# US 10,370,577 B2 · Self-repairing cement polymer composites and processes of making and using same

> Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt

- Number: US 10,370,577 B2
- Document ID: US10370577B2
- Status: Granted
- Kind: B2
- Application number: 15/677,993
- Filed: 2017-08-15
- Published: 2018-02-15
- Granted: 2019-08-06
- Earliest claimed: 2016-08-15
- Assignees: Battelle Memorial Institute
- Applicants: Battelle Memorial Institute
- Inventors: Carlos A. Fernandez; Phillip K. Koech; Wooyong Um; Vassiliki-Alexandra Glezakou; Jaehun Chun; M. Ian Childers; Manh Thuong Nguyen; Kenton A. Rod
- Web page: https://patentgrep.com/patent/US10370577B2

## CPC

- C09K 8/467: containing additives for specific purposes
- C04B 24/16: Sulfur-containing compounds
- C04B 24/281: {Polyepoxides}
- C04B 24/32: Polyethers, e.g. alkylphenol polyglycolether
- C04B 28/04: Portland cements
- E21B 33/14: for cementing casings into boreholes
- C04B 2103/0062: {Cross-linked polymers}
- C09K 8/428: {for squeeze cementing, e.g. for repairing}
- C09K: MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C04B: LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE {(roofing granules E04D7/005)}; CERAMICS (devitrified glass-ceramics C03C10/00); REFRACTORIES; TREATMENT OF NATURAL STONE
- E21B: EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS

## Abstract

New cement-polymer composites and processes of making and using are detailed. One exemplary cement-polymer composite include a Portland cement, an epoxide polymer, a thiol-containing crosslinking agent, and an optional phase separation inhibitor. These composites are dynamically self-healing, mechanically robust, and thermally stable in high temperature environments and can be expected to increase service lifetimes in various applications including energy producing wellbores.

## Claims

### Claim 1

A method of forming a self-repairing cement-polymer composite matrix, comprising the steps of:
introducing a cement-polymer composite-forming slurry comprising a cement-containing material, an epoxide polymer and/or epoxide oligomers thereof, a crosslinking agent, and an optional phase-separation inhibitor combined in an aqueous medium to a receiving location so as to contact structures and materials therein;
curing the composite-forming slurry to form a self-repairing and self readhering cement-polymer composite matrix comprising chemical bonds between compounds therein and the structures and materials in the receiving location; and
dynamically self-repairing structural breaches in the composite matrix by reforming chemical bonds between compounds therein and/or with the structures and materials bonded thereto restoring at least partial strength thereto and/or reducing permeability by up to about 90% therein.

### Claim 2 (depends on 1)

The method of claim 1 further including the step of forming the cement-polymer composite-forming slurry by combining the cement-containing material, the epoxide polymer and/or epoxide oligomers, the crosslinking agent, and the optional phase-separation inhibitor in the aqueous medium prior to introducing the composite-forming slurry into the receiving location.

### Claim 3 (depends on 1)

The method of claim 1, wherein the epoxide polymer comprises an epoxy-terminated polysulfide polymer.

### Claim 4 (depends on 1)

The method of claim 1, wherein the epoxide polymer comprises a terminal epoxide group.

### Claim 5 (depends on 1)

The method 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.

### Claim 6 (depends on 1)

The method of claim 1 wherein the phase separation inhibitor is a polymer having at least one terminal functional group reactive with the epoxide polymer and/or epoxide oligomers selected from the group consisting of amines; thiols; epoxides; alcohols; amides; carboxylates; carbonyls; and combinations thereof.

### Claim 7 (depends on 1)

The method of claim 1 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.

### Claim 8 (depends on 1)

The method of claim 1 wherein the epoxide polymer comprises an epoxy-terminated polysulfide polymer; the crosslinking agent is a tetrathiol; and the phase separation inhibitor is a PEO surfactant.

### Claim 9 (depends on 1)

The method of claim 1 wherein the self-repairing step includes a process selected from thiol metathesis; thiolate exchange; epoxide ring opening; metal coordination; ionic coordination; Diels-Alder bonding; and combination thereof.