Patent Application
20180044473
The invention relates to the use of dicyanamide-containing ionic liquids which accelerates the cure and decreases the cure temperature of cyanate esters to form unique thermoset polymers having a triazine network.
The unique ring-forming trimerization cure mechanism and rigid thermoset structure of cyanate ester resins (CEs) give them a range of valuable properties for high performance materials applications. Nair, C. et al., Cyanate Ester Resins, Recent Developments. Springer Berlin/Heidelberg. 2001; Vol. 155, pp 1-99.
The trimerization of cyanate ester monomers can occur without additives, although this is thought to proceed due to the presence of trace monomer synthesis catalysts or residual phenols as taught by Chen, C.-C. et al. (A kinetic study on the autocatalytic cure reaction of a cyanate ester resin, Journal of Applied Polymer Science 2004, 92 (5), 3067-3079). Typically, active hydroxyl donors such as nonylphenol in concert with metal catalysts such as titanium, cobalt, copper, chromium, iron, tin, zinc, or manganese are used to accelerate cure speed and extent. A simplified scheme of trimerization is shown in
These catalysis systems have several downsides. Nonylphenol acts as an endocrine mimic, with metabolic and reproductive consequences in many aquatic species, with feminization of males, sterility, and juvenile death occurring with concentrations as low as 8.2 μg/L, as discussed in Soares, A. et al. (Nonylphenol in the environment: A critical review on occurrence, fate, toxicity and treatment in wastewaters. Environment International 2008, 34 (7), 1033-1049); and Giger, W. et al. (4-Nonylphenol in sewage sludge: accumulation of toxic metabolites from nonionic surfactants. Science 1984, 225 (4662), 623-625). Metallic coordination catalysts, particularly copper, have been shown to accelerate hydrolysis within cured cyanate ester resins, leading to significant network degradation, Tg loss, and blistering, see Hong, S.-G. et al. (Catalytic effects of copper oxides on the curing and degradation reactions of cyanate ester resin. Journal of Applied Polymer Science 2007, 104 (1), 442-448); Zacharia, R. E. et al. (Effect of catalyst on the thermal degradation of a polycyanurate thermosetting system. Journal of Applied Polymer Science 1997, 64 (1), 127-131); and Marella, V. V., et al. (Hydrolytic degradation of highly crosslinked polyaromatic cyanate ester resins. Polymer Degradation and Stability 2014, 104 (0), 104-111).
Accordingly, it is an object of certain embodiments of the present invention to provide a curable composition which can be cured to form a thermoset polymer having a triazine network, wherein the thermoset polymer has a range of valuable properties for high performance materials applications.
Another object of certain embodiments of the present invention is to incorporate ionic liquids comprising dicyanamide anions that accelerate the cure of the curable composition to form the thermoset polymer having a triazine network.
Another object of certain embodiments of the present invention is to use a synthesis strategy which modifies the network structure and removes or reduces the need for metal catalysts which contribute to cyanate ester degradation, potentially decreasing the rate of hydrolytic degradation and its associated Tg loss.
An aspect of the invention is a curable composition for preparing a thermoset polymer having a triazine network, said curable composition comprising: (a) a cyanate ester monomer; and (b) at least one ionic liquid comprising a dicyanamide anion. An advantage of the invention incorporating the curable composition is that the reaction temperature can be lowered when compared to conventional methods.
Another aspect of the invention is a method of preparing the thermoset polymer having a triazine network comprising combining, in any order, the following: (a) a cyanate ester monomer, and (b) at least one ionic liquid comprising a dicyanamide anion to form a mixture, and heating the mixture to a temperature sufficient to cause a curing reaction to thereby form the thermoset polymer having a triazine network.
Another aspect of the invention is a thermoset polymer having a triazine network, wherein:
the polymer comprises a triazine ring (II) bonded to two oxygen atoms and a nitrogen anion, wherein each of the two oxygen atoms are members of a different cyanurate ester functional group connected to the network, and wherein the nitrogen anion is bonded to a triazine ring (III), and
wherein the polymer further comprises a triazine ring (IV) bonded to three oxygen atoms, wherein each of the three oxygen atoms are members of a different cyanurate ester functional group connected to the network.
Another aspect of the invention is drawn to a thermoset polymer having a triazine network, wherein the polymer comprises a triazine ring (I) bonded to two oxygen atoms and a nitrogen anion, wherein each of the two oxygen atoms are members of a different cyanurate ester functional group connected to the network, and wherein the nitrogen anion is bonded to a carbon atom of a cyano group.
The thermoset polymer having a triazine network of the present invention can be tailored to have a range of valuable properties for high performance materials applications. Glass transition temperatures (Tg) in the range of 180-400° C. promise applications in high temperature performance composites, and a Tg above hot solder temperatures makes the inventive thermoset polymer a promising substitute for epoxies in the microelectronics industry. Other significant properties include good fracture toughness, excellent substrate adhesion, low shrinkage, and low moisture uptake. For these and other applications in the electronics, communications, and aerospace industries, the properties of the inventive thermoset polymer make them attractive replacements for common thermosetting systems such as epoxies or maleimides.
For illustrative purposes, the principles of the present invention are described by referencing various exemplary embodiments thereof. Although certain embodiments of the invention are specifically described herein, one of ordinary skill in the art will readily recognize that the same principles are equally applicable to, and can be employed in other apparatuses and methods. Before explaining the disclosed embodiments of the present invention in detail, it is to be understood that the invention is not limited in its application to the details of any particular embodiment shown. The terminology used herein is for the purpose of description and not of limitation. Further, although certain methods are described with reference to certain steps that are presented herein in certain order, in many instances, these steps may be performed in any order as may be appreciated by one skilled in the art, and the methods are not limited to the particular arrangement of steps disclosed herein.
It must be noted that as used herein and in the appended claims, the singular forms “a”, “an”, and “the” include plural references unless the context clearly dictates otherwise. As well, the terms “a” (or “an”), “one or more” and “at least one” can be used interchangeably herein. It is also to be noted that the terms “comprising”, “including”, and “having” can be used interchangeably.
The term “resin” as used herein means an oligomer or polymer having a two or three-dimensional network structure depending on the extent of the cure.
The term “alkyl” as employed herein refers to straight, branched, cyclic, and/or substituted saturated moieties having a carbon chain of from about 1 to about 100 carbon atoms.
The term “alkenyl” as employed herein refers to straight, branched, cyclic, and/or substituted unsaturated moieties having a carbon chain of from about 3 to about 10 carbon atoms.
The term “aryl” as employed herein refers to single and multi-ring aromatic compounds that may include alkyl, alkenyl, aralkyl, amino, hydroxyl, alkoxy, and/or halo substituents, and/or heteroatoms including, but not limited to, nitrogen, oxygen, and sulfur.
An aspect of the invention is a curable composition for preparing a thermoset polymer having a triazine network, said curable composition comprising:
(a) a cyanate ester monomer, and
(b) at least one ionic liquid comprising a dicyanamide anion.
Preferably, the ratio of cyanate ester monomer to dicyanamide is 2:1 to 400:1, and more preferably, the ratio is 9:1 to 400:1. Most preferably, the ratio is 20:1 to 400:1.
In the curable composition of the present invention, it is preferred to not add metals which can catalyze trimerization of cyanate ester monomer under curing conditions. Metals which can catalyze trimerization of cyanate ester monomer under curing conditions may be present as an impurity in a concentration of less than 10 ppm, preferably less than 1 ppm. These metals include at least one of titanium, cobalt, copper, chromium, iron, tin, zinc, and manganese.
Ionic liquids are used in the curable composition that comprises a dicyanamide anion as an initiator for the cyanate ester cure. Ionic liquids are non-volatile, environmentally benign, and non-toxic. The term “ionic liquid” (IL) generally refers to a salt comprising an anion and a cation As used herein, the term, “ionic liquid” refers to a salt comprising an anion and a cation and capable of melting at a temperature falling within a range not higher than the curing temperature of the resin. Preferably, the ionic liquid is a molten salt at an ambient temperature comprising an anion and a cation. Room temperature ionic liquids (RTILs) are ionic liquids which have melting points below room temperature, i.e. (<23° C.). RTILs are characterized by being non-volatile, they typically have negligible vapor pressure, are typically non-flammable and have a high thermal stability. In addition, RTILs may exhibit a wide temperature range for liquid phase of up to about 300° C. RTILs are highly solvating, yet non-coordinating and make good solvents for many organic and inorganic materials. RTILs also have an adjustable pH.
In the curable composition of the invention, it is desirable that the ionic liquid uniformly liquefies at or below the curing temperature, and from the viewpoint of readily preparing the composition, the melting point of the ionic liquid is preferably lower than an ambient temperature such as 23° C.
In an aspect of the invention, the ionic liquid comprises the dicyanamide anion and at least one cation selected from the group consisting of imidazolium, phosphonium, pyridinium and pyrrolidinium. Preferably said cation is selected from the group consisting of 1-ethyl-3-methyl imidazolium, 1-(3-cyanopropyl)-3-methyl imidazolium, trihexyltetradecylphosphonium, 1-(2-hydroxyethyl)-3-methylimidazolium, 1-butyl-3-methyl pyridinium, and 1-butyl-1-methyl-pyrrolidinium.
In addition to the dicyanamide anion, the ionic liquid can include anions such as alkyl sulfate anions such as ethyl sulfate, tosylate anions, tetrafluoroborate ion, bis(trifluoromethylsulfonyl) imide anions, and halide anions such as a fluoride ion, a chloride ion, a bromide ion, and an iodide ion.
Ionic liquids may be prepared in any suitable, conventional manner. For producing the ionic liquid, an anion exchange method that comprises reacting a precursor comprising a cation moiety such as an alkylimidazolium, alkylpyridinium, alkylammonium or alkylsulfonium ion and a halogen-containing anion moiety, with NaBF4, or the like, can be employed. Alternatively, an acid ester method comprising reacting an amine substance with an acid ester to introduce an alkyl group can be employed. Another method involves neutralization of an amine with an organic acid to give a salt. Other suitable, conventional methods may also be employed. In the neutralization method with an anion, a cation and a solvent, the anion and the cation are used in an equivalent amount, and the solvent in the obtained reaction liquid is evaporated away. The residue may be used directly as it is; or an organic solvent (e.g., methanol, toluene, ethyl acetate, acetone) may be further added thereto and the resulting liquid may be concentrated.
The ionic liquids may optionally be substituted with one or more groups selected from hydroxyl, cyano, vinyl, acrylate, methacrylate, epoxy, ether and carboxyl groups to provide additional reactivity and/or functionality to the ionic liquids. Ionic liquids substituted with mixtures of such groups may also be employed. Although not specifically defined, the amount of the ionic liquid to be added to the curable composition may be any amount which is sufficient for achieving at least some and preferably complete resin curing.
With respect to the cyanate ester monomer, preferably the cyanate ester monomer has two or more cyanate ester groups bonded to a core which is an optionally substituted aryl, alkyl or aralkyl group. The core is depicted as R1 in the first structure of
It is also envisioned to be able to incorporate tricyanate esters, tetracyanate esters, or higher-order polycyanate esters in the curable composition.
In an embodiment, a dicyanate (Primaset LECY) and/or a polyphenolic (Primaset PT30) resin can be used as shown in
The concentration of the cyanate ester monomer in the curable composition is 67 to 99.75 mol %, preferably, 90-99.75 mol % and most preferably, 95 to 99.75 mol %.
As noted in the mechanism described in
An aspect of the invention is a method of preparing a thermoset polymer having a triazine network comprising combining, in any order, the following:
(a) a cyanate ester monomer; and
(b) at least one ionic liquid comprising a dicyanamide anion;
to form a mixture, and heating the mixture to a temperature sufficient to cause a curing reaction to thereby form the thermoset polymer having a triazine network.
An advantage of the present invention is the fact that the curing temperature can be decreased by using the RTILs without the need for added metal catalysts. The temperature of the curing reaction can be 80-350 C. Preferably, the curing temperature is 90-350 C. Most preferably, the curing temperature is 105-350 C.
An aspect of the invention is a thermoset polymer having a network comprised of triazine rings (Formulae 1-3). The unique aspect of this invention is that at least some rings incorporate a dicyanamide anion (Formula 1). Alternatively, some dicyanamide ions may be incorporated into two adjacent rings, providing an ionic amine linkage between them. (Formula 2). In the case of anionic structures, an associated cation must be present, and can vary in structure. Depending on the ratio of dicyanamide to cyanate ester monomer, some rings may also have no dicyanamide structure (Formula 3).
As shown in Formula 1, the inventive thermoset polymer has a triazine network, wherein the polymer can comprise a triazine ring (I) bonded to two oxygen atoms and a nitrogen anion. Each of the two oxygen atoms are members of a different cyanurate ester functional group connected to the network, and wherein the nitrogen anion is bonded to a carbon atom of a cyano group.
As shown in Formula 2, the thermoset polymer having a triazine network can comprise a triazine ring (II) bonded to two oxygen atoms and a nitrogen anion, wherein each of the two oxygen atoms are members of a different cyanurate ester functional group connected to the network, and wherein the nitrogen anion is bonded to a triazine ring (III).
A+ as shown in Formulae 1 and 2 can be any cation that does not adversely affect the properties of the thermoset polymer.
As shown in Formula 3, the thermoset polymer having a triazine network can comprise a triazine ring (IV) bonded to three oxygen atoms, wherein each of the three oxygen atoms are members of a different cyanurate ester functional group connected to the network, as shown in Formula 3.
In an embodiment of the invention, the thermoset polymer having a triazine network has all of Formulae 1, 2 and 3. In another embodiment, the thermoset polymer having a triazine network has Formulae 2 and 3. In yet another embodiment, the thermoset polymer having a triazine network has Formula 1. Moreover, in another embodiment, the thermoset polymer having a triazine network has Formulae 1 and 3.
As shown in the mechanism of
As mentioned above, the inventive thermoset polymer having a triazine polymer has no added metals used to catalyze the synthesis of the polymers. This provides an advantage over conventional polymers synthesized with metal catalysts, because the metals remaining in conventional polymers can also catalyze the degradation of the polymer when the polymer is exposed to high temperatures. As such, the inventive thermoset polymer having a triazine polymer has a high resistance to: i) network degradation; ii) Tg loss under humid conditions; and iii) blistering. For instance, the inventive thermoset polymer having a triazine network has a glass transition (Tg) temperature of 180 to 400 C. Preferably, the Tg is 220 to 370 C, and most preferably, the Tg is 260 to 360 C.
The following examples are illustrative, but not limiting, of the methods and compositions of the present disclosure. Other suitable modifications and adaptations of the variety of conditions and parameters normally encountered in the field, and which are obvious to those skilled in the art, are within the scope of the disclosure.
Liquid samples were mixed in a 20 ml vial, and 10-20 mg samples removed for testing. Samples were crimped into a TA Instruments Q 2000 Differential Scanning Calorimeter (“DSC”) having a hermetically sealed DSC pan and run through a temperature ramp procedure from room temperature to 350° C. at a ramp rate of 10° C./min (for IL/LECY) or 5° C./min (for IL/PT-30) (wherein PT-30 is a polyphenolic cyanate ester).
Liquid samples were mixed in a 20 ml vial and placed between two 25 mm diameter×4 mm thickness NaCl single-crystal optical elements with a 25 μm spacer. This salt plate apparatus was placed in an isothermal aluminum cell inside a Thermo-Nicollet 6700 FTIR spectrometer. A series of transmission spectra were taken with a resolution of 8 cm−1. Degradation samples were measured in a Thermo Nexus 670 near-FTIR, with the transmission beam passing directly through the treated 1.5 mm-thick sample.
0, 0.5, 1, 2, 5, and 10% EMIM-DCN (“EMIM” is 1-ethyl-3-methyl imidazolium) in LECY Samples were poured into 60×15×4 mm rectangular molds, and cured at 80° C./12 h, 100° C./4 h, 120° C./4 h, 150° C. 2 h, followed by a 300° C. post-cure for 1 h (“slow” cure pathway). For hydrolytic degradation testing, 2% w/w EMIM-DCN samples with a 30×12×3 mm rectangular size were cured at 105° C./12 h, 130° C./2 h, 220° C./2 h, followed by a post-cure at 300 C for 1 h (“fast” cure pathway). To determine Tg for all samples, DMA was performed in a TA Instruments 2980 DMA from room temperature to 350° C. with a temperature ramp of 2° C./min.
DMA samples were conditioned and monitored following the procedure of Marella et al., supra. This procedure involves long-time humidity conditioning (up to 5 weeks @85° C./85% RH), thermal drying, and analysis by gravimetric mass uptake, mass-calibrated near-FTIR, and DMA. This method explicitly measures both degree of hydrolysis (by mass and IR) and the consequences of that hydrolysis on the temperature performance of the polymer. Data for 2% w/w EMIM-DCN in LECY were compared with LECY samples catalyzed with 2 phr nonylphenol/160 ppm Cu2+.
An exemplified embodiment of the present invention of the formulation and cure procedure is presented as follows. Mix 5% by weight EMIM-DCN into a solution of Primaset LECY with a sonicator, rotational mixer, or impeller-driven mixer. After mixing, degas under vacuum. Pour the solution into molds of the desired shape for thermal curing. Cure at 105° C. for 12 h, 130° C. for 2 h, and 220° C. for 2 h. At this stage, the network has gelled and the part will retain shape. If desired, the part can be removed from the mold. Optionally within or without the mold, the part can be post-cured at 300° C. for one hour.
Calorimetry, FTIR, and DMA were used to characterize the interaction between LECY and dicyanamide-containing ionic liquids. DSC shows the effect of cure acceleration by concentration and cation type. DMA on cured samples shows the effect of initiator and thermal history on Tg. Isothermal, time-resolved FTIR spectroscopy separately shows the interaction between DCN anions and cyanate ester functional groups, the formation of triazine rings, the formation of reaction intermediates, and the formation of side-products.
In addition to curing studies, a humidity-conditioning degradation experiment was run, comparing 2% EMIM-DCN with a typical metal/hydroxyl catalyst system (2 phr nonylphenol/150 ppm Cu2). This experiment included dry and wet mass uptake, Tg drop by DMA, and near-FTIR spectroscopy to determine the nature of the degradation reaction.
Five other DCN-containing RTILs were tested under the same conditions, including: 1-butyl-3-methyl imidazolium dicyanamide (BMIM-DCN), 1-butyl-3-methyl pyridinium dicyanamide (BMPyridinium-DCN), and 1-butyl-1-methyl-pyrrolidinium dicyanamide (BMPyrolliinium-DCN), 1-(3-cyanopropyl)-3-methyl imidazolium dicyanamide (CNMIM-DCN), 1-(2-hydroxyethyl)-3-methylimidazolium dicyanamide (OHMIM-DCN) at equivalent molarities. All DCN-containing RTILs significantly accelerated cure. OHMIM-DCN cured at a slightly lower temperature than the others, likely acting as a hydroxyl donor in addition to the DCN interaction.
The cyanate region shows peaks for both cyanate ester (2267 and 2233 cm−1) and dicyanamide (2225, 2194, and 2130 cm−1). Additionally, a new peak at 2171 cm−1 is formed, although it disappears after the post-cure. For analytical purposes, the peak at 2267 cm−1 is useful as a marker for the cyanate ester functionality, while the peak at 2194 cm−1 is useful as the marker for dicyanamide functionality. The peak at 2233 cm−1 appears as a composite of two peaks that appear at similar locations, the 2233 cm−1 1 peak of cyanate ester and the 2225 cm−1 peak of dicyanamide. As both decrease together, it is expected to have the same behavior, but is less analytically useful due to the overlap. The new peak formed at 2171 cm−1 is likely a cyanate peak.
The spectroscopy of triazine formation shows two peaks at 1563 and 1366 cm, indicating that the resin product is the same triazine ring as in the metal- and auto-catalyzed case. Significantly, the saturation of the triazine peaks occurs more slowly than the decrease in cyanate groups, indicating the presence of an intermediate. Also appearing in the fingerprint region are two transient peaks at 1677 and 1060 cm−1. They trend together, peaking at a relatively short time, and slowly decreasing over the remainder of the experiment. These peaks provide clues as the identity of the reaction intermediate, and likely correspond to C═N and C—N stretching, respectively.
Two peaks are used for reference. In the fingerprint region, the aromatic C—C stretching of the bisphenol E polymer backbone (from LECY) at 1501 cm−1 provides a convenient reference peak for quantitative analysis. Additionally, the 2973 cm−1 aromatic C—H stretch, also corresponding to the Bisphenol E polymer backbone, provides a redundant, roughly equivalent reference. Comparing analysis performed based on either of the reference peaks yielded practically indistinguishable results, confirming that the effects noted in this section are fundamental, rather than artifacts of wavelength-based FTIR intensity effects.
In order to test for hydrolytic degradation behavior, the methodology of Marella et al., supra, was used to compare 2% EMIM-DCN and unpublished results from our research group on 2 phr nonylphenol/160 ppm Cu2+ catalyzed LECY. Samples were dried, humidity conditioned, and then re-dried after conditioning. After cycling, mass uptake, near-FTIR, and DMA measurements were taken. Mass uptake corresponds to hydrolysis product formation, the nature of which is corroborated by FTIR. DMA indicates the degree to which hydrolytic degradation affects Tg.
The identity of the mass uptake results is verified by near-FTIR.
Hydrolytic degradation affects glass transition temperature.
Without being bound to theory, it is believed based on the FTIR data (Table 1,
The dicyanamide anion is herein referred to as an initiator, and not a catalyst, because the dicyanamide anion becomes part of the triazine ring.
The decrease in dicyanamide (2130 cm−1), corresponding in time to the decrease in cyanate ester groups (2267 cm−1), indicate that the dicyanamide group is participant in the primary reaction. Further, the appearance of a shifted peak in the cyanate region (2171 cm−1), indicates a change in the structure to which the cyanate is bonded. Thus, the dicyanamide is present in the triazine ring structure, leaving an unreacted cyanamide. Finally, based on the appearance of a large hydroxyl peak (3350 cm−1) and the disappearance of the shifted cyanate peak (2171 cm−1), it is presumed that this cyanamide is further hydrolyzed during post-cure.
With respect to side reactions, cyanate ester synthesis is complicated with monomer carbamate formation, and the cured resin is affected by hydrolytic degradation through both ring-opening and chain scission mechanisms. In addition to those reactions, the cyanamide group attached to triazine ring from this mechanism (representing the cyanate peak at 2171 cm−1) show signs of hydrolysis during the high temperature post-cure, simultaneous to the appearance of a broad hydroxyl peak (3350 cm−1). This demonstrates that an additional side reaction that should be considered is the reduction of unreacted cyanamides. Since this reaction does not affect the network structure, the Tg is unlikely to be affected by this side reaction.
The observed loss of Tg with increasing RTIL content and the variance with cure schedule (
Cross-linking density is reduced as the dicyanamide replaces a LECY monomer. While the dicyanamide does have two functional groups, the small size and limited flexibility of the amide linker between them effectively prevents the reaction of both end groups. However, it is possible that both end cyanate groups of dicyanamide react.
Water uptake, hydrolytic degradation rates, and Tg dropoff were compared for 2% w/w EMIM-DCN cured LECY and Cu2+/nonylphenol cured LECY. Equilibrium water uptake was determined from mass uptake (
The main conclusion is that non-toxic dicyanamide-containing RTILs act as initiators for cyanate ester resin systems by a unique mechanism involving the dicyanamide anion to create a high-Tg resin with low-temperature curing parameters. This initiation involves a direct reaction with the dicyanamide anion, creating an anionic thermoset structure with an ionically associated cation. Cation structure influenced the degree of initiation, especially in the case of a hydroxyl-containing cation. Increased RTIL content shows a plasticization effect due to the decrease in cross-linking density. Tg of the resin also showed great sensitivity to thermal cure schedule design; in at least one case (2% RTIL, Tg=270° C.), the plasticization effect was minimal at an RTIL loading that offered effective cure acceleration allowing for optimization of the cure conditions.
The resulting matrix showed lower equilibrium water uptake (1.5% vs 1.8%), and similar hydrolytic degradation and Tg reduction rates after exposure to a humid environment, when compared with a metal/hydroxyl-catalyzed cyanate ester.
The foregoing examples have been presented for the purpose of illustration and description only and are not to be construed as limiting the invention in any way. The scope of the invention is to be determined from the claims appended hereto.
Other embodiments of the present disclosure will be apparent to those skilled in the art from consideration of the specification and practice of the embodiments disclosed herein. It is intended that the specification and examples be considered as exemplary only, with a true scope of the disclosure being indicated by the following claims.
All documents mentioned herein are hereby incorporated by reference in their entirety or alternatively to provide the disclosure for which they were specifically relied upon.
The foregoing embodiments are susceptible to considerable variation in practice. Accordingly, the embodiments are not intended to be limited to the specific exemplifications set forth herein. Rather, the foregoing embodiments are within the spirit and scope of the appended claims, including the equivalents thereof available as a matter of law.
The applicant(s) do not intend to dedicate any disclosed embodiments to the public, and to the extent any disclosed modifications or alterations may not literally fall within the scope of the claims, they are considered to be part hereof under the doctrine of equivalents.
This invention was made with government support under Grant W911NF-06-2-0013 awarded by the Army Research Laboratory (ARL). The Government has certain rights in this invention.
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/US2016/015604 | 1/29/2016 | WO | 00 |
| Number | Date | Country | |
|---|---|---|---|
| 62109365 | Jan 2015 | US |
