Self-repairing cement polymer composites and processes of making and using same
Examples of novel self-repairing cement-polymer composites and processes of making and using are detailed that address various problems in prior art cements. These matrices, compositions and materials that are more mechanically robust, thermally stable and chemically resistant and demonstrate better bonding to various structures and materials, than other self-healing cements known in the prior art. When in place under preselected conditions (the formulation of the slurry can be modified for optimal effectiveness under various conditions) the organic, cross linking and cement forming portions within the slurry form interconnecting chemical bonds and cures to form a self-repairing and self-re-adhering cement polymer composite matrix in the receiving location.
1. A self-repairing cement-polymer composition comprising:
a cement-containing material comprising at least one material selected from the group consisting of mortars: limes: limestone fines: fly ash; granulated blast furnace slags: concretes: ordinary Portland cements having fractions of inorganic oxides including calcium oxide: silicon oxide, and aluminum oxide, and combinations thereof:
an unencapsulated epoxide polymer having at least one disulfide (S—S) group therein, and a crosslinking agent;
all combined to form a dynamically self-repairing cement polymer matrix that reforms chemical bonds between compounds when subjected to preselected conditions.
2. The self-repairing cement-polymer composition of claim 1 further comprising a phase separation inhibitor.
3. The self-repairing cement-polymer composition of claim 2 wherein the unencapsulated epoxide polymer comprises an epoxy-terminated polysulfide polymer; the crosslinking agent is a tetra thiol; and the phase separation inhibitor is a PEO surfactant.
4. The self-repairing cement-polymer composition of claim 2 wherein the phase separation inhibitor is a polymer having at least one terminal functional group selected from the group consisting of amines; thiols; epoxides; alcohols; amides; carboxylates; carbonyls; and combinations thereof, that is reactive with the unencapsulated epoxide polymer.
5. The self-repairing cement-polymer composition of claim 4 wherein the phase separation inhibitor is selected from the group consisting of poly(ethylene glycol) diglyceryl ethers (PEO); poly(ethylene) glycols (PEG); bisphenol diglycidyl ethers (BPA); and combinations thereof.
6. The self-repairing cement-polymer composition of claim 1 wherein the unencapsulated epoxide polymer comprises an epoxide oligomer.
7. The self-repairing cement-polymer composition of claim 1 wherein the crosslinking agent includes a functional group selected from the group consisting of hydrogen; alcohol; thiol; ether; ester; amine; amide; and combinations thereof.
8. The self-repairing cement-polymer matrix of claim 1 wherein self-repair includes a process selected from the group consisting of thiol metathesis; thiolate exchange; epoxide ring opening; metal coordination; ionic coordination; Diels-Alder bonding; and combinations thereof.
9. A self-repairing cement-polymer slurry comprising:
a cement containing material comprising at least one material selected from the group consisting of mortars; limes; limestone fines; fly ash; granulated blast furnace slags; concretes; ordinary portland cements having fractions of inorganic oxides
including calcium oxide; silicon oxide, and aluminum oxide, and combinations thereof;
an unencapsulated epoxide polymer having at least one disulfide (S—S) group therein, a crosslinking agent; and an aqueous solvent
all combined to cure under preselected conditions and to form a dynamically self repairing cement polymer matrix that reforms chemical bonds between compounds when subjected to said preselected conditions.
10. The self-repairing cement-polymer slurry of claim 9 wherein self-repair includes a process selected from the group consisting of thiol metathesis; thiolate exchange; epoxide ring opening; metal coordination; ionic coordination; Diels-Alder bonding; and combinations thereof.
11. The self-repairing cement-polymer matrix of claim 9 further comprising a phase separation inhibitor.
12. The self-repairing cement-polymer slurry of claim 9 wherein the unencapsulated epoxide polymer comprises a terminal epoxide group.
13. The self-repairing cement-polymer slurry of claim 9 wherein the crosslinking agent includes a functional group selected from the group consisting of hydrogen; alcohols; thiols; ethers; esters; amines; amides; and combinations thereof.
14. The self-repairing cement-polymer composition of claim 9 wherein the phase separation inhibitor includes at least one terminal functional group reactive with the epoxide thereof selected from the group consisting of amines; thiols; epoxides; alcohols; amides; carboxylates; carbonyls; and combinations thereof.
15. The self-repairing cement-polymer composition of claim 14 wherein the phase separation inhibitor is selected from poly(ethylene glycol) diglycidyl ethers (PEO); poly(ethylene) glycols (PEG); bisphenol diglycidyl ethers (BPA); and combinations thereof.
16. The self-repairing cement-polymer composition of claim 9 wherein the unencapsulated epoxide polymer comprises an epoxy-terminated polysulfide polymer; the crosslinking agent is a tetrathiol; and the phase separation inhibitor is a PEO surfactant.
17. A cement-polymer composite-forming slurry, comprising:
a cement containing material comprising at least one material selected from the group consisting of mortars; limes; limestone fines; fly ash; granulated blast furnace slags; concretes; ordinary portland cements having fractions of inorganic oxides including calcium oxide; silicon oxide, and aluminum oxide, and combinations thereof;
an unencapsulated epoxide polymer having at least one disulfide (S—S) group and at least one terminal epoxide group therein;
a crosslinking agent including a functional group selected from the group consisting of hydrogen; alcohol; thiol; ether; ester; amine; amide; and combinations thereof; and
a phase separation inhibitor that is reactive with the unencapsulated epoxide polymer, the phase separation inhibitor selected from the group consisting of poly(ethylene glycol) diglycidyl ethers (PEO); poly(ethylene) glycols (PEG); bisphenol diglycidyl ethers (BPA); and combinations thereof;
the cement containing material, the unencapsulated epoxide polymer, the crosslinking agent, and the phase separation inhibitor all combined to form a dynamically self-repairing cement polymer matrix that reforms chemical bonds between compounds using a process selected from the group consisting of thiol metathesis; thiolate exchange; epoxide ring opening; metal coordination; ionic coordination; Diels-Alder bonding; and combinations thereof when subjected to preselected conditions.