Self-healing and adaptive materials and systems

Abstract

Solid electrolyte and at least one of piezoelectric and thermoelectric materials are incorporated into material systems to provide them with self-healing and adaptive qualities. The piezoelectric and thermoelectric constituents convert the mechanical and thermal energy, respectively, concentrated in critical areas into electrical energy which, in turn, guides and drives electrolytic transport of mass within solid electrolyte towards and its electrodeposition at critical areas to render self-healing and adaptive effects. Material systems incorporating the solid electrolyte but not the piezoelectric and thermoelectric constituents are also amenable to healing and adaptive effects through external application of electric potential for electrolytic transport of mass towards and its electrodeposition at critical areas.

Description

This invention was made with U.S. government support under Contract W911W6-04-C-0024 by U.S. Army. The U.S. government has certain rights in the invention.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The invention is generally related to self-healing and adaptive materials. Particularly, the invention is directed to materials which can alter their internal mass distribution in response to stress and temperature gradients in order to optimally utilize the available structural substance in critical areas subjected to stress and temperature rise.

2. Description of the Relevant Art

Altering service environments as well as damaging effects change the stress and/or temperature distribution within structures. Biological systems such as bone are capable of adapting to changes in stress distribution through transport of substance towards and its deposition at highly stressed areas. This adaptive/self-healing capability enables biological structural systems make optimal use of available materials as new circumstances evolve. Various efforts have been made to develop synthetic materials which mimic the self-healing/adaptive qualities of biological systems.

U.S. Pat. No. 6,518,330 discloses a self-healing material with the polymeric healing agent stored in microspheres which are dispersed within the material systems. Damage (cracking) of the material would cause breakage of the microspheres and release of the healing agent, which fills the crack and rebonds the crack faces. U.S. Pat. No. 5,790,304 discloses self-healing coatings incorporating sacrificial constituents which react with oxygen at defects (e.g., cracks and voids) to produce compounds which condense on such defects and thereby restore the integrity of coating. U.S. Pat. No. 5,965,266 discloses a self-healing high-temperature materials incorporating constituents capable of reacting with oxygen to produce compounds to plug cracks and mitigate access of oxygen to the core of the material. U.S. Pat. No. 4,599,256 discloses a high-temperature material incorporating multiple constituents which, when exposed to the elevated service temperature at cracks, react with each other to produce compounds which seal the cracks. U.S. Pat. No. 5,738,664 discloses a material incorporating a viscous flowable constituent which can flow into defects to restore the integrity of the material.

The above inventions rely on damaging effects (e.g., cracks) to either release the healing agent or to promote chemical reactions (e.g., upon exposure to oxygen or elevated temperatures) which render self-healing and adaptive effects. Unlike the invention described herein, they do not rely on electrolytic mass transport to strengthen highly stressed areas, and they do not convert the destructive mechanical energy concentrated in critical areas to electrical potential and energy which guide and drive the self-healing/adaptive effects.

SUMMARY OF THE INVENTION

It is an object of this invention to provide solid material systems within which substance can be transported for an optimum mass distribution to be realized.

It is another object of this invention to convert the destructive mechanical and/or thermal energy concentrated within critical areas of the material into the electrical energy needed to drive the mass transport phenomenon.

It is another object of this invention to convert the stress and/or temperature gradients within the material into the electric potential which guides transport of mass towards critical areas.

It is another object of this invention to integrate the energy conversion and mass transport capabilities into a material system which is inherently capable of transporting substance towards critical areas to render self-healing and adaptive effects.

Applicant has discovered that electrolytic transport and electrodeposition of mass within solid electrolytes can strengthen and densify areas within which electrodeposition has taken place. Applicant has also discovered that the piezoelectric effect can generate sufficient electric potential and energy, by conversion of mechanical energy, to drive and guide electrolytic mass transport within solid electrolyte.

According to the invention, there is provided composite materials incorporating solid electrolyte and at least one of piezoelectric and thermoelectric constituents, which can strengthen and densify highly stressed areas through electrolytic mass transport and electrodeposition.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows a fiber reinforced composite under stress, where rupture of one fiber has caused local stress rise in an adjacent fiber.

FIG. 2 shows a carbon fiber which has received a hybrid coating comprising a piezoelectric layer and a solid electrolyte layer with dissolved metal salt.

FIG. 3 shows the cross-section of the carbon fiber which has received a hybrid coating comprising a piezoelectric layer and a solid electrolyte layer (with dissolved metal salt).

FIG. 4 shows a carbon fiber with piezoelectric and solid electrolyte coating layers where local stress rise within fiber has prompted piezo-induced electric potential difference along the fiber surface which, in turn, drives electrolytic phenomena within the solid electrolyte layer which transport mass towards and electrodeposit it at the highly stressed area.

FIG. 5 shows a layered composite incorporating piezoelectric, solid electrolyte, conductive and structural layers, experiencing a local stress rise under concentrated force, with piezo-driven electrolytic mass transport and deposition strengthening the highly stressed area where the concentrated force is applied.

FIG. 6 shows a layered composite incorporating piezoelectric, solid electrolyte, conductive and structural layers, experiencing a local stress rise due to the presence of a manufacturing defect, with piezo-driven electrolytic mass transport and deposition strengthening the highly stressed area around the manufacturing defect.

FIG. 7 shows a cylindrical structural element, made of a layered composite incorporating piezoelectric, solid electrolyte conductive and structural layers, subjected to a gradient stress system, with piezo-driven electrolytic mass transport and deposition strengthening regions within the structural element which are subjected to higher stress levels.

FIG. 8 shows a layered composite incorporating solid electrolyte layer, conductive and structural layers, subjected to a structural damage, where electrolytic mass transport and deposition via external power supply is used to strengthen the damaged area.

FIG. 9 shows a thermal protection coating on a substrate, with thermoelectric and solid electrolyte layers introduced as coating constituents, where a damage to thermal protection coating causes local temperature rise, with electrolytic mass transport and deposition driven by thermoelectric effect bracing the damaged area.

FIG. 10 shows the solid electrolyte specimen sandwiched between two aluminum electrodes which are connected to a DC power supply.

FIG. 11 shows the cathode electrode where electrodeposition of copper has taken place for the case with solid electrolyte incorporating dissolved copper salt but no copper filler.

FIG. 12 shows the cathode electrode where electrodeposition of copper has taken place for the case with solid electrolyte incorporating both dissolved copper salt and copper filler.

FIG. 13 shows the electrolysis cell comprising a solid electrolyte sheet sandwiched between two stainless steel electrodes.

FIG. 14 shows a piezo-driven electrolysis test set-up where a piezoelectric sheet is subjected to stress in order to generate the electric potential and charge needed to drive electrolysis phenomena within a solid electrolyte.

FIG. 15 shows: (a) solid electrolyte sheet (with dissolved metal salt) prior to piezo-driven electrolysis; (b) the cathode face of the solid electrolyte sheet after piezo-driven electrolysis, where electrodeposition has taken place; and (c) the anode face of the solid electrolyte sheet after piezo-driven electrolysis.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS OF THE INVENTION

Damaging effects, changes in service environment and manufacturing defects modify the stress and/or temperature distributions which develop within materials, with local stress and/or temperature rise occurring in critical areas which govern eventual failure. Material systems can optimally utilize their available material resources through partial transport of these resources towards critical areas which experience local stress and/or temperature rise, where the rise in material concentration can render strengthening and densification effects to mitigate the initiation or propagation of damage.

Solid electrolytes are solids which can dissolve metal salts. Electrolytic phenomena can occur within solid electrolytes, and can be used to transport structural substance towards and deposit it at particular locations in order to strengthen such locations. The structural substance is present in solid electrolyte in the form of dissolved salt; additional structural substance can be introduced in the form of metals which are in contact with the solid electrolyte.

The electrolysis phenomena within solid electrolyte can be guided and driven by the piezoelectric effect. Piezoelectric and thermoelectric materials generate electric potential and charge under stress and temperature gradient, respectively. If piezoelectric and thermoelectric materials are in proper contact with a solid electrolyte, the electric potential resulting from stress and/or temperature gradients can guide and the corresponding electric charge can drive electrolytic phenomena within the solid electrolyte to transport structural substance towards and deposit it at critical areas experiencing stress and/or temperature rise. The combination of solid electrolyte with at least one of piezoelectric and thermoelectric materials can thus be used to develop material systems which can partially adapt their internal mass distribution to internal stress and/or temperature systems which are altered by at least one of damaging effects, changing service environments, and manufacturing defects.

Material systems incorporating solid electrolyte, piezoelectric, thermoelectric and other constituents can assume diverse configurations. One configuration introduces the solid electrolyte and at least one of piezoelectric and thermoelectric constituents as a multilayer coating system on reinforcing fibers in composites. One other configuration comprises solid electrolyte matrices reinforced with at least one of piezoelectric and thermoelectric fibers; yet another configuration is in the form of laminated composites comprising solid electrolyte, at least one of piezoelectric and thermoelectric, and other layers. Alternatively, the piezoelectric and thermoelectric constituents could be absent, with external power supply used to adjust distribution of structural substance within the solid electrolyte constituent of the material systems.

FIGS. 1 through 4 present the example configuration where the piezoelectric and solid electrolyte constituents are introduced as a hybrid coating on reinforcing fibers in a composite system. FIG. 1 shows a fiber reinforced composite comprising reinforcing fibers and the matrix subjected to external stress; rupture of one fiber is shown to cause local stress rise in an adjacent fiber. FIG. 2 shows a length segment of a carbon fiber that has received a hybrid coating comprising a piezoelectric layer and a solid electrolyte layer with dissolved metal salt. FIG. 3 shows the cross section of the carbon fiber which has received the piezoelectric and solid electrolyte coating layers. FIG. 4 shows the same fiber as in FIGS. 2 and 3 subjected to local stress rise along its length. The stress gradient in piezoelectric material produces electric potential on the surface of the piezoelectric layer which is in contact with the solid electrolyte. This electric potential drives electrolytic transport of metal cations within the solid electrolyte and their electrodeposition at the highly stressed location along the fiber length. This electrodeposition strengthens the fiber at the highly stressed location where fiber rupture could otherwise occur. This process of mass transport towards and its deposition at the highly stressed location would, in the example of FIG. 1, strengthen the damaged zone of the composite material where fiber rupture has occurred, and could thus mitigate the propagation of an otherwise catastrophic failure process.

The examples of FIGS. 1 through 4 introduced the self-healing features of the invention. FIG. 5 depicts the adaptive features of the invention in an example where the piezoelectric and solid electrolyte constituents are introduced as layers within a laminated structural material. Application of a concentrated force in this example, with the laminated composite placed on a flat surface, causes a local stress rise which drives electrolytic mass transport and electrodeposition phenomena to strengthen the highly stressed region under the concentrated force. FIG. 6 presents the laminated composite of FIG. 5 subjected to tensile stress, where a local stress rise is caused by a manufacturing defect, and the electrolytic mass transport and electrodeposition phenomena strengthen the critical area around the defect. FIG. 7 presents a cylindrical element made of a laminated composite similar to that presented in FIG. 5, with an eccentric load generating an unsymmetric stress distribution; electrolytic mass transport and electrodeposition phenomena in this case tend to normalize the stress distribution and approach an optimum use of structural materials. Finally, FIG. 8 shows an application where the piezoelectric constituent is not present, and external application of electric potential drives the electrolytic mass transport and electrodeposition phenomena within solid electrolyte to strengthen a damaged location of the material system.

The key applications of the technology introduced above focus on structural applications where conversion of mechanical to electrical energy drives electrolytic phenomena which strengthen highly stressed areas of the structure. Piezoelectricity is the specific effect which converts mechanical energy to electrical energy in structural applications. Another implementation of the technology is in thermal protection systems where conversion of thermal energy to electrical energy, via the thermoelectric effect, drives electrolysis phenomena within solid electrolyte to transport substance towards and deposit it at locations experiencing elevated temperature in order to enhance local thermal protection qualities. FIG. 9 shows an application where damage to thermal protection coating causes a local rise in temperature of the substrate with thermoelectric and solid electrolyte coating layers. The thermoelectric effects generates electric potential which guides electrolytic transport and deposition of mass at damaged area in order to restore the integrity of the damaged protective coating.

INVENTION AND COMPARISON EXAMPLES

Example 1

Solid electrolytes were prepared with dissolved metal salt, without and with fine copper filler. Electrolysis phenomena occurring in the context of a solid electrolyte, causing electrodeposition of metal at cathode, were verified experimentally.

Materials

Poly(acrylonitrile) (PAN, M_w=86,200), ethylene carbonate (EC, 98%), propylene carbonate (PC, 99%), copper (II) trifluoromethanesulfonate (CuTf, 98%), copper powder (3 micron, dendritic, 99.7%), and acetonitrile (99.93%+, HPLC grade) were purchased from Aldrich, and were used without any further purification. The use of copper slat in this investigation implies that copper is the metal to be ionically transported and electrodeposited to render self-healing effects. A variety of other metals (nickel, etc.) can replace copper in the process.

Preparation of Solid Electrolyte without Copper Filler

PAN (1.06 g or 20 mole %), EC (3.6 g or 41 mole %) and CuTf (1.8 g or 5 mole %) were weighed into a ceramic crucible and mixed well before adding PC (3.4 g or 34 mole %). PC was then added, and the blend was stirred until thorough dissolution and a mixture of uniform light blue color was obtained. The mixture was then heated to 120° C. and maintained at this temperature for 45 minutes (using a temperature-programmed oven with heating rate of 20° C./min, and total heating duration of 51 minutes). The mixture was allowed to cool down to room temperature, and was then vacuum dried for 24 hours, and further dried at 60° C. under vacuum for 2 hours. The end product was light green in color, and it was pressed to yield the test specimen.

Preparation of Solid Electrolyte with Copper Filler

The copper salt dissolved in solid electrolyte can act as the source of metallic ion to be transported and deposited for self-healing effects. In addition, one can add copper fillers to raise the quantity of metal available to render self-healing effects. In order to prepare the PAN-based solid electrolyte incorporating copper filler, first PAN, EC and CuTf were weighed in a ceramic crucible, and mixed well before adding PC. PC was then added, and the mix was magnetically stirred until thorough dissolution (a uniform mixture) was achieved after about 1 hour. Different amounts of copper particles were then added to the mix and magnetically stirred until a mixture with uniform light brown/blue color was obtained; the intensity of brown color depended on the dosage of copper filler. The mixture incorporated 1.0 g of water for 10% filler content. The remaining steps in synthesis and pressing of solid electrolyte specimens with copper filler were similar to those taken for the specimen without filler.

Experimental Procedure

The solid electrolyte was tightly sandwiched between two aluminum electrodes, as shown in FIG. 10, and a constant voltage was applied for a period of three days. After three days, the aluminum electrodes at anode and cathode were inspected visually.

Test Results and Discussion

Since the solid electrolyte has some copper salt dissolved in it, even with no copper filler added to the solid electrolyte, indications of electrodeposition of copper was observed to occur on the aluminum sheet at cathode, as shown in FIG. 11, with no such deposition observed at anode.

Copper fillers were added to the PAN-based solid electrolyte to complement the dissolved metal salt as the source of metal for electrolysis processes which render self-healing effects. In the case of solid electrolyte with metallic filler, dispersed copper fillers as well as the dissolve copper salt were the sources of copper for the electrolysis process. FIG. 12 shows the aluminum sheet surface at cathode after application of constant voltage. Electrodeposition of copper on aluminum sheet at cathode is apparent in FIG. 12, with no such deposition observed at anode.

Example 2

Materials: The materials used for preparation of PVDF-HFP solid electrolyte included poly(vinylidine fluoride-co-hexafluropropylene) (PVDF-HFP) (pellets, crystalline copolymer, 15% HFP, average M_w˜400,000), ethylene carbonate (EC, 98%), propylene carbonate (PC, 99%), copper (II) trifluoromethanesulfonate (CuTf, 98%), and tetrahydrofuran (THF, 99.9+HPLC grade, inhibitor free). The electrodes were made of 50 micron thick stainless steel shims. The copper salt was used in this verification study as an example; other metal salts could replace the copper salt to yield self-healing and adaptive effects by deposition of metals with higher performance-to-weight rations than copper.

Two different solid electrolytes were prepared by varying the proportions of copper salt, EC and PC while keeping the PVDF-HFP percentage constant. In order to prepare the solid polymer electrolyte with 3% copper ion concentration, PVDF-HFP was dissolved in THF (30% by weight, 3 g) at 60° C. Subsequently, CuTf (1.8084 g), EC (3.5224 g) and PC (1.7865 g) were added to the mix (70% by weight at CuTf:EC:PC ratios of 1.0:8.0:3.5), and dissolved until a uniform solution was obtained. The solution was cast on a Petri dish, and left at room temperature until all the THF was evaporated. A free standing polymer sheet of blue/green color was obtained, which was cut into pieces for use in electrochemical experiments. Since the most common coordination number of copper is four, each copper ion will bind with four fluorine atoms (FIG. 12a). This defines the maximum copper ion-to-polymer molar ratio of 2, which guides our efforts to increase the concentration of copper ions in PVDF-HFP.

In order to prepare the solid polymer electrolyte with 6% copper ion concentration, PVDF-HFP was dissolved in THF (30% by weight, 3 g) at 60° C. Subsequently, CuTf (3.6168 g), EC (1.7612 g) and PC (0.89325 g) were added to the mix (70% by weight at CuTf plus EC plus PC), and dissolved until a uniform solution was obtained. The solution was cast on a Petri dish, and left at room temperature until all the THF was evaporated. A free standing polymer sheet of blue/green color was obtained, which was cut into pieces for use in electrochemical experiments. Since the most common coordination number of copper is four, each copper ion will bind with four fluorine atoms. This defines the maximum copper ion-to-polymer molar ratio of 2, which guides efforts to increase the concentration of copper ions in PVDF-HFP.

Experimental Procedures

In order to validate piezo-induced electrolysis within solid electrolyte, PVDF-HFP specimens with dissolve copper salt was sandwiched between two stainless steel electrodes, as shown in FIG. 13. Piezoelectric (PZT fiber reinforced composite) sheets were then subjected to repeated stress application, as shown schematically in FIG. 14, and the piezo-induced voltage was applied between the electrodes. Current was measured at pico amp precision (between the piezo-setup and electrodes). The basic elements of the test set-up are depicted in FIG. 13. The current flowing through the solid electrolyte was found to be 20 μA; a load frequency of 3 Hz was used in this experiment which lasted 18 hours. After this period, the solid electrolyte surfaces at anode and cathode were inspected visually, and were subjected to hardness tests (ASTM D 2240) in order to assess any changes in mechanical attributes associated with electrolytic mass transport and deposition.

Experimental Results

The experimental results provided clear evidence of metal deposition at cathode interface under piezo-driven electrolysis in solid electrolyte. FIG. 15a shows the solid electrolyte with dissolved metal salt prior to piezo-driven electrolysis. Observation of the cathode and anode interfaces of the solid electrolyte after the test, shown in FIGS. 15b and 15c, respectively, provided clear evidenced for piezo-driven electrolysis at cathode. After piezo-driven electrolysis, the solid electrolyte adhered to the electrode at cathode. The hardness values at anode and cathode after piezo-driven electrolytic mass transport and deposition were 33.3 and 48.1 Shore A (ASTM D 2240), respectively, compared with a hardness value of 34.0 Shore A (ASTM D 2240) for the solid electrolyte prior to piezo-driven electrolysis. The results indicate more than 40% gain in hardness (representing mechanical attributes) at cathode where electrodeposition has taken place, confirming the gain in mechanical properties at cathode associated with piezo-driven electrolysis within solid electrolyte. On the other hand, anode experiences only about 2% loss of hardness, indicating that the local gains in mechanical performance at cathode are achieved through piezo-driven electrolysis without any major loss of mechanical performance elsewhere.

Claims

1. Self-healing and adaptive materials and systems incorporating solid electrolytes with dissolved salts, and at least one of piezoelectric and thermoelectric materials, wherein gradient stress or temperature distributions indicating development of critical areas with elevated stress or temperature levels induce, via at least one of piezoelectric and thermoelectric effects, gradient electric potentials which transport substance towards and deposit it at said critical areas by electrolytic processes within solid electrolyte, rendering self-healing and adaptive effects.

2. The self-healing and adaptive materials and systems of claim 1, wherein at least one of structural, protective and functional constituents are incorporated to meet service requirements.

3. The self-healing and adaptive materials and systems of claim 1, wherein the solid electrolytes are at least one of inorganic, organic and composite ion-conducting materials.

4. The self-healing and adaptive materials and systems of claim 1, wherein the salts dissolved in solid electrolytes are metal salts, with self-healing and adaptive effects involving electrolytic transport of metal cations and electrodeposition of metals at critical areas.

5. The self-healing and adaptive materials and systems of claim 1, wherein the salts dissolved in solid electrolytes are metal salts, and metal fillers are also incorporated into the solid electrolyte, with electrostripping of metal fillers providing additional metal cations to be transported and electrodeposited to render self-healing and adaptive effects.

6. The self-healing and adaptive materials and systems of claim 1, wherein the piezoelectric constituents are at least one of inorganic, organic and composite piezoelectric materials.

7. The self-healing and adaptive materials and systems of claim 1, wherein the thermoelectric constituents are at least one of metallic, inorganic, organic and composite thermoelectric materials.

8. Materials and systems that are amenable to externally stimulated healing and adaptive effects, incorporating solid electrolytes with dissolved salts and optionally at least one of structural, protective and functional constituents, wherein external application of electric potential to the system transports substance towards and deposits it at said critical areas by electrolytic processes within solid electrolyte, to heal damaged or defective areas, or to adapt the material to new service requirements.

9. The materials and systems of claim 8, wherein at least one of structural, protective and functional constituents are incorporated to meet service requirements.

10. The materials and systems of claim 8, wherein the solid electrolytes are at least one of inorganic, organic and composite ion-conducting materials.

11. The materials and systems of claim 8, wherein the salt dissolved in solid electrolyte is a metal salt, with the healing and adaptive effects involving electrolytic transport of metal cation and electrodeposition of metal at critical areas.

12. The materials and systems of claim 8, wherein the salt dissolved in solid electrolyte is a metal salt, and metal fillers are also incorporated into the solid electrolyte, with electrostripping of metal fillers providing additional metal cations to be transported and electrodeposited to render self-healing and adaptive effects.