimen before heating in FIG. 7B and the specimen after heating at 500° F. in FIG. 7C.

(8) FIGS. 8A-C show results of lab testing at 1700° F. of cement-zirconium tungstate (ZT3).

DETAILED DESCRIPTION OF THE DRAWINGS

(9) The invention is based on compensating for the expansion of pavement concrete with a matching contraction of cement-zirconium tungstate (CZT) composites in the joints. To achieve this, the coefficient of thermal expansion (CTE) of the composite should be lower or a match to the positive CTE of concrete (7-12×10.sup.−6/° C.). The required value was achieved by adding negative CTE materials to a cement matrix. The expected coefficient of thermal expansion was estimated using Turner's model shown in Table 1. Based on these estimations, cement-quartz (Q1), cement-quartz-zirconium tungstate (Q-ZT-2) and cement-zirconium tungstate (ZT3) were considered as shown in Table 2.

(10) As shown in FIG. 1A, specimens having 2″×0.25″ square cross sections and ends flat and parallel to within 0.001 inch were fabricated as per ASTM E228-06, “Standard Test Method for Linear Thermal Expansion of Solid Materials”.

(11) The general synthesis scheme for making the sealant materials is summarized in FIG. 1B. Three different types of sealant material specimens 1 were prepared: cement quartz (Q1), cement quartz zirconium tungstate (Q-ZT-2) and cement zirconium tungstate (ZT3). The sample materials were mixed with water for 10 minutes to make pastes. The water content was varied to obtain consistencies suitable for molding.

(12) The pastes were placed in a wood mold 3 and cured at 100% humidity for 4 days as shown in FIG. 1C. The specimens 1 were extracted from the mold 3 as shown in FIG. 1D and were tested without further processing. FIG. 1E is a cross-sectional view of specimen 1.

(13) The composites were thoroughly characterized. Thermo-gravimetric analysis (TGA) was used to study the thermal stability of materials, in all three specimens on heating as shown in FIGS. 2A-C. The overall mass losses for cement quartz, cement quartz zirconium tungstate and cement zirconium tungstate were 12.3%, 19.5% and 16.2%, respectively, during the first cycle with no significant change observed in subsequent cycles. The cement-quartz specimen shows two steps, 3% from room temperature to 200° C. and 9.3% from 600 to 1000° C. Cement-quartz-zirconium tungstate and cement-zirconium tungstate show ˜10%, ˜4%, ˜6% mass loss in the 100-200° C., 450-500° C. and 600-1000° C. ranges. The changes in the low-temperature and high-temperature ranges can be attributed to trapped moisture and decomposition of a structural hydroxyl group on the specimen surface respectively.

(14) The shrinkage and surface changes for Q1, Q-ZT-2 and ZT3 were examined by placing a 40×10×10 mm in an open air box furnace, heating the specimens to 1,000° C. and then allowing the specimens to cool to room temperature. Volume reductions of 24%, 12% and 14% were observed after 25 cycles in Q1, Q-ZT-2 and ZT3, respectively, as shown in FIGS. 3A-C. The first cycle resulted in maximum shrinkage in agreement with mass-loss data. The reduction was due to evaporation of water and consequent shrinkage of the matrix. Both are known characteristics of cement materials. Specimens of Q1 and Q-ZT-2 exhibited numerous stress cracks. These cracks are considered normal and can be avoided by modifying material composition.

(15) Chemical stability of specimens 1 was determined by exposure to Anderol ROYCO 782 Hydraulic Fluid (MIL-H-83282), AeroShell Turbine Oil 500 (MIL-L-23699), and JP-5 jet fuel (FIG. 4). All the samples showed negligible change in volume and no visible physical or chemical change. The increase in weight of 6.5-8% was observed in the specimens. The weight increases can be attributed to absorption of fluid into the pores of the specimens 1 as shown in Table 3.

(16) Thermal expansion of the samples was measured as a function of temperature as shown in FIG. 5. Q-ZT-2 and ZT-3 expanded from 20° C. to 100° C. and contracted from 100° C. to 1,000° C. The average coefficient of thermal expansion (CTE) was estimated based on a linear best-fit analysis of the data and listed in Table 4. The CTE of ZT3 specimen is found to be 8.9×10.sup.−6° C..sup.−1 for 20-100° C. and −18×10.sup.−6° C..sup.−1 in 100-1,000° C. temperature range. Those results showed a 40% less positive and 44% less negative CTE compared to the equivalent ranges in pure cement. The CTE of ZT3 is thus found to be in the desired range for concrete expansion joints.

(17) As shown in FIG. 6A, in order to examine the stability of sealant materials 5, tests were performed involving exposure of concrete panels 7 to gas flames 9 at 550±50° F. and 1,700° F. The test was used to study the thermal stability of specimens. FIG. 6B shows the laboratory set up with the concrete panels 7, the sealant 5, thermocouple 11 and the blow torch 13.

(18) Unreinforced 6×6×1 inch Portland cement concrete (PCC) panels were fabricated and used as shown in FIGS. 7A-C. A slot 0.25 inch wide and 0.50 inch deep was cut and filled with sealant. The samples were cured at 100% humidity for 4 days. The panels were clamped facing a gas flame 9 with thermocouples 11 installed at various locations on the sealant 5, within the sealant and on the concrete 7 two inches away from the hottest spot 15, as shown in FIGS. 7A-C.

(19) In a typical test, the sealant surface was maintained at either ˜500° F. for 15 minutes or 1,700° F. for 20 seconds. After each exposure, the specimen 1 was visually inspected to document change in material appearance or loss of adhesion as shown in FIG. 7C. Measurements were repeated twenty times to evaluate long-term durability of the material.

(20) No loss of material or adhesion was observed in the heated zone 17 as shown in FIG. 8. No flame, charring or physical change was observed on the sealant 5, suggesting that the sealant material retains its original physical properties. Preliminary studies show that the CZT composite outperforms existing polymer-based sealant materials.

(21) While the invention has been described with reference to specific embodiments, modifications and variations of the invention may be constructed without departing from the scope of the invention, which is defined in the following claims.

(22) TABLE-US-00001 TABLE 1 Formulation for concrete joint sealant composite. Form- Type glass/cement ZT ulations of glass Vol. % Wt. % Vol. % Wt. % CTE(/° C.) 1 Cement/ 22/78% 25/75%  0%  0% −9.63 × 10−6 quartz 2 Cement/ 93% 89%  7% 11% — quartz 3 Cement 83% 75% 17% 25%   −28 × 10−6 4 Cement 63% 51% 37% 49%   −23 × 10−6 5 Cement 53% 41% 47% 59%   −21 × 10−6

(23) TABLE-US-00002 TABLE 2 Cement based formulations mix ratios. Formulation 1 Formulation 2 Formulation 3 Component Q1 (g/wt. %) (C-Q-ZT-2) (g/wt. %) (ZT3) (g/wt. %) Cement(g)  83 g 26.5%  166 g   59% 166 g 59% Quartz(g) 230 g 73.5% 57.5 g 20.5%  0 g  0% Zirconium  0 g   0% 57.5 g 20.5% 115 g 41% Tungstate(g) Water(g) 150 g —  150 g —  75 g —

(24) TABLE-US-00003 TABLE 3 Quantitative analysis of specimens in various chemical environments. Cement-quartz- Cement-Zirconium Zirconium Tungstate Tungstate Types of Wt. Vol. Wt. Vol. Chemical Change (%) Change (%) Change (%) Change (%) JP-5 jet fuel 7.0 0 7.1 0 AeroShell 8.0 0 7.5 0 Turbine Oil 500 Anderol 7.7 0 6.5 0 ROYCO 782 Hydraulic Fluid

(25) TABLE-US-00004 TABLE 4 Coefficient of thermal expansion of various materials. Materials Temperature (° C.) CTE (×10.sup.−6 ° C..sup.−1) Cement-Quartz-  20-100 11 Zirconium Tungstate  100-1000 −8.85 Cement-zirconium  20-100 8.94 Tungstate  100-1000 −18.5 Concrete  20-1000 7.2 Cement  20-150 14.8 150-871 −32.8