Shape memory polymers (SMP) and other shape memory materials (SMM) are smart materials used in reconfigurable structures. Smart materials include piezoelectric, shape memory alloys, and SMPs. Smart materials are practical for various applications, including: shape memory alloys in orthodontic treatments; piezoelectric actuators for control of micro air vehicles; shape memory polymers as cardiovascular stents; and a multitude of smart materials for the morphing of aircraft structures. SMMs are valued for their potential use in adaptive structures in various applications, such as, micro air vehicles (MAVs) and morphing aircraft. SMPs have the ability to change their shape upon application of external stimuli, such as, temperature, electricity, magnetism, or light. For example, Veriflex-S® is an SMP that uses an external thermal stimulus to allow reconfiguration and recovery. Veriflex SMPs have been used in applications that include active disassembly for recycling, deployment of satellite solar panels, and deployable aircraft wings.
Veriflex-S® can display two stiffnesses and material behaviors characterized by a high glassy modulus and a low rubbery modulus. At temperatures below its glass transition temperature (Tg), the material is relatively stiff and has a high elastic modulus. When the SMP is heated above its Tg, the modulus drops by several orders of magnitude. This transition from the glassy to the rubbery state is illustrated in
A major deficiency of shape memory material (SMM) unimorphs, which comprise an active SMM layer and an inactive support material, is a permanently unrecovered shape after a single or multiple stimulus cycles. Hence there is a need for a means to assist the recoverability of SMPs, such as, Veriflex-S®. To this end, an SMP in a unimorph composite actuator (UCA) configuration has the potential to promote recovery in excess of 95% of the SMP article. A UCA is an element with a bi-stable configuration consisting of one active layer—the SMP—to which the stimulus is applied and an inactive layer that supports the active layer.
Embodiments of the invention are directed to a unimorph composite actuator (UCA) incorporating lateral curvature in a substrate to give excellent shape recovery to an SMM unimorph. UCAs, according to an embodiment of the invention, comprise an SMP layer bonded to a curved substrate. The UCA employs a lateral curvature that significantly reduces the residual deformation while increasing shape memory recoverability, which could be tailored to enhance the performance of shape memory polymers in reconfigurable arrangements. Recoveries of the UCAs are more than an order of magnitude better than traditional flat UCAs. Although the following disclosure is exemplified by the use of SMPs, any SMM can be used, including shape memory alloys (SMAs) and piezoelectric materials, where unlike that shown in
The UCA can be used in any device that requires switching between two states, one state being a deformed state and the other being the equilibrium state that is fixed into the SMP upon its formation. Though the exemplary embodiments are for a simple UCA that has lateral curvature, which resembles a portion of a cylinder in shape that has a length parallel to the central axis of the cylinder and a width that is perpendicular to the hypothetical central axis, the UCAs according to embodiments of the invention can have other shapes as long as curvature in at least one dimension is present. The UCA comprises an “elastic” substrate that is capable of being bent or otherwise deformed or deflected along at least one axis or other defining curve of the equilibrium state. The substrate can be a composite, a metal, or a thermoplastic, which is employed at temperatures such that at the highest temperature encountered by the UCA no flow results in the substrate; for example, all temperatures are below a substrate material's glass transition temperature (Tg) or melting temperature (Tm). The substrate is sufficiently thin, such that a reversible deflection along a defining axis or defining curve can be performed at an accessible force for the use of the UCA but inherently the substrate will return to its desired shape. For example, the UCA can be employed as an airfoil when in the equilibrium state and transformed into a more compact state for storage of the device employing the airfoil.
The SMP can be a polymeric system that is covalently or physically cross-linked, such that there is no relative disorientation of the effective cross-links upon heating above the polymer's Tg, such that the cross-linking sites cannot exchange and cannot translate into other positions that generate an energetically preferable state. The effective cross-linking density is at a level that does not restrict deformation of the polymeric network when the temperature is raised above the Tg of a continuous or semi-continuous phase within the network. In general, the SMP can be in the form of: (I) a chemically cross-linked glassy thermoset; (II) a chemically cross-linked semi-crystalline rubber; (III) a physically cross-linked thermoplastic; and (IV) a physically cross-linked block copolymer. Of the (I) chemically cross-linked glassy thermosets, exemplary SMPs are: P(MMA-co-VP)-PEG semi-IPNs; copolyester; P(AA-co-MMA)-PEG; PMMA-PBMA copolymers; PET-PEG copolymers; P(MA-co-MMA)-PEGs; Soybean oil copolymers with styrene and DVB; styrene copolymers; thermosetting PUs (water swollen); thermosetting PUs (ester type); dehydrochlorinated cross-linked PVC; polynorbornene; or ultrahigh MW PMMA. Of the (II) chemically cross-linked semi-crystalline rubbers, exemplary SMPs are: Poly-caprolactone; EVA+nitrile rubber; PE, Poly-cyclooctene; PCO-CPE blend; PCL-BA copolymer; Poly(ODVE)-co-BA; or EVA+CSM. Of the (III) physically cross-linked thermoplastics, exemplary SMPS are: POSS telechelics; PLAGC multiblock copolymers; Aramid/PCL; PVDF/PVAc Blends; Poly(ketone-co-alcohol); PCL-b-ODX; PLA/PVAc blends; Poly(1-hexadecene)-co-PP; PE-co-PMCP; POSS-PN block copolymers; PA-PCL Polyamides; PET-co-PEOs; PE-co-Nylon 6; or PS-TPB. Of the (IV) physically cross-linked block copolymers, exemplary SMPs are: POSS/PDLA-co-PCL/MDI; 4,4′-Dihydroxybiphenyl (DHBP)/PCL blend with phenoxy resin or PVC/Hexamethylene diisocyanate (HDI); 1,6-HD/HDI-1,2-BD/4,4′-MDI; 1,4-Butanediol/Poly(ethylene adipate)/MDI; 1,4-Butane glycol, ethylene glycol, bis(2-hydroxyethyl) hydroquinone, bisphenol A+ethylene oxide, and/or bisphenol A+propylene oxide/Polypropylene glycol, 1,4-butaneglycol adipate, polytetramethylene glycol, polyethylene glycol, and/or bisphenol A+propylene oxide/2,4-Toluene diisocyanate, 4,4′-diphenyl-methane diisocyanate, and/or hexamethylene diisocyanate; 1,4-BD/Poly(tetramethylene glycol) (PTMG)/MDI; 1,4-BD/PCL diol/MDI; BEBP or BHBP/PCL diol/MDI; DHBP/PCL diol, 4000 Da/HDI; 1,4-BD/Poly(tetramethylene oxide) glycol/(PTMO) MDI; or BD+DMPA/PCL diol, 2000, 4000, 8000 Da/MDI. The transition region, as shown in
Where the SMM is a SMA, materials that can be used include, but are not limited to, Ag—Cd 44/49 at. % Cd, Au—Cd 46.5/50 at. % Cd, Cu—Al—Ni 14/14.5 wt. % Al and 3/4.5 wt. % Ni, Cu—Sn approx. 15 at. % Sn, Cu—Zn 38.5/41.5 wt. % Zn, Cu—Zn—X (X═Si, Al, Sn), Fe—Pt approx. 25 at. % Pt, Mn—Cu 5/35 at. % Cu, Fe—Mn—Si, Pt alloys, Co—Ni—Al, Co—Ni—Ga, Ni—Fe—Ga, Ti—Pd in various concentrations, Ni—Ti (˜55% Ni), Ni—Ti—Nb, and Ni—Mn—Ga. Piezoelectric material that can be employed include, but are not limited to, Lead zirconate titanate (Pb[ZrxTi1-x]O3 0≦x≦1), Potassium niobate (KNbO3), Lithium niobate (LiNbO3), Lithium tantalate (LiTaO3), Sodium tungstate (Na2WO3), Zinc oxide (ZnO), Ba2NaNb5O5, Pb2KNb5O15, Sodium potassium niobate ((K,Na)NbO3), Bismuth ferrite (BiFeO3), Sodium niobate NaNbO3, Bismuth titanate Bi4Ti3O12, Sodium bismuth titanate Na0.5Bi0.5TiO3, and Polyvinylidene fluoride (PVDF).
The UCA can be prepared by forming or providing the substrate in a desired shape, including the curvature that is needed for the UCAs, according to embodiments of the invention. The SMP can then be combined with the substrate. The combination can be constructed by forming the SMP on the substrate or by adhering the SMP to the substrate. The UCA can be mechanically deformed at temperatures above the Tg, or the Tm, of the SMP and allowed to cool to a temperature below the Tg, or Tm, of the SMP. This transformation locks the UCA in the deformed state, which is not in the thermodynamic minimum conformation, but is retained in this stressed state while the temperature is maintained below that of a thermal transition region, as shown in
Sample UCAs consist of an SMP layer bonded to a graphite fiber/epoxy substrate. Flat carbon fiber composite unimorphs and transverse curvature carbon fiber composite unimorphs were fabricated as follows. A single layer of a [±45°] oriented, plain weave, bi-directional carbon fiber epoxy resin sheet was cut and placed on a Teflon covered plate or a curved tooling board. The [±45°] fiber configuration was used versus a [0°/90°] because it allowed for the CF to be rolled to a smaller diameter in the stored state and was more stable during storage. The assembly was covered by an additional layer of Teflon, vacuum bagged, and cured at 130° C. for four hours. After curing, the carbon fiber composite was cut to the appropriate size. A styrene copolymer network, Veriflex-S® shape memory polymer, Cornerstone Research Group, Inc., USA panel was bonded to the carbon fiber composite using Araldite 2011, a two-part epoxy. The UCAs were coated with a base coat of flat white spray paint and randomly speckled for digital image correlation (DIC) using flat black spray paint.
The DIC system is a non-contact full-field shape and deformation technique developed at the University of South Carolina. The DIC system employed used two Point Grey Research 5-megapixel grayscale cameras to simultaneously capture images of the random speckle pattern applied to the samples. The cameras were calibrated via a high contrast dot pattern of known diameter and spacing. A 9×9 grid of points with a separation of 10 mm was used for calibration. After calibration, the system was used to photograph the UCA and determine deflection as a function of time. Reference images of the beams were initially taken after the samples were painted. Subsequent images were taken before starting each testing cycle. These images were contrasted against images taken over the hour observation time to determine the deflection as the sample cooled. Images were captured via VIC Snap 2009 and processed via VIC-3D 2009 to determine deformations.
A transversely curved UCA was monitored during the deployed and stored cooling stages to develop a cooling profile over time. The UCA was outfitted with two Omega SA1 self-adhesive K-type thermocouples. A thermocouple was placed in the center of the UCA on both the top and bottom surfaces to monitor temperature.
The UCAs were placed in a Sun Systems Model EC12 environmental chamber and the temperature was brought to a desired value greater than the SMP's Tg. The temperature was monitored via a thermocouple inside of the chamber and confirmed via a Fluke 561 series infrared thermometer. Beam samples were placed on a Teflon plate within the chamber to allow for full expansion under elevated temperature conditions.
Upon removal from the environmental chamber, samples were folded into a U-shaped configuration, as shown in
Step 1. Acquire an initial (reference) image of the undeformed speckle pattern on the UCA.
Step 2. Place the undeformed UCA in the environmental chamber for one hour at 85° C.
Step 3. Bend the UCA into a U-shaped configuration within the holder and cool for one hour in the stored configuration.
Step 4. Return the UCA to the environmental chamber at 85° C. for one hour.
Step 5. Remove the UCA from the oven.
Step 6. Monitor the UCA via DIC while cooling to room temperature.
Before the UCAs were characterized as a unit the constituents, the plain weave; bi-directional carbon fiber; and the Veriflex-S® SMP were characterized individually. The epoxy and spray paint were not characterized due to their negligible thickness, 0.15 mm and 0.05 mm, respectively, with respect to the SMP and substrate (1.6 mm and 0.35 mm respectively) in the UCA. The Young's modulus and Poisson's ratio for both of these materials were calculated from a combination of tension tests and DIC to measure the full-field displacements under loading conditions at room temperature. The material properties for the CFRP were gathered with the fibers in the [±45°] orientation to coincide with the substrate lay-up. The load and corresponding strains were used to calculate the values provided in Table 1, below. Coefficient of thermal expansion (CTE) was determined by placing the specimens on a specialized hot plate and monitoring strain with respect to temperature via DIC. These strain values were validated by measuring the CTE of an aluminum sample concurrently with the Veriflex-S® and CFRP. Glass transition temperatures were taken from the manufacturer's respective published values. The glass transition temperature of the carbon fiber refers to the epoxy matrix's transition temperature, which is well above the glass transition temperature of Veriflex-S® and the experimental operating temperature. Coefficient of variation (CV), which is defined as the ratio of the standard deviation to the mean, is provided to display the extent of variability of the data.
Out-of-plane deflection (w) of the UCA was performed using UCAs of 200 by 38 mm that are flat (zero curvature) or have a 63.5 mm radius of curvature carbon fiber epoxy composite substrates. The substrates had a thickness of 0.35 mm. A 12.7 mm wide and 1.6 mm thick strip of flat SMP adhered via a 0.15 mm thick layer of Araldite® 2011 epoxy to the center of the carbon fiber substrate. The total UCA thickness was 2.15 mm which included a 50 μm layer of paint on the substrate surface for DIC measurements.
Processing of the acquired DIC data was carried out to determine the deflection for each UCA over time. Processing involved collecting the XYZ coordinates and UVW displacements for the centerline of each sample at desired times. Using an Excel spreadsheet, deformation (W) data was sorted by time and shifted to the desired coordinate system using MATLAB. Once transformed into the X-Z plane, the data are rotated to eliminate rigid body motion, assuring rotation of the sample in the X (lengthwise) direction to maintain correct displacement directions. After rotation, vertical translation to the X-axis ensures all images can be compared in the same coordinate system. This process is illustrated in
The cooling temperature as a function of time was measured during cool down for the deployed state, Step 7 of
Data for the flat and concave curved UCAs were collected in two minute intervals for the entire thirty minutes of cooling. The centerline shape was measured for the reference (before any temperature cycle) and at various times after the temperature cycle. To obtain the deformation, the reference shape was subtracted from the shape after the temperature cycle. To obtain the out-of-plane position (z+w) the residual deformation (w) seen was added to the original undeformed shape (z) of the UCA before the thermo-mechanical cycle. To properly control for manufacturing defects, only the deflection from the original shape is included in the resulting deflections. Repeatability and uncertainty experiments were performed during initial experiments and detailed experiments and expanded design space experiments, respectively. These results confirm the repeatability and statistical significance of the experimental results.
Table 2, below, shows the maximum out-of-plane deflection for flat and curved samples.
Preliminary tests clearly show transverse curvature of a unimorph substrate substantially improves shape recovery of the UCAs. Additional curved UCAs were prepared with concave orientation (saddle configuration) and with convex orientation (trough configuration). The convex sample was constructed to determine the effect on the residual deformation in an alternate orientation. The convex UCAs were monitored via DIC for thirty minutes during the cool down, as had been the UCAs. Table 3, below, shows maximum out-of-plane deviation with respect to time for the convex sample versus the original concave sample. The concave sample deflects only 0.36 mm, whereas the convex sample deflects 1.29 mm in the same time period. The convex sample behaves similarly to the concave sample with respect to relaxation. Both samples reach maximum deflection in approximately six minutes and decrease in deflection somewhat up to the thirty minutes.
Testing was carried out with additional concave curved UCAs to determine the repeatability of testing results and any residual deformation as additional deflection cycles were performed on UCAs. A series of four consecutive tests were conducted and compared at the maximum out-of-plane position (Z+W) time of six minutes, as well as at the end of the data collection period. Table 4, below, shows that there is high reproducibility of the UCAs, where the data range varied 40 μm at six minutes and 30 μm at 60 minutes.
The preceding tests clearly show that the concept of applying transverse curvature to a unimorph substrate substantially improved shape recovery. After determining the maximum out-of-plane deflections and their relation to transverse curvature the DIC data acquired was also used to view strain fields as the UCAs cooled. The strain fields were found to be fairly uniform for all samples so the center section of each UCA was selected as the area of interest, evaluated and averaged to get an average strain value at specific times during the cooling cycle. The area of interest is exhibited in the area inside of the dashed lines. The averaged values from the area of interest are shown where it was again confirmed that a majority of the deformation occurs in the first six minutes. All of the strains at thirty minutes are less than approximately 0.12% at the center of the UCA with the highest strains seen in the transverse direction of the concave UCA followed closely by flat UCA in the longitudinal direction.
Also extracted from the DIC data for the deployed configuration was the transverse direction out-of-plane position. This data was processed in the same manner as the out-of-plane deformation; however it was taken at the center of the UCA perpendicular to the lengthwise direction.
Additional tests were performed on a second concave curved sample to determine the repeatability of testing results and if additional residual deformation occurred when additional thermo-mechanical cycles were performed on the UCA. A series of four consecutive tests were conducted and compared at the maximum out-of-plane position (z+w) at six minutes as well as at the end of the data collection time.
Table 5 shows the data varied by only 40 μm at six minutes and 30 μm at 60 minutes, which are acceptable ranges for repeatability.
Deformed/Stored Configuration Results
In addition to determining the characteristics of UCAs in the deployed configuration, Step 7 of
After determining the cooling profile in the stored configuration, the DIC data acquired in the stored configuration was evaluated for the strain fields during cooling and out-of-plane position of the three types of UCAs.
The out-of-plane deformation in the transverse direction was extracted from the DIC data to determine the effect of transverse curvature in the stored configuration. This data was processed in the same manner as the out-of-plane deformation; however, as stated previously, it was taken at the center of the UCA perpendicular to the lengthwise direction.
The concave curved UCA was tested and compared to the baseline flat UCA in the expanded design space, but the convex curved UCA was not tested as it performed an order of magnitude worse than the concave UCA despite having the same amount of transverse curvature. As illustrated in
Table 6 shows the different curvatures, thicknesses, and widths examined and their respective designations.
All samples were tested for a minimum of three thermo-mechanical cycles and the data was analyzed and the maximum out-of-plane deflection was calculated for each UCA. The flat and high transverse curvature samples with thick SMP and intermediate substrate width, were identical to the flat and concave samples tested previously. All previously tested samples were tested for a minimum of three thermomechanical cycles and the maximum out-of-plane deflection was calculated for each UCA, and is tabulated in Table 7, below, and plotted as bar charts in
As the UCA's curvature increases, the amount of residual deformation decreases dramatically. For example, the out-of-plane deflection decreases from 27.7 mm for the flat 38.1 mm wide samples to 0.34 mm and 0.22 mm for the 127 and 63.5 mm radius of curvature samples, respectively. Deflection decreases as the UCA's width increases from 25.4 to 38.1 mm. Increasing the UCA's width from 38.1 to 50.8 mm does not decrease the deflection as markedly as the increase in width from 25.4 to 38.1 mm, and in some cases, increases the deflection. The trend of maximum deflection of the UCA's width is shown in
When progressing from the stored state, Step 4 of
An increase in curvature significantly reduces residual deflection and greater recovery of the UCA. The flat sample 000_08_381 has a maximum deflection of 27.7 mm, while increasing the curvature to the 127 mm sample decreases maximum deflection by two orders of magnitude to 0.34 mm. The trend of maximum deflection versus increasing curvature is shown in
Eight 000_08_381 samples and eight 625_08_381 samples were tested to determine the out-of-plane deflection ranges for the UCAs and determine the statistical significance of curvature on the measured deflection.
Experiments were conducted to record the deflection angle (°) for use to determine the shape fixity or shape retention loss of the stored UCA specimens over time. Ideally, a programmed UCA would be heated above Tg, mechanically deformed into the stored configuration, cooled below Tg, and would be capable of holding the desired stored shape indefinitely without shape retention loss and have deflection angle less than or equal to zero.
Post-processing of UCA images were required to determine the deflection angle for each UCA over time. Post-processing was accomplished via MATLAB where each image was evaluated with an edge detection algorithm to find the boundaries of the UCA. The image was then filtered to eliminate any white noise the edge detection procedure incorrectly interpreted as a boundary of the UCA. Finally, the image was evaluated on both sides to find the angle of the outer edges of the UCA. This was accomplished by plotting lines along the outer edges of the UCA and finding the angle of each side with respect to a vertical line at the mid-plane. Positive deflection was recognized as angles returning the UCA back to the original/programmed state and negative deflection as angles further establishing the UCA in a stored configuration. A deflection angle of zero would correspond to UCAs that retained the U-shaped stored configuration without any relaxation or contraction. This process is illustrated in
Data for the flat, concave, and convex UCA samples were collected at various intervals to establish a pattern of relaxation or contraction in the stored configuration. Initial testing determined that the deflection angle of the UCAs displayed asymptotic behavior and thus images over several time scales were needed. The deflection angle versus time for the first hour, over four hours, and over seven days is shown in
The preliminary tests on concave UCAs showed that applying concave transverse curvature to a unimorph substrate did not substantially hinder the shape fixity of the UCA. The tests show that a UCA with concave transverse curvature tends to have less shape retention loss than flat UCAs with all other parameters identical. For the UCAs of Table 6, decreasing SMP thickness tends to decrease the deflection angle and allow the UCA to contract further into the stored configuration, as shown in
The development of deflection angle versus time for the thin SMP, intermediate substrate UCAs, with flat, low, and high transverse curvatures is shown in
It should be understood that the examples and embodiments described herein are for illustrative purposes only and that various modifications or changes in light thereof will be suggested to persons skilled in the art and are to be included within the spirit and purview of this application.
This application claims the benefit of U.S. Provisional Application Ser. No. 62/008,201, filed Jun. 5, 2014, the disclosure of which is hereby incorporated by reference in its entirety, including all figures, tables and drawings.
This invention was made with government support under sub-contract 11-S587-102-01-C1, prime contract FA8650-07-D-5800, awarded by the Air Force Research Laboratory. The government has certain rights in the invention.
Filing Document | Filing Date | Country | Kind |
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PCT/US2015/034432 | 6/5/2015 | WO | 00 |
Number | Date | Country | |
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62008201 | Jun 2014 | US |