42nd AIAA/ASME/SAE/ASEE Joint Propulsion Conference & Exhibit 9 - 12 July 2006, Sacramento, California

AIAA 2006-4718

HIGH PRESSURE COPVS FOR CRYOGENIC STORAGE APPLICATIONS

James Patterson HyPerComp Engineering, Inc. Brigham City, UT Tom DeLay Nonmetallic Materials and Manufacturing Processes NASA-Marshall Space Flight Center Huntsville, AL Judy Schneider, Justin Jackson, Paul Allison Department of Mechanical Engineering Mississippi State University Mississippi State, MS

ABSTRACT
A collaborative team of researchers at HyPerComp Engineering, Inc. (HEI), the NASA-MSFC, and Mississippi State University (MSU) has been working to develop a complete understanding of the whole picture of designing, fabricating, and utilizing composite over-wrapped pressure vessels (COPVs) capable of performing extraordinarily well at cryogenic liquid nitrogen (LN2) temperatures. The intent is to develop the necessary understanding and technology to produce high performance, light weight, reliable cryogenic vessels for aerospace launch vehicles and space exploration. In addition to constituent material coupon, neat resin, and single fiber testing, extensive use of actual COPVs for burst and cycle/burst testing at both LN2 and ambient conditions has been performed. To date the following has been demonstrated: Standard composite material systems demonstrate reduced COPV ultimate performance at cryogenic temperatures. Testing and life cycle performance verification must be performed under actual service conditions; cryogenic exposure with subsequent ambient ultimate testing can lead to misleading conclusions. Experimental fiber/resin material systems have demonstrated potentially excellent COPV performance at cryogenic conditions. This developing understanding of how composite materials behave at cryogenic conditions, specifically when used in filament wound composite pressure vessels, has resulted in the development of superior cryogenic COPV designs utilizing materials and processes optimized for performance at LN2 temperatures. Additional efforts to evaluate radiation effects as well as impact sensitivities in cryogenic environments are on going in order to further develop the whole picture understanding. KEY WORDS: Applications Cryogenic, Pressure Vessels/Tanks/Storage Vessels, Testing/Evaluation, Impact, Radiation

1
This material is declared a work of the U.S. Government and is not subject to copyright protection in the United States.

1. BACKGROUND/INTRODUCTION
NASA has recently announced plans for new launch vehicles to replace the space shuttle which includes the crew exploration vehicle (CEV) and the crew launch vehicle (CLV). The new CEV and CLV programs have a very aggressive schedule and will likely use proven technology where applicable. The upper stage, or crew transport portion, of the CEV is designed with a pressure fed propulsion system that will require relatively high pressure (350 psi) storage tanks for liquid cryogenic propellents. In addition, these tanks may also contain 6,000 psi helium pressurant tanks, also subjected to cryogenic temperatures. In contrast to the low pressure (175-200 psi) tanks from previous pump fed systems, it may well be advantageous to construct these new storage tanks in a manner similar to filament wound ambient COPV tanks with the additional challenge of cryogenic exposure. The basic research and evaluation documented here has direct application to the design and manufacturing of these cryogenic COPVs for storage of cryogenic propellants in support of the CEV propulsion system. This development effort has been conducted independent of any specific composite tank program by taking a fundamental building -block approach toward COPV development. A key aspect of this research is the ability to leverage the results obtained by partnering with a team consisting of the NASA-MSFC, university researchers (MSU), and a private company (HEI), all of whom have extensive COPV development and materials testing experience. The development concept has been to understand composite materials performance on small cryogenic COPVs then optimize this performance for larger structures. Rather than treating the development process in series, testing of candidate material systems has been evaluated by COPV tests in parallel with the material development and material testing. Based on the initial single cycle burst test results, suitable candidate COPVs were down-selected for additional cyclic thermo-pressure evaluation. These additional COPVs are fabricated and subjected to multiple fill-and-drain pressure cycles with LN2 prior to a final LN2 burst test. This allows the material performance to be evaluated after being subjected to both thermal and mechanical cycling. Extensive cycling of the test articles is still ongoing at this time. In order to help understand which material properties correlate with improved burst performance, materials testing was conducted as a parallel effort to characterize the constituent resin and fiber properties. Neat resin samples were cast into tensile coupons and evaluated at ambient and LN2 temperatures. The same testing was also done with dry fiber tows and single fibers. The interaction of the resin and fiber was initially evaluated with short-beam-shear composite coupons at ambient and LN2 temperatures.

2. TECHNICAL DISCUSSION
2.1 Defining the baseline development charter and test specifics. The baseline charter of this multi-faceted development has been to develop a sound understanding of how high performance composite pressure vessels may be used in cryogenic applications. In order to accomplish this, the effort has focused primarily on utilizing actual

COPVs in the majority of the test scenarios, with test findings verified and supplemented by laboratory testing of constituent materials in neat resin, fiber strand, and coupon form. In rough order of priority the efforts were designed to accomplish the following: 1. Examine state-of-the-art composite material systems and fabrication techniques in COPVs to determine their applicability for cryogenic applications. a. The primary focus has been on identifying material systems that lend themselves to the application with only secondary focus on developing specific processing for any specific material system. b. The use of metal liners has minimized the need and the ability to examine stress/strain cracking and permeation in the test specimens; efforts focused on optimizing ultimate pressure vessel material performance (delivered tensile strength) at LN2 conditions. 2. Develop a design foundation understanding of the constituent characteristics of both materials and pressure vessel designs necessary for superior cryogenic performance. a. Materials laboratory testing has been utilized to help identify key characteristics. 3. After identifying shortcomings in standard well characterized material systems, identify new material systems with potential for cryogenic applications. 4. Develop an understanding of cryogenic COPV life cycle capabilities and limitations including: a. Potential pressure/thermal cycle degradation. b. Impact performance under cryogenic conditions. c. Potential radiation effects. d. Stress rupture potential. 5. Scale up the developed technology into a path-finder COPV geometry in order to verify capabilities and applicability. At this writing efforts on items 1 through 3 are quite mature with additional work underway to develop item 4a through c life cycle capabilities. The path forward for items 4d, stress rupture, and 5, has yet to be defined. The selection of a baseline test geometry was driven by the nature of the proposed testing and the means of accomplishing the tests. The baseline geometry for the pressure vessel uses a standard test evaluation bottle (STEB) design . This is a dual ported vessel, approximately 6 in diameter and 20 in long, with a 2 gal water volume. An aluminum liner is used as both bladder and wind mandrel. Early determination was to evaluate each selected material systems in each of the following screening COPV tests: (1) Population number one would be the baseline ambient pressure vessel burst performance of the selected material system. (2) Population number two would be the LN2 pressure vessel burst performance of the selected material system. (3) Population number three would be the post cycle test LN2 pressure vessel burst performance of the selected material system. Baseline cycle testing subjected suitable specimens to 5 complete thermal/pressure cycles to 80% of the ambient burst level.

In addition to the COPV testing noted above, significant testing was performed on neat resin samples in order to determine their characteristics and behavior at both ambient and LN2 temperatures. Carefully prepared resin specimens were tensile tested under both ambient and LN2 conditions, strain was measured using a cryogenically rated MTS extensometer; engineering values for modulus, ultimate tensile stress, and strain to failure were measured. In similar fashion composite specimens of the various material systems were tested in short beam shear (SBS) tests at both temperature extremes in order to evaluate the interlaminar shear strengths of the test materials. Having found very limited data on fiber properties at cryogenic temperatures it was decided to test dry fiber specimens at ambient and LN2 temperatures. While this proved challenging the data to date suggests that in general the carbon tows seem unaffected by these temperature extremes. 2.2 Select of candidate materials. The selection of candidate fiber and resin (matrix) materials was process, performance, and availability driven. Since the primary focus of the effort is geared toward weight sensitive, high performance aerospace applications, the fibers selected for inclusion in the test matrix were intended to represent current state-of-the-art choices that might be made for a filament wound COPVs. Although many fibers were initially evaluated, the following constitute the majority of the current data base: (1) Torays T-1000 12k high performance fiber was a natural selection due to its demonstrated applicability for high performance pressure vessels. (2) Torays M30S fiber, while slightly less capable than the T-1000, was examined due to its very high performance vs cost ratio. (3) Hexcels IM7 fiber was chosen based on its outstanding track record for use in aerospace pressure vessel applications. The initial selection of resin (matrix) material was made primarily on demonstrated performance in COPVs and/or other aerospace applications. Two representatives of the EPON resin series (828 and 862/W) were selected as strong representatives of workhorse wet winding materials commonly used in the COPV industry. A pre-preg material from TCR Composites Inc. (UF 3325-95) was selected based on its excellent COPV performance at ambient temperatures. The Fiberite 977 resin was selected as a well characterized material historically chosen for many aerospace structural applications, including tankage with dual storage and primary structural requirements. It deserves to be noted that these current commercially available matrix materials, while demonstrating excellent performance in many applications, were never specifically developed for cryogenic applications. They are, however, natural candidates for inclusion in this cryogenic COPV development program. It also should be noted that the efforts summarized herein did not focus on primary structure applications, rather the focus was on COPV ultimate burst capability, especially that following representative life cycling scenarios. The NASA-MSFC and HEI in-house resin formulations were also examined based on their perceived characteristics at LN2 temperatures (strain to failure, crack resistance, etc.) Experimental NASA-MSFC systems included TD-111103, TD-72204, TD 111903, and TD-469.

The experimental HEI-535 system was also included based on early demonstrated LN2 COPV performance. As with any experimental/developmental effort, resources were limited and as such not all fibers were tested in all resin systems. 2.3 Design of test specimens. All COPV test efforts utilized seamless spun aluminum liners as the inner wall of the pressure vessel. This technique has proven to be an extremely cost effective manner of producing a COPV, providing a leak proof bladder as well as wind tooling for the composite overwrap. An additional important aspect is that this design philosophy reflects current design and fabrication techniques used in the vast majority of COPVs currently being planned or produced. Table I summarizes the build details of the test COPV in comparison with the industry standard ASTM pressure vessel: Table I. Baseline Geometry STANDARD ASTM D-2585 Mandrel Configuration Compacted Sand mandrel O.D. Mandrel thickness Wind sequence Wind tension (per tow) Helical angle (average) # of tows Hoop band width Helical band width Typical burst psig (T-1000) 5.75 in N/A XOOXOO 10 lbf 11 degrees 2 0.18 in 0.20 in 5,100 psi

HEI TEST VESSEL 6061-T6 Aluminum 6.42 in 0.12 in OOOX 10 lbf 8 degrees 4 0.50 in 0.38 in 4,500 psi

All baseline ambient burst testing was performed with water; all cryogenic burst and cycle testing was performed using LN2. Compressed air or helium up to 10,000 psi was utilized over LN2 in a cascade pressure vessel to effect cryogenic pressurization. Neat resin tensile testing was used to determine the stress-strain response of the neat resins at both ambient temperature and submersed in LN2. ASTM standard D 638 [1] provided the baseline for the LN2 tests. A slight modification was made to ASTM standard Type IV specimen regarding the transition curvature to eliminate stress risers occurring in regions where the material was more rigid [2].

An estimate of the interlaminar shear strength (ILSS) was determined by use of the SBS test, outlined in ASTM Standard D 2344 [6]. The SBS test specimen was cut from the thickened hoop section of a COPV with standard dimensions as noted in Table I. This test permits a statistically significant number of SBS to be machined from a single COPV. The thickness of the coupons ranged between 0.13 to 0.16 in with allowances for final finishing. 2.4 Fabrication of test specimens.

While specimen fabrication and testing continues at this writing, well in excess of 200 COPVs have been fabricated and tested. COPV fabrication and testing were conducted at both HEI and the NASA-MSFC with very comparable results. Figure 1 shows a standard liner installed on the winding machine. COPVs fabricated at the NASA-MSFC were made using an EnTec model number 5K48W-180-4 filament winding system. The fiber tension was tightly controlled ( 0.02 oz-f) by a tensioner creel from Helman Engineering Inc. and was set and monitored for all winding. All fiber over-wrap parameters for the COPVs were precisely replicated so that an accurate comparison of different resins could be made. The parameters of the fibers include: number of fiber tows, bandwidth of the combined tows, fiber tension, wind angles and layer sequence.

Figure 1. COPV being wound at the NASA-MSFC. At HEI all of the pre-preg winding was performed on an Entec model PW12 laboratory-winding machine. This machine and the associated delivery system have been specifically configured to wind with pre-preg fiber. All wet resin winding was performed on an Entec model PW65H-1204-25 winding machine with a fiber/resin delivery system specifically set for wet winding. The cure cycles and profiles used followed resin suppliers recommendations and/or profiles that had previously been demonstrated to product excellent results in COPVs. Material systems requiring vacuum bagged cure used a Rietschle type VCB-20 (02) vacuum pump followed by curing in a BlueM model number EM-9665R1G-MPZ.GOP oven. Neat resin specimens were cut from a 0.13 in thick cast sheet of resin. The resins were thoroughly mixed and de-gassed in a vacuum chamber before curing to ensure consistent test

results. As previously mentioned, SBS specimens were first wound on a standard aluminum liner and subsequently cut from sections removed from the mandrel, post cure. 2.5 LN2 test assembly. A schematic of the LN2 COPV test assembly is shown in Figure 2; similar facilities were established at both HEI and the NASA-MSFC.

Figure 2. Schematic of the LN2 burst facility at HEI. The test assembly utilized high pressure air or helium over LN2 in a cascade cylinder in order to pressurize the test vessel with high pressure LN2. Early testing demonstrated the necessity of a high pressure cascade cylinder with significantly greater strength and capacity ahead of the test specimen in the test assembly. This effectively kept the test specimen filled with LN2, helping significantly with temperature stability and elimination of gaseous (higher energy release) bursts. In addition the test specimen was immersed in LN2 to maintain specimen test temperature. Both the high pressure gas over nitrogen cascade vessel and the test vessel were contained in separate protective and insulated chambers in order to contain the released energy of any pressure vessel rupture. Figure 3 shows an HEI engineer making final data acquisition attachments in preparation for a LN2 burst test. Figure 3. LN2 Burst Preparation

While cryogenic cycle testing was conducted at both facilities the NASA-MSFC facility was found to be preferred since it allowed for a more automated (i.e. efficient) testing scenario. This proved invaluable for tests involving more than just a few cycles. Additional thermal/pressure cycle tests are ongoing at this writing. Figure 4 shows the NASA-MSFC facility used for the LN2 cycle test. Figure 4. NASA-MSFC LN2 Burst Facility 2.6 Conducting the various tests. All constituent material tensile tests were conducted on a Model 5869 Instron 50 kN electromechanical load frame. Figure 5 shows a cryostat to hold a LN2 bath which was constructed from a 10 gal container insulated with polyurethane foam and rigidly fixed to the load frame. Strain was measured using a cryogenically rated MTS extensometer. The same load frame was utilized for the cryogenic SBS testing. Figure 6 shows a MSU Graduate student preparing a specimen for cryogenic SBS testing.

Figure 6. Short Beam Shear Testing Figure 5. Materials Evaluation Testing As noted, prior to conducting any cryogenic testing on the vessels it was necessary to establish the baseline ambient performance of the candidate material systems. Several vessels from each raw material configuration were hydroburst at ambient conditions using HEIs model 82053 Haskel Test Pack hydrostatic burst pump, shown in Figure 7. This pump and test equipment is rated to 30,000 psig burst capability.

Figure 7. Hydrostatic Burst Stand. Figure 8. Completion of a LN2 Burst Test. Subsequent to the cryogenic hydroburst tests the candidate materials were evaluated in cryogenic burst tests with LN2. Figure 8 shows both the cryogenic burst protective test chamber and the cascade vessel chamber just moments after a successful cryogenic burst test as evidenced by the LN2 evaporating along the ground. The rise rate for the pressurization was approximately 85 100 psi/sec. Extreme care was taken to keep the test vessel at LN2 temperatures with the LN2 either being poured directly over the vessel or the vessel actually submerged in LN2 until the actual burst; in this manner all materials were evaluated at the same temperature. After each burst the cascade vessel was refilled with LN2; the goal being to ensure a hydraulic burst mode (i.e. no gaseous nitrogen in the test vessel) while testing at LN2 temperatures. 2.7 Evaluating the test data.

A cursory examination of the raw pressure vessel burst data might lead one to believe that in some instances the cryogenic performance of the COPVs actually improved over the demonstrated ambient performance. This would be an erroneous conclusion. The apparent improvement is in fact due to improved performance of the aluminum liner at LN2 temperatures (a well understood behavior) and NOT improved composite performance. Since the composite vessels were fabricated and tested over an aluminum liner it was necessary to understand the performance and contribution of the liner to the burst performance at the temperatures evaluated. To accomplish this several bare (i.e. no overwrap) aluminum liners of the exact configuration as those used in the test specimens were tested at both ambient and LN2 temperatures. Figure 9 shows typical results from the bare aluminum liners; note the significantly higher ultimate burst performance of the liner in LN2. The data obtained from this test correlated well with published aluminum properties at ambient and LN2 temperatures [12].

2500

2000

LN2
1500 Pressure (psi) 1000

Ambient
500 0

-500 0 5 10 15 20 Time (sec) 25 30 35 40

Figure 9. Ambient vs. LN2 Burst of Aluminum Liner. In order to totally understand the performance of the composite material being evaluated it is necessary to analytically back-out the delivered fiber strength at ultimate burst pressure. This is done using finite element analysis, the model of which incorporates the varying properties of the aluminum liner as well as those of the composite over-wrap and effectively accounts for all contributing factors to the whole COPV structural system. The delivered fiber strength values shown throughout this document were derived in this manner. As used in this document, the term delivered fiber stress refers to that stress demonstrated at failure in actual COPV burst tests. This differs significantly from manufacturers specified fiber stress which is a strand tensile measurement and does reflect the effects of pressure vessel processing.

3. RESULTS AND DISCUSSION

Presented in chart form, Figures 10 through 12 summarize the COPV results from the numerous tests and are grouped according to the common fiber system. The charts are color coded to show the various test conditions; the first red bar shows ambient COPV burst performance; the second light blue shows LN2 COPV single cycle burst performance (i.e. no hold and no thermal/pressure cycling); the third dark blue, when present, shows LN2 COPV burst performance following 5 complete thermal/pressure cycles. Note, not all the COPVs have been cycle tested at this time as testing is ongoing. A standard cycle test would chill the vessel to LN2 temperature, pressurize with LN2 to 80% of demonstrated ambient burst pressure, then drain and warm the vessel back to ambient conditions; this would be repeated 5 times prior to LN2 burst test. All test data has been shown as a function of delivered fiber strength (i.e. demonstrated fiber strength in actual pressure vessel burst tests).

10

T1000 Fiber Data

1100 Ambient Cryogenic Cryo Cycle/Burst

1000

900 Delivered Fiber Strength (ksi)

800

700

600

500

400 EPON 828 EPON 862/W TCR 3325 977 Resin System TD 111103 HEI 535 TD 72204

Figure 10. Comparison of delivered fiber strength for various resins with T-1000 fiber. Figure 10 shows the data for the Toray T-1000 fiber, arguably the highest performance fiber currently available on the market. While in general the data for any given material was extremely consistent, with low coefficient of variations (CV), the LN2 cycle data for the EPON COPVs with T-1000 fiber was extremely variable and as such is not shown (missing dark blue bars); additional testing is required for these materials. The TCR-3325 material system has a tremendous track record at ambient conditions but, like the EPONs displays a sizable reduction in performance at LN2 temperatures. The 977 material showed such significant LN2 degradation that cycling to 80% of ambient burst pressure was not possible. The remaining 3 systems shown utilize experimental resin systems and all 3 showed relatively good performance at LN2 temperatures. The TD-111103 data showed in excess of 100% of manufacturers certified fiber strength. While this is not unheard of, it is rare enough to deserve further evaluation. However, the resources were not available at this time to repeat this test. The HEI-535 demonstrated the best performance in the post LN2 cycle tested COPVs, and is the only material tested that displayed improved performance over single cycle LN2 burst data.

11

M30SC Fiber Data

750

Ambient Cryogenic Cryo Cycle/Burst

700

650 Delivered Fiber Strength (ksi)

600

550

500

450

400

350

300 TD 111103 TD 111903 EPON 862/W TD 469 Resin System NP WD TCR 3339 TD 72204

Figure 11. Comparison of delivered fiber strength for various resins with M30SC fiber. Figure 11 summarizes the COPV data obtained using the Toray M30S fiber, a slightly lower performance fiber compared to T-1000 but arguably the greatest bang for the buck relative to price vs performance. Since the M30S/ EPON 862/W material showed significant degradation in LN2 testing the EPON 828 was not tested since they are similar resins. Both the NP (Newport) WD resin and the TCR pre-preg , also demonstrated significant LN2 degradation. In fact the only systems showing good LN2 performance with the M30S fiber were the two experimental resins, TD-111103 and TD 111903. Figure 12 summarizes the COPV data using the IM7 fiber. Once again the HEI-535 and the TD-111103 showed excellent promise for utilizing this fiber in LN2 applications. The IM7/977 material system was of specific interest as there is a wealth of industry experience with this system for numerous applications. However, it provided at best lackluster performance in LN2 COPVs testing.

12

IM7 Fiber Data

1000 Ambient Cryogenic Cryo Cycle/Burst

900

Delivered Fiber Strength (ksi)

800

700

600

500

400 EPON 828 HEI 535 977 Resin System TD 111103 TD 72204

Figure 12. Comparison of delivered fiber strength for various resins with IM7 fiber. It was found that LN2 temperatures degrade COPV performance, as evidenced by the burst pressure, if the material and process have not been developed for this specific application. Increased performance was observed for new materials, specifically developed for this application. The HEI 535 resin with T-1000 fiber has demonstrated fiber translation in excess of 100% of fiber manufacturers certified strengths at LN2 temperatures. Observations from this overall effort include the following. It is vital that cryogenic COPVs are demonstrated and validated at their operational temperatures. We have found through first hand experience that it is misleading to cycle a COPV with LN2 followed by ambient burst tests with water and to design a COPV based on subsequent ambient temperature performance. Cryogenic COPV design must be based on ultimate demonstrated performance at cryogenic temperatures. If the COPV design is intended for multiple cycle usage, then it is imperative to cryogenically test the COPVS with a series of thermo/pressure cycles to evaluate the potential for degradation of performance and reliability. Initial cryogenic thermo/pressure cyclic data suggested that those resin systems which display a significant initial cryogenic performance knockdown, also continue to display a degradation as a function of thermo/pressure cycles. By contrast those systems which display little cryogenic degradation, or even improved performance at cryogenic temperatures, tended to show relatively little if any continuing degradation.

13

Based on the presented data, those systems which displayed the highest burst pressure and/or delivered fiber strength were down selected for additional and greater numbers of cyclic pressurization tests. This testing is ongoing at this writing and is not presented in this paper [8]. Since not everyone is familiar with the use of delivered fiber strength as a performance criteria, the data has been used in the preliminary design of a COPV that might be utilized in an upper stage launch vehicle. Figure 13 shows how the demonstrated material performance values would affect the actual hardware weight. For this exercise we have assumed that the vessel is weight/performance driven and is designed using the high performance T-1000 fiber along with the demonstrated cryogenic performance of 3 state-of-the-art resins and HEIs 535 resin (having the highest performing cryogenic data to-date). We have also assumed that the performance demonstrated in 6.4 in diameter test vessels translates directly into larger diameter tanks, obviously the actual scale up factor remains an unknown. The target pressure vessel, used to obtain the design weights in Figure 13, has an overall diameter of 67 in, a dome to dome length of approximately 51 in (including a short cylindrical section), and an overall volume of 76 ft3. Assumed performance requirements are a service pressure of 380 psi with a factor of safety of 2.0. To achieve these performance requirements, the projected composite weight using the T-1000 fiber with selected resin, are summarized in Figure 13. Since it is assumed that the vessel would have a very thin, non-structural metallic liner of exactly the same thickness and weight for all potential composite materials, its weight has not been included.

26.0 $1,120,000 24.0 COPV Composite Wt. (kg) (Not Including Liner) $960,000 22.0 $800,000 Potential Launch System Cost Increase

20.0

$640,000

$480,000 18.0 $320,000 16.0 $160,000 14.0 $0

12.0 HEI 535 UF 3325 EPON 862 977-2

-$160,000

T1000 FIBER SYSEM

Figure 13. Optimized Materials Reduce COPV Weight.

14

The left hand Y axis in Figure 13 shows preliminary design composite weight while the right hand axis show the potential launch vehicle increased cost as a function of weight. A generic value of $100,000 per kg (2.2 lbf) of added weight has been assumed for upper vehicle weight/cost penalty.

4. SUMMARY
Great strides have been made in the understanding of how composite materials perform in COPVs at cryogenic temperatures. A significant performance degradation is observed in burst test results between ambient and LN2 testing in many commercially available resins. However, a few experimental fiber/resin systems were found which did not degrade at LN2 temperatures. The HEI 535 resin with T-1000 fiber has demonstrated fiber translation near 100% at LN2 temperatures. This material performance and reliability ultimately translates to a significant weight savings on a cryogenic COPV design. Our cryogenic COPV research has been demonstrated on a significant number of 2 gal vessels and is scaleable to larger structures. A method has been initiated to correlate the cryogenic material testing of composite coupon samples and their constituents (fiber, matrix resin, fiber sizing etc.) to potential use on actual cryogenic COPVs. The understanding of composite materials used in the fabrication of COPVs for cryogenic fuel storage should be valuable to a variety of programs involving the storage and transport of cryogenic propellents. This knowledge is also applicable to aerospace launch vehicle programs (including DOD and space tourism) requiring higher pressure cryogenic fluid containment.

5. SUPPORTING RESEARCH ACTIVITIES

Initial work has been done involving the impact resistance of a COPV demonstrated by a modified version of the 30 caliber bullet D.O.T. test [9]. The test is similar to the D.O.T. test but the vessel is pressurized with 3,000 psi LN2. Although the issue of damage tolerance on composite materials at ambient conditions has been studied; evaluating the actual impact on a cryogenic COPV is necessary. High, medium and low velocity impact studies at cryogenic temperatures are planned. Plans are made to combine the new cryogenic resin technology with a hybrid fiber structure. A hybrid tank structure (combining T-1000 carbon and Zylon fibers) has resulted in a robust tank structure able to pass significant low and high velocity impact tests that typical pressure vessels cannot. An interesting correlation has been made between performance at cryogenic temperatures and noticeable improvement in impact damage tolerance. MSU will perform single fiber pull-out at cryogenic temperature tests to understand the fiber resin interface. Work is planned with fiber producers to enhance performance based on fiber surface treatment/morphology. The architecture of the CEV and CLV vehicle may require long term (6 month) storage of cryogenic propellents. Our studies can be extended to evaluate the effect of LN2 temperatures on the performance and reliability of composite materials in COPVs during long term use. This could include high cycle and long term environmental exposure tests. The effort may be later

15

expanded to the development of an all-composite tank structure and provide a springboard for studies in micro-meteorite damage or long term fuel storage. Studies are ongoing to evaluate the effects of radiation on the COPV materials [10]. Future COPV tests will be planned in accordance with the new standard for space system COPVs [11]. This standard is intended to provide guidance for the implementation of an industry-developed pressure vessel standard. Important inclusions in this standard are: system threat analysis, development test program impact damage-tolerance test procedures, leak-before-burst test method, stress rupture life data evaluation techniques, vibration test methods, and qualificationby-similarity criteria. An on-gong part of this effort is the testing of additional COPV systems, using cyclic thermopressure cycles prior to a LN2 burst test. This will allow further investigation of the various candidate material systems to survive expected operational loading.

6. ACKNOWLEDGMENTS
This effort was performed under contracts: NCAM-LP # 58404-511 (MSU), NASA-STTR Phase I Contract #NNM05AA61C (HEI/MSU) and NASA-SBIR Phase I Contract # NNM05AA45C (HEI/MSU).

7. REFERENCES
1) 2) 3) 4) 5) 6) 7) 8) ASTM D 638-91, Standard Test Method for Tensile Properties of Plastics (1991). J.R. Jackson, J.A. Schneider, T. DeLay, Tensile Properties of Epoxy Resins at Cryogenic Temperature," 50th International SAMPE Symposium, May 2005, Long Beach, CA. NASA Phase II SBIR, Cryogenic evaluation of typical and experimental filament wound materials, Contract #NNM04AB16C, HyPerComp. Engineering, Utah, POP: 6/04-7/06. D4018-99, Standard Test Methods for Properties of Continuous Filament Carbon and Graphite Fiber TOWs (2004). D3379-75 e1, Standard Test Method for Tensile Strength and Young's Modulus for High-Modulus Single-Filament Materials (1989). ASTM Standard D 2344-00, Standard Test Method for Short-Beam Strength of Polymer Matrix Composite Materials and Their Laminates (2000). Schneider, J.A., Helman, M., DeLay, T.K., Effect of Fiber Tension on COPV Performance, 51st International SAMPE Symposium, April 30-May 4, 2006, Long Beach, CA. Schneider, J.A., Patterson, J.E., DeLay, T.K., Design methodology for cryogenic composite overwrapped pressure vessel development, 42ND AIAA/ASME/SAE/ASEE Joint Propulsion Conference, June 9-12, 2006, Sacramento, CA. Code of Federal regulations, Department of Transportation (CFR-DOT), 1996a, Basic requirements for Fully Wrapped Fiber reinforced Aluminum Lined Cylinders, Title49, CFR 107.105 Standard Allison, P.G., Jackson, J.R., Schneider, J.A., Noorda, R., Patterson, J., DeLay, T.K., Radiation effects on cryogenic COPV performance, 51st International SAMPE Symposium, April 30-May 4, 2006, Long Beach, CA. ANSI/AIAA S-081: Space Systems Composite Overwrapped Pressure Vessels, Jan. 2003. MIL 5, Materials Handbook.

9)

10)

11) 12)

16