Patent Application
20180051147
The present invention relates generally to the field of damage- and impact-tolerant carbon-fiber-reinforced composites [“CFRCs”] and more particularly to damage- and impact-tolerant CFRC structures for structural aerospace applications.
CFRCs are known in the art. They generally comprise a matrix, such as a polymer resin, for example an epoxy or other polymer, and a reinforcement of carbon fibers. The carbon fibers might also contain other fibers, such as aluminum or glass. Structures of various aerospace applications are often made in whole or in part of CFRC.
The initiation and propagation of damage ultimately results in failure of aerospace structural components. Typical structural repairs often result in damaging practices, where material is ground away and holes are drilled to secure patches, which can act as new sites for damage. By healing known damage or by providing healing material to areas that are suspected to incur damage, improved safety can be realized. Damage-tolerant, self-healing structural systems provide a route towards this objective. Effective self-repair, however, requires that these materials heal quickly following low- and mid-velocity impacts, while retaining structural integrity. Although there are materials known to possess this characteristic, such is not the case for structural engineering systems.
Self-healing materials display the unique ability to mitigate incipient damage and have built-in capability to substantially recover structural load transferring ability after damage. Structures that make use of self-healing engineering materials produce a healing response from a change in the material's chain mobility as a function of the damage mechanism/condition involved. This type of material will possess better mechanical properties, healing capability at elevated temperatures, faster healing rates (less than 100 microseconds), and healing without the need of foreign inserts or fillers (via structural chemistry). These materials might have application as structural aerospace applications.
In recent years, researchers have studied different “self-healing mechanisms” in materials as a collection of irreversible thermodynamic paths where the path sequences ultimately lead to crack closure or resealing. Crack repair in polymers using thermal and solvent processes, where a healing process triggered with heating or with a solvent has been studied. A second approach involves the autonomic healing concept, where healing is accomplished by dispersing a microencapsulated healing agent and a catalytic chemical trigger within an epoxy resin to repair or bond crack faces and mitigate further crack propagation. A related approach, the microvascular concept, utilizes brittle hollow glass fibers in contrast to microcapsules filled with epoxy hardener and uncured resin in alternate layers, with fluorescent dye. An approaching crack ruptures a hollow glass fiber, releasing a healing agent into the crack plane through capillary action. A third approach utilizes a polymer that can reversibly re-establish its broken bonds at the molecular level by either thermal activation (e.g., based on Diels-Alder rebonding), or ultraviolet light. A fourth approach, structurally dynamic polymers, are materials that produce macroscopic responses from a change in the materials' molecular architecture without heat or pressure. A fifth approach, self-healing fiber-reinforced composites, involves integrating self-healing resins into fiber reinforced composites. Various chemistries have been used based on some of the aforementioned approaches described above. Although significant recovery (>90 percent) of virgin neat resin material properties have been reported, this range has not been the case for fiber-reinforced composites made from them.
The aforementioned self-healing approaches that address the repair or mitigation of crack growth and various damage conditions in materials, have the following disadvantages: (1) Slow rates of healing; (2) Use of foreign inserts in the polymer matrix that may have detrimental effects on composite performance; (3) Samples have to be held in intimate contact or under load and/or fused together under high temperature for long periods of time; and (4) The material may not be considered a structural load-bearing, material.
For example, ionomers containing ionic groups at low concentrations (<15 mol percent) along the polymer backbone. In the presence of oppositely-charged ions, these ionic groups form aggregates that can be activated by external stimuli such as temperature or ultraviolet irradiation. One such ionomer, poly(ethylene-co-methacrylic acid) [EMAA], also known under the trade name Surlyn®, undergoes puncture reversal (self-healing) following high-velocity ballistic penetration. The heat generated from the damage event triggers self-healing in this material. Although EMAA polymers possess excellent puncture healing properties, their low tensile modulus (308 MPa) limits their use as an engineering polymer in structural aerospace applications.
Also, a self-healing composite laminate system that possesses aerospace quality consolidation with fiber volume fraction (FVF) of up to 57 percent and void volume fraction of less than two percent does not currently exist. Most self-healing composite laminates that have been reported possess 20-30 percent fiber volume, which is well below aerospace industrial standards for fiber-reinforced composites (FRC).
A need exists for an inherently self-healing composite laminate matrix that does not rely on foreign inclusions for self-repair and which has mechanical properties with potential for aerospace applications. A need further exists for an appropriate process for making such a matrix, for an appropriate process for making CFRCs from such a matrix, and for repairing such CFRCs.
A composite comprising a combination of a polybutadiene graft copolymer matrix and a carbon-fiber reinforcement is provided. Additionally, a method of fabricating a composite comprising the steps of manufacturing a pre-impregnated unidirectional carbon fiber preform by wetting a plurality of carbon fibers with a solution, the solution comprising a self-healing polymer and a solvent, and curing the preform, is provided. Moreover, a method of repairing a damage composite of the invention is provided. Other features and advantages will become apparent upon a reading of the attached specification, in combination with a study of the drawings.
The organization and manner of the structure and operation of the invention, together with further objects and advantages thereof, may best be understood by reference to the following description, taken in connection with the accompanying drawings, wherein like reference numerals identify like elements in which:
While the invention may be susceptible to embodiment in different forms, there is shown in the drawings, and herein will be described in detail, specific embodiments with the understanding that the present disclosure is to be considered an exemplification of the principles of the invention, and is not intended to limit the invention to that as illustrated and described herein. Therefore, unless otherwise noted, features disclosed herein may be combined together to form additional combinations that were not otherwise shown for purposes of brevity.
In one embodiment, a polybutadiene graft copolymer (PBg) was selected as a matrix in carbon-fiber-reinforced composites due to its higher mechanical and thermal properties as compared to the other self-healing thermoplastics which have been studied. According to material suppliers, PBg has a glass transition temperature (Tg)=80 degrees Celsius (° C.), room temperature (RT) tensile strength of 37 MPa, RT tensile modulus of 2.47 GPa, and a 7.5 percent elongation at break. The tensile modulus of the neat polymer is about 10 percent lower than the 2.76 GPa required of matrix polymers typically used in aerospace primary structural applications. In one embodiment, the matrix is a polybutadiene graft copolymer matrix, such as a polybutadiene graft copolymer comprising poly(butadiene)-graft-poly(methyl acrylate-co-acrylonitrile). In an embodiment, the self-healing polymer comprises poly(butadiene)-graft-poly(methyl acrylate-co-acrylonitrile). In some embodiments, the matrix is a soluble matrix that allows for processing of the self-healing thermoplastic composite. In further embodiments, the solvent used to process the matrix is N-methylpyrrolidone.
Structures using self-healing polymer matrices such as, for example, PBg provide the following advantages: (1) increased damage tolerance compared to thermosetting polymer matrices which incur a greater extent of impact damage as compared to PBg composites, based upon C-scan data; (2) Self-repairing polymer matrices provide a route for recovery of a large proportion of the pristine mechanical properties, thus extending the life of the structure; (3) Since self-healing is an intrinsic property of the matrix material, this matrix can be treated a direct substitute to conventional thermosetting matrices that do not possess self-healing characteristics; (4) The intrinsic healing of PBg does not require the introduction of microcapsules needed by other healing polymer matrices described in the prior art section; it therefore has the advantage of not needing microcapsules which can act as defect initiators in the composite; (5) As long as there is no loss of matrix material incurred in the damage event, PBg can self-heal repeatedly, compared to the microcapsule approach, where healing is limited by the amount of monomer present at the site where damage occurs. In some embodiments, the self-healing polymer is able to heal crack(s) and/or puncture(s) in the structure.
A composite fabrication process cycle was developed from composite precursor materials to fabricate composite laminates for aerospace structures. The precursor material is a pre-impregnated unidirectional carbon-fiber preform, also known as a prepreg. In the prepregging process, the high-strength, structural reinforcing IM7 carbon fiber is wetted by a solution containing the self-healing PBg polymer dissolved in N-Methylpyrrolidone (NMP). Precursor materials in the form of unidirectional prepreg are widely used in the aerospace industry to fabricate and manufacture aerospace composite structures for both commercial and military aviation and space launch vehicle systems. The experimental prepreg containing the puncture-self-healing polymer PBg was characterized and a cure cycle developed to be used in fabrication of composite laminate test coupons from this novel prepreg material.
A self-healing thermoplastic PBg, poly(butadiene)-graft-poly(methyl acrylate-co-acrylonitrile), a polybutadiene graft copolymer, was obtained in pellets from Sigma-Aldrich. The chemical structure of this PBg is shown in
As a first step in determining the CFRC processing temperature window, the glass transition (Tg) of the PBg polymer pellets was verified by conducting a dynamic temperature scan in nitrogen from 25° C. to 300° C. at 5° C./min in a Netzsch 204-F1 Phoenix® differential scanning calorimeter (DSC). In addition to the dynamic scan in DSC, dynamic temperature scans in nitrogen from 25° C. to 300° C. at 5° C./min were conducted using a Netzsch TG-209-F1 Libra® thermo-gravimetric analyzer (TGA) to determine the decomposition temperature of the pristine PBg polymer.
Residual solvent content in IM7/PBg prepreg was obtained from end-roll specimens of the prepreg batch, designated tape machine run # (TM-341), using a dynamic temperature scan from a thermo-gravimetric analyzer (TGA) under a nitrogen purge from 25° C. to 300° C. at five ° C./min. The TGA was a Netszch TG-209-F1 Libra® TGA. This data was also used to determine the temperature which would be required to remove the volatiles (NMP) from the IM7/PBg prepreg during CFRC processing. Using these results to initially select an isothermal dwell temperature in the CFRC processing prior to the compaction step, the time duration of this proposed dwell was determined by performing an isothermal scan at 150° C. and 225° C. in TGA of the IM7/PBg prepreg. Using a specimen from the TM341 roll of IM7/PBg prepreg, the mass evolution of the material during the proposed CFRC process cycle was determined in the Netzsch TGA by heating to 150° C. at 5° C./min and holding for one hour under nitrogen purge and then heating from 150° C. to the mold compaction temperature of 225° C. at five ° C./min and holding for two hours.
The PBg polymer was molded into neat resin disks 2.54 cm in diameter by 1.5 millimeters (mm) in thickness for rheological characterization in a Rheometrics ARESV® parallel plate rheometer. All of the rheology results presented in this study were collected using a cyclic strain of two percent. A dynamic temperature scan in nitrogen was conducted from 25° C. to 285° C. at 5° C./min. Based on the results of the TGA thermogram, an isothermal temperature scan at 150° C. and 225° C. was performed on the solution of NMP containing 31 percent solids PBg to determine the change in the dynamic viscosity as the matrix material devolatilizes during the proposed processing cycle.
Pellets of the PBg polymer were dissolved in anhydrous NMP by continuously stirring for 48 hours at 25° C. under nitrogen purge. The resulting uniform mixture contained 31 percent solids in NMP by weight. The Brookfield viscosity of the resulting solution at 25° C. was determined to be 21.12 Pa*sec (211.20 poise). This viscosity was acceptable for the solution prepregging process. Two experimental batches of PBg prepreg were fabricated with prepregging equipment. The 22 to 25 centimeters (cm) wide prepregs were fabricated using 90 unsized IMT-12K tows by introducing the PBg-NMP polymer in solution to the unsized IM7 fiber via the dip tank in the prepregging process. Using an established procedure of weighing, oven drying, and reweighing samples of the prepreg, the resulting fiber areal weight (FAW), PBg resin and NMP solvent content of these two experimental batches were determined.
The processing cycle determined following the above tests was then used to fabricate three [45/0/−45/90]4s IM7/PBg panels including geometries of 7.6 cm×7.6 cm, 15.2 cm×15.2 cm, and 30.5 cm×30.5 cm. Material from the first prepreg batch was processed in stainless steel closed molds using a TMP® three-ton vacuum press with a layer of breather and release cloth separating the stack of prepreg from the stainless steel mold base and plunger. A 15.2 cm×15.2 cm [45/0/−45/90]4s panel was fabricated in the same mold and vacuum press using Cytec IM7/977-3 toughened epoxy prepreg and the Cytec recommended processing cycle, C-49. Both the IM7/PBg and the IM7/977-3 15.2 cm×15.2 cm panels were cross-sectioned at the center using a wet saw and then potted and polished for optical microscopy in a Reichert MEF4 M microscope. Following ASTM D3171, FVF/VVF analysis by acid digestion were conducted for this IM7/PBg panel and three subsequently processed 15.2 cm×15.2 cm IM7 PBg panels. Based on these results, six additional [45/0/−45/90]4s 15.2 cm×15.2 cm IM7/PBg panels were fabricated from prepreg batch (TM-340) and six from prepreg batch (TM-341) in the vacuum press for the purpose of determining the compression after impact (CAI) strength of these composite materials after low-velocity impact damage.
Nine IM7/PBg panels were prepared as test coupons and subjected to low-velocity impact according to ASTM D7136. A spherical tup was used to impact each 15.2 cm×10.1 cm coupon at the center. The average coupon thickness of the six panels fabricated from prepreg batch TM340 was 5.40 mm, and an impact energy of 36.08 J was used to damage these coupons. The six panels fabricated from prepreg batch TM-341 had an average thickness of 4.62 mm. Four of these six panels were damaged using an impact energy of 31.09 J. Non-destructive evaluation (NDE) by through-transmission, time-of-flight c-scan of these impacted panels was conducted using a Sonotek® c-scan with a 10 MHz transducer. After c-scan of all of the damaged coupons, one of the coupons from the panels fabricated using the TM-340 prepreg batch and three of those fabricated using the TM-341 batch were randomly selected and subjected to an elevated temperature/pressure healing cycle in the vacuum press using the following cycle:
25° C. to 225° C. at five ° C./min under full vacuum;
hold at 225° C. for 30 minutes under full vacuum and 1.7 MPa pressure; and
cool down the vacuum press to 25° C. at five ° C./min under full vacuum. In some embodiments, the vacuum press is cooled such that the sample cools slowly while still under full vacuum.
Both pristine and damaged IM7/PBg quasi-isotropic laminates were tested according to ASTM D7137 using a CAI test fixture in an MTS 250KN Load Frame. In addition, the pristine compression strength of the IM7/PBg was determined by mounting these pristine 15.2 cm×10.1 cm coupons in the CAI fixture and loading them in axial compression.
The Tg of the polymer was determined at the inflection in the heat vs temperature curve shown in
The results of the dynamic temperature scan in TGA shown in
Residual solvent trapped in the prepreg will result in composite parts with high void content. The thermogravimetric scan shown in
Using these results, an isothermal dwell temperature of 150° C. in the CFRC processing cycle was initially selected to devolatilize the IM7/PBg prepreg prior to the compaction step at 225° C. The temperature of 150° C. also coincides with the reduced viscosity determined by rheological analysis. The time required in the proposed devolatilization dwell was investigated by isothermal TGA of the IM7/PBg prepreg. Shown in
Having determined the Tg and the decomposition temperature of the PBg polymer, the CFRC processing temperature window exists between about 75° C. and about 300° C. Thermoplastic polymers are typically difficult to process as matrix in CFRC because the long molecular chains of these polymers make the bulk material highly viscous. Knowing the thermal processing window, the dynamic viscosity versus temperature of the PBg polymer was determined via parallel plate rheology. The dynamic-temperature rheology scan in
After determining the mass evolution in TGA of the IM7/PBg prepreg during the proposed CFRC processing devolatilization step at 150° C. and compaction step at 225° C., the effect of these processing dwells on the dynamic viscosity of the PBg polymer was investigated in parallel plate rheology. The results of this isothermal temperature scan performed using the PBg-NMP prepregging solution are shown in
The resin film infusion (RFI) process is preferable to alternative methods that require an intermediate step of pre-impregnating carbon fiber tows with resin. However, the photomicrograph in
It is noted that the PBg resin was able to flow around the IMT-6K fiber tows in the biaxial fabric, but does not penetrate the tows. In fact the tows which are 90-degrees to the plane are clearly surrounded by a region of voids. Based on these results, the effort to fabricate CFRC with PBg thermoplastic matrix focused on the development of a processing method with an intermediate prepreg material.
Two experimental batches of PBg prepreg were fabricated using prepregging equipment. The fiber areal weight (FAW), PBg resin and NMP solvent content of these two experimental batches are displayed in Table 1.
Based on the results obtained in the thermal and rheological analysis of the IM7/PBg experimental prepreg, the processing cycle in the vacuum press for the IM7/PBg composite was selected to be:
Using these conditions, three [45/0/-45/90]4s panels measuring 7.6 cm×7.6 cm, 15.2 cm×15.2 cm, and 30.5 cm×30.5 cm were fabricated. Upon visual inspection, all three of these panels exhibited higher consolidation quality than the previous RFI panels. Both the IM7/PBg and the IM7/977-3 15.2 cm×15.2 cm panels were cross-sectioned at the center using a wet saw and then potted and polished for photo microscopy. The resulting images are shown side-by-side for comparison in
The micrographs in
Nine IM7/PBg panels were subjected to low-velocity impact resulting in an average damage dent depth of 1.9 mm (0.075 in). The damage regions of all the impacted coupons were analyzed by c-scan. A representative image of the damage incurred in the IM7/PBg panels is shown in
Four of the BVID IM7/PBg panels were subjected to an elevated temperature/pressure healing cycle described above and then tested to failure in compression to determine the influence of the cycle on the IM7/PBg composite CAI failure strength. The time-of-flight c-scan image of one of these IM7/PBg panels before and after, healing is shown in
The results of the axial compression of the two pristine IM7/PBg coupons, the five BVID coupons and the four BVID coupons subjected to an elevated temperature/pressure healing cycle are shown in
All of the coupons failed due to fiber micro-buckling. In the five BVID coupons, this failure initiated at the site of the impact damage and propagated across the width of the coupons. The four IM7/PBG coupons containing BVID which were subjected to an elevated temperature/pressure healing cycle also failed due to fiber microbuckling initiating at the original impact site and propagating across the 10.2 cm width of the coupons. The pristine compressive strength resulting from this limited sample of coupons of quasi-isotropic laminates was about 52 percent of the compressive strength of the 675 MPa reported for a typical toughened epoxy 32-ply quasi-isotropic CFRC intended for aerospace structure.
The CAI strength of the BVID coupons appears to be independent of the prepreg batch. This is expected since the failure of these coupons is dominated by the impact damage and in this study the impact energy used for BVID was varied to account for the panel thickness variation resulting from prepreg batch inconsistency. The inconsistency of the prepreg batches was not of significant concern at this initial phase in the study given that all of the IM7/PBg prepreg were considered experimental. The differences in the batch to batch quality is noted in Table 1 and demonstrates that there is considerable room for improvement in both the quality of the prepreg and the resulting mechanical performance of CFRC panels fabricated from the intermediate material. In addition to the inconsistencies in the experimental prepreg, the fiber/matrix interface is not optimized with fiber sizing used to optimize the interfacial adhesion in toughened epoxy CFRCs.
Regardless of prepreg batch, there was a significant improvement in the failure strength of the BVID coupons subjected to an elevated temperature/pressure healing cycle vs the BVID panels which were not healed. The TM340 batch of damaged IM7/PBg panels exhibited a 64 percent retention of compressive strength. The retention of compressive strength of coupons fabricated from this same batch of prepreg, which were subjected to BVID and then the elevated temperature/pressure healing cycle was found to be 80 percent. However, the large error associated with the BVID-Heal coupons from the second prepreg batch (B2) indicates that this notable improvement in compressive strength may be just as dependent on the quality of the CFRC laminate as it is on the healing capability of the matrix. The non-autonomic healing cycle utilized in this initial study amounts to reprocessing of the amorphous thermoplastic PBg matrix in the IM7/PBg composite.
The composite of the present invention will be useful for structures in applications such as, but not limited to, structural components that can be incorporated into vehicles such as aircraft, rotorcraft, and spacecraft. Particular applications that can include these structural components are by way of example and not limitation, combat aircraft, large military transport and bomber aircraft, commercial transport, small transport, general aviation, military rotorcraft, commercial and general aviation rotorcraft, spacecraft, and missiles.
While preferred embodiments of the present invention are shown and described, it is envisioned that those skilled in the art may devise various modifications of the present invention without departing from the spirit and scope of the appended claims.
This patent application is a divisional of U.S. Non-Provisional patent application Ser. No. 14/881,899 filed on Oct. 13, 2015, which was a divisional application of U.S. Non-Provisional patent application Ser. No. 13/774,422 filed on Feb. 22, 2013 (issued as U.S. Pat. No. 9,156,957 on Oct. 13, 2015), which claims the benefit of and priority to U.S. Provisional Application Ser. No. 61/602,717, filed Feb. 24, 2012, for “Puncture Healing Thermoplastic Resin Carbon Fiber Reinforced Composites Towards More Damage/Impact Tolerant Systems”. The contents of the foregoing applications are hereby incorporated by reference in their entireties.
This invention described herein was made in the performance of work under a NASA contract and by employees of the United States Government and is subject to the provisions of Public Law 96-517 (35 U.S.C. §202) and may be manufactured and used by or for the Government for governmental purposes without the payment of any royalties thereon or therefor.
| Number | Date | Country | |
|---|---|---|---|
| 61602717 | Feb 2012 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | 14881899 | Oct 2015 | US |
| Child | 15729189 | US | |
| Parent | 13774422 | Feb 2013 | US |
| Child | 14881899 | US |
