Cement slurries, cured cement and methods of making and use of these

Patent metadata

Field	Value
Publication number	US-12371375-B2
Application number	US-202418626703-A
Country	US
Kind code	B2
Filing date	Apr 4, 2024
Priority date	Nov 11, 2020
Publication date	Jul 29, 2025
Grant date	Jul 29, 2025

Abstract

Cement slurries, cured cements, and methods of making cured cement and methods of using cement slurries are provided. The cement slurries have, among other attributes, improved expanding capabilities and may be used, for instance, in the oil and gas drilling industry. The cement slurry comprises water, a cement precursor material, and an expanding agent. The expanding agent comprising at least a poly(acrylic acid)-metal oxide nanocomposite, where the metal oxide comprises MgO, CaO, or both, and the poly(acrylic acid) comprises a t-butyl terminal group, an isobornyl terminal group, or both.

First claim

What is claimed is:

1. A method of producing a poly(acrylic acid) block copolymer-metal oxide nanocomposite comprising:
synthesizing a poly(acrylic acid) block copolymer comprising a t-butyl terminal group, an isobornyl terminal group, or both via reversible addition-fragmentation chain transfer (RAFT) polymerization; and
grafting the poly(acrylic acid) onto MgO nanocomposites, CaO nanocomposites, or both, thereby forming the poly(acrylic acid)-metal oxide nanocomposite.

2. The method of claim 1 , further comprising producing a cement slurry by mixing water, a cement precursor material, and an expanding agent comprising at least the poly(acrylic acid)-metal oxide nanocomposite.

3. The method of claim 2 , in which the cement slurry further comprises from 15 to 100 mol. % acid catalyst relative to combined moles of the t-butyl terminal group and the isobornyl terminal group.

4. The method of claim 3 , in which the acid catalyst comprises sulfonic acid, para-toluene sulfonic acid, hydrochloric acid, trifluoroacetic acid, aqueous phosphoric acid, molecular iodine, zinc bromide, or combinations thereof.

5. The method of claim 3 , in which the sulfonic acid comprises para-toluenesulfonic acid.

6. The method of claim 2 , in which:
the cement precursor material comprises calcium hydroxide, silicates, belite (Ca 2 SiO 5 ), alite (Ca 3 SiO 4 ), tricalcium aluminate (Ca 3 Al 2 O 6 ), tetracalcium aluminoferrite (Ca 4 Al 2 Fe 2 O 10 ), brownmillerite (4CaO·Al 2 O 3 ·Fe 2 O 3 ), gypsum (CaSO 4 ·2H 2 O), Portland cement precursor, siliceous fly ash, calcareous fly ash, slag cement, or combinations of these; and
the cement slurry optionally comprises sodium oxide, potassium oxide, limestone, lime (calcium oxide), hexavalent chromium, trivalent chromium, calcium aluminate, quartz, silica fume, or combinations of these.

7. The method of claim 2 , in which the cement slurry contains from 0.1 to 10 wt. % BWOC of one or more additives selected from the group consisting of accelerators, retarders, extenders, suspending agents, weighting agents, fluid loss control agents, lost circulation control agents, surfactants, antifoaming agents, and combinations of these.

8. The method of claim 1 , in which synthesizing via reversible addition-fragmentation chain transfer (RAFT) polymerization comprises:
providing 2-(Butylthiocarbonothioylthio) propanoic acid as a RAFT agent;
providing tert-butyl acrylate, isobornyl acrylate, or both, as monomers; and
providing 4,4′-azobis(4-cyanovaleric acid) as an initiator.

9. The method of claim 2 , in which the expanding agent comprising at least the poly(acrylic acid)-metal oxide nanocomposite has a structure of:

where XO is MgO, CaO, or both; a ranges from 1 to 100; and b ranges from 1 to 100.

10. The method of claim 2 , in which the expanding agent comprising at least the poly(acrylic acid)-metal oxide nanocomposite has a structure of:

where XO is MgO, CaO, or both; a ranges from 1 to 100; and b ranges from 1 to 100.

Assignees

• Saudi Arabian Oil Co

Inventors

• Musso Simone
• Shanmugam Sivaprakash

Classifications

• C09K8/473

  Density reducing additives, e.g. for obtaining foamed cement compositions · CPC title

• C08L51/10

  grafted on to inorganic materials · CPC title

• C08F220/06

  Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof · CPC title

• C04B2103/0061

  Block (co-)polymers · CPC title

• C04B2103/0059

  Graft (co-)polymers · CPC title