Light weight proppant with improved strength and methods of making same
Methods are described to make strong, tough, and/or lightweight glass-ceramic composites having a crystalline phase and an amorphous phase generated by viscous reaction sintering of a complex mixture of oxides and other materials. The present invention further relates to strong, tough, and lightweight glass-ceramic composites that can be used as proppants and for other uses.
1. A method for producing a proppant comprising
a. forming, a green body comprising a hollow template from a green body material comprising
i. at least one metal oxide or precursor thereof that is capable of forming a crystalline phase in said proppant, and
ii. at least one amorphous material containing at least one entrapped vaporizable material, and
iii. at least one fluxing agent
b. reactive sintering said green body under reactive sintering conditions to form a sintered body comprising at least one crystalline phase, at least one amorphous phase, and having gas bubbles contained therein, and wherein said gas bubbles are optionally at least partially surrounded by at least one glassy compound, and a majority of said gas bubbles are not in contact with each other; and wherein said reactive sintering forms at least one mullite whisker phase and an amorphous phase in said template.
2. The method of claim 1 , wherein said metal oxide or precursor thereof comprises aluminum hydroxide, bauxite, gibbsite, boehmite, or diaspore, or any combination thereof.
3. The method of claim 1 , wherein said metal oxide or precursor thereof has a particle size distribution, d as , of from about 0.5 to about 15, wherein, d as ={(d a90 −d a10 )/d a50 } wherein d a10 is a particle size wherein 10% of the particles have a smaller particle size, d a50 is a median particle size wherein 50% of the particles have a smaller particle size, and d a90 is a particle size wherein 90% of the particle volume has a smaller particle size.
4. The method of claim 3 , wherein the median particle size, d a50 , is from about 0.01 μm to about 100 μm.
5. The method of claim 1 , wherein said at least one metal oxide comprises a first metal oxide and a second metal oxide, wherein said first metal oxide and said second metal oxide are different from each other.
6. The method of claim 5 , wherein said second metal oxide has a particle size distribution, d ss , of from about 0.5 to about 15, wherein, d ss ={(d s90 −d s10 )/d s50 } wherein d s10 is a particle size wherein 10% of the particles have a smaller particle size, d s50 is a median particle size wherein 50% of the particles have a smaller particle size, and d s90 is a particle size wherein 90% of the particle volume has a smaller particle size.
7. The method of claim 6 , wherein the median particle size, d s50 , of said second metal oxide is from about 0.01 μm to about 100 μm.
8. The method of claim 1 , wherein said amorphous material containing at least one entrapped vaporizable material comprises perlite, a stober silica, pumice, andesite, scoria, volcanic glasses, or any combination thereof.
9. The method of claim 1 , wherein said vaporizable material comprises water (H 2 O), carbon dioxide (CO 2 ), sulfur dioxide (SO 2 ), hydrogen sulfide (H 2 S), nitrogen, argon, helium, neon, methane, carbon monoxide (CO), hydrogen, oxygen, hydrogen chloride (HCl), hydrogen fluoride (HF), hydrogen bromide (HBr), nitrogen oxide (NOx), sulfur hexafluoride (SF 6 ), carbonyl sulfide (COS), volcanic gases, or any combination thereof.
10. The method of claim 1 , wherein said amorphous material that contains at least one entrapped vaporizable material has a lower specific gravity than other components forming said green body.
11. The method of claim 1 , wherein said amorphous material containing at least one entrapped vaporizable material has a particle size distribution, d as , from about 1.0 to about 6.0, wherein, d as ={(d a90 −d a10 )/d a50 } wherein d a10 is a particle size wherein 10% of the particles have a smaller particle size, d a50 is a median particle size wherein 50% of the particles have a smaller particle size, and d a90 is a particle size wherein 90% of the particle volume has a smaller particle size.
12. The method of claim 11 , wherein the median particle size, d a50 , of said amorphous material containing at least one entrapped vaporizable material is from about 0.01 μm to about 100 μm.
13. The method of claim 1 , wherein said fluxing agent comprises nepheline syenite, feldspar, synthetic day, natural clay, or any combination thereof.
14. The method of claim 1 , wherein said method further comprises forming said green body around the template so as to encapsulate said template.
15. The method of claim 1 , wherein said sintering is performed in the presence of a gas, wherein said gas comprises from about 100 ppm to about 100% by weight oxygen.