DEGRADABLE COMPOSITE STRUCTURES

• US 20170369708A1
• Filed: 12/18/2015
• Published: 12/28/2017
• Est. Priority Date: 12/22/2014
• Status: Active Grant

• Current Assignee: Schlumberger Technology Corporation (SLB)
• Original Assignee: Schlumberger Technology Corporation (SLB)
• Inventors: Kokel, Philip, Zhu, Shitong S., Godfrey, Matthew, Qu, Meng, Pabon, Jahir A., Lou, Yucun, Auzerais, Francois M., Rowatt, John David, Kats, Roman, Joshi, Gauri, Amarante, Miranda
• Granted Patent: US 11,136,461 B2
• Time in Patent Office: Days
• CPC Class Codes: C08K 2003/222 Magnesia, i.e. magnesium oxide
• CPC Class Codes: C08K 3/013 Fillers, pigments or reinforcing additives
• CPC Class Codes: C08K 3/22 of metals
• CPC Class Codes: C08K 5/20 Carboxylic acid amides
• CPC Class Codes: C08K 7/02 Fibres or whiskers
• CPC Class Codes: C08K 7/14 Glass
• CPC Class Codes: C08L 101/12 characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity liquid crystal materials or compositions C09K19/00
• CPC Class Codes: C08L 101/16 the macromolecular compounds being biodegradable
• CPC Class Codes: C08L 67/04 Polyesters derived from hydroxycarboxylic acids, e.g. lactones C08L67/06 takes precedence
• CPC Class Codes: C09K 8/035 Organic additives

Abstract

Embodiments may generally take the form of a degradable composite structure and a method for controlling the rate of degradation of a degradable composite structure. An example embodiment may take the form of a degradable polymer matrix composite (PMC) including a matrix having: a degradable polymer, a fiber reinforcement, and particulate fillers. The fiber loading is between approximately 10% to 70% by weight and the particulate loading is between approximately 5% to 60%.

Claims

1. A degradable polymer matrix composite (PMC) comprising:

a matrix comprising;

a degradable polymer;

a fiber reinforcement, wherein the fiber loading is between approximately 10% to 70% by weight; and

particulate fillers, wherein the particulate loading is between approximately 5% to 60%.

2. The PMC of claim 1, wherein the degradable polymer comprises at least one selected from the group represented by:

aliphatic polyesters, poly(lactic acid) (PLA), poly(ε

-caprolactone), poly(glycolic acid) (PGA), poly(lactic-co-glycolic acid), poly(hydroxyl ester ether), polyhydroxyalkanoate (PHA), poly(hydroxybutyrate), poly(anhydride), polycarbonate, poly(amino acid), poly(ethylene oxide), poly(phosphazene), polyether ester, polyester amide, polyamides, sulfonated polyesters, poly(ethylene adipate), polyhydroxyalkanoate, poly(ethylene terephtalate), aliphatic polyethers, poly(butylene terephthalate), poly(trimethylene terephthalate), poly(ethylene naphthalate), polyamide (nylon), polyurethane and copolymers.

3. The PMC of claim 2, wherein the degradable polymer comprises blends, derivatives or a combination of the degradable polymers.

4. The PMC of claim 1, wherein the fiber reinforcement comprises continuous fibers.

5. The PMC of claim 1, wherein the fiber reinforcement comprises discontinuous fibers.

6. The PMC of claim 1, wherein the fiber reinforcement comprises continuous and discontinuous fibers.

7. The PMC of claim 1, wherein the fiber reinforcement comprises one or more of:

glass fiber, carbon fiber, polymer fiber, boron, ceramic, and metal fiber.

8. The PMC of claim 1, wherein the fiber reinforcement comprises at least one of:

water soluble fibers, acid soluble fibers, and biodegradable fibers.

9. The PMC of claim 1, wherein the particulate filler comprises at least one of:

clay, talc, aluminum trihydrate (Al(OH)₃), calcium carbonate, magnesium carbonate, glass beads, silica, silicate minerals, microspheres, ceramic particles, metals powders, mica, and Al₂O₃.

10. The PMC of claim 1 further comprising at least one of:

a flame retardant, an impact modifier, a coupling agent, a plasticizer, a pigment, a UV stabilizer, an antioxidant, and an anti-fouling agent.

11. The PMC of claim 10, having one or more of:

thermal conductivity, electrical conductivity, UV stability, and fire resistance.

12. The PMC of claim 1 further comprising at least one of:

carbon black, carbon nanotubes, graphite and graphite nano-platelets (GNP), core-shell polymers, rubber particles, and PHA (Metabolix), plasticizers, silane, 2-hydroxyethylmethacrylate acid phosphate, 2-hydroxyethyl methacrylate phosphates, long chain fatty acids, and their ester derivatives of long chain fatty acids.

13. The PMC of claim 1 further comprising a catalysts to control the rate of matrix degradation.

14. The PMC of claim 13, wherein the catalyst comprises at least one of:

Ca(OH)₂;

Mg(OH)₂;

CaCO₃;

Al(OH)₃;

Borax;

MgO;

CaO;

ZnO;

CuO;

Al₂O₃;

ZrO₂;

oxides of titania, zirconia, magnesia, a base or a base precursor in the form of particles, films, sheets, foams or combination of these shapes.

15. The PMC of claim 13, wherein the catalyst comprises water soluble and phase changing fillers.

16. The PMC of claim 15, wherein the water soluble and phase changing filler comprises at least one of:

salt (NaCl), KCl, ZnCl₂, CaCl₂, MgCl₂, NaCO₃, KCO₃, potassium phosphate (KH₂PO₄, K₂HPO₄, K₃PO₄), and sulfonate salts such as sodium benzenesulfonate (NaBS), sodium dodecylbenzenesulfonate (NaDBS), water soluble/hydrophilic polymers, poly(ethylene-co-vinyl alcohol) and poly(vinyl alcohols) (PVOH), modified PVOH.

17. The PMC of claim 1, wherein the PMC comprises one of:

a layered structure of composite tapes, films, foams and a composite tape of a solid catalyst.

18. The PMC of claim 17, wherein the tape is pre-treated and rendered porous.

19. The PMC of claim 17 further comprising a layer of a film of solid acid, base, or catalyst.

20. The PMC of claim 1 further comprising heating materials that generate heat.

21. The PMC of claim 1 further comprising at least one of a hydrolosis inhibitor and a low energy additive.

22. The PMC of claim 1 being shaped into a generally cylindrical or spherical shape for use as part of a tool deployed in a well.

23. The PMC of claim 22, wherein the PMC is integrated into a perforating gun.

24. The PMC of claim 22, wherein the PMC is a frac ball.

25. A method of manufacturing the PMC of claim 1.