HOLLOW POLYIMIDE MICROSPHERES

Abstract: A shaped article composed of an aromatic polyimide has a hollow, essentially spherical structure and a particle size of about 100 to about 1500 mu m, a density of about 1 to about 6 pounds/ft<3> and a volume change of 1 to about 20% by a pressure treatment of 30 psi for 10 minutes at room temperature. A syntactic foam, made of a multiplicity of the shaped articles which are bonded together by a matrix resin to form an integral composite structure, has a density of about 3 to about 30 pounds/ft<3> and a compression strength of about 100 to about 1400 pounds/in<2>.

Description: HOLLOW POLYIMIDE MICROSPHERES Ongin of the Invenϋon The invenUon descnbed herem was jointly made by employees of the Umted States Government and employees of Unitka Ltd In the performance of work under NASA MO A, SAA #385 Background of the Invention 1 Field of the Invention The present mvention relates generally to polyimides It relates in particular to shaped articles composed of aromatic polyimides. especially hollow microspheres 2 DescnpUon of the Related Art High performance polyimides are presently employed in a number of applications, for example m joining metals to metals, and in joining metals to composite structures in the aerospace industry In addition, polyimides are rapidly finding new uses as foam insulation in cryogenic applications and as structural foam, having increased structural stiffness without large weight mcreases Foams of vaπous densities and thermal and mechanical properties are now being required for future reusable launch vehicles, mantime ships, and aircraft Polyimide foam matenals have a number of beneficial attributes m these applications, such as high temperature and solvent resistance, flame resistance, low smoke generation, high modulus and chemical and hot water resistance U S Patents 5,147,966 and 5,478,916 disclose polyimides that can be melt processed into vaπous useful forms such as coartngs, adhesives, composite matrix resins and films These polyimides are prepared from vanous diamines and dianhydπdes m vaπous solvents The use of monoanhydπdes as endcappmg agents is also disclosed m these patents to control the molecular weight of the polymers and, m turn, to make them easier to process m molten form The use of ethers to make polyimide adhesives was disclosed m U S Patent 4,065,345, which demonstrates another method to produce polyimide resin systems Figure 1 shows the method employed by these patents to produce polyimides U S Patent 3,483,144 discloses a process for making polyimide foam by ball milling a mixture of monomers and heating the mixture to 300°C In all cases, the foams produced by this patent are the result of dianhydπdes or tetraacids being dissolved b> a diamine upon melting The ensuing reaction produces water and thus foams the molten mateπal Figure 2 illustrates the process to make foam by this patent The state-of-the-art technology for making polyimide foams as disclosed in U S Patents 5,298,531, 5,122,546, 5,077,318, and 4,900,761 utilizes soluϋons of diamines and dianhydnde deπvatives in a low molecular weight alkyl alcohol solvent Polyimide precursor solutions and powders therefrom are then processed mto foams through the expulsion of water and alcohol (R-OH) during the thermal lπudization process In these cases the alcohol solvent reacts initially with the dianhydπde to form a covalently bonded specie referred to as a dialkylester-diacid (DAD A) before the aromatic diamine is added The aforementioned patents also illustrate the use of blowing agents to aid in the foaming process The blowing agents utilized by these patents serve as a separate entity and usually result in a foam that has residual blowing agent within its cell walls Figure 3 demonstrates the state-of-the-art m this foam preparation technology Howsoever useful, these related art foam products and processes do not provide for all that is required m present and future applications In particular, they do not provide for efficient and efficacious repair of foam insulation already in place, for example on aircraft, spacecraft, and maritime ships Moreover, they do not readily and effectively afford the preparation of syntactic foam structures, the demand for which continues to increase because of their beneficial attributes U S Patents 4,407,980, 4,425,441, and 4,433,068 disclose the preparation of macro balloons made from a mixture of polyimide and polyinude-amide polymers, the particle size thereof being at least 0 5 - 10mm Because these structures are not pure polyimide products, they are found wantmg in respect of thermal stability and non-flammabihty Because these structures are macrospheres, they lack the wide range of utility that would be afforded by microspheres Summary of the Invention It is accordingly a pnmary object of the present mvention to provide what is lacking m the related art, viz , a foam-hke product which can provide for efficient and efficacious repair of foam insulation already in place, for example on aircraft, spacecraft, and maπtime ships, and which readily and effectively affords the preparation of syntactic foam structures It is a related object of the present mvention to provide a polyimide foam-like product which has all of the attributes characteπstic of polyimides, and which in addition can supply what has been found wanting m the related art It is another related object of the present invention to provide a syntactic foam structure which has properties and characteπstics which meet present and future demands These objects and their attending benefits are achieved and the disadvantages of the related art are avoided, by the present invention In one aspect thereof the present invention is a multiplicity of hollow polyimide microspheres 1 e , shaped articles, each of which has an aromatic polyimide shell, a hollow mteπor. and an essentially spheπcal structure with a particle size between about 100 and about 1500 μm In another aspect thereof, the present invention is a syntactic foam, which is made up of a multiplicity of shaped articles accordmg to the present mvention, which are bonded together by a matπx resin to form an integral, composite structure having a density according to ASTM D-3574A of between about 3 and about 30 pounds/ft 3 and a compression strength accordmg to ASTM D-3574C of between about 100 and about 1400 pounds/in 2 Bnef Descnption of the Drawmgs For a more complete understanding of the present invention, including its primary and related objects and benefits, reference should be made to the Descnption of the Preferred Embodiments, which is set forth below This Descnption should be read together with the accompanying Drawings, wherein FIG 1 is a process schematic representing a standard process for preparing polyimides, FIG 2 is a process schematic representing a related art preparation of polyimide foam by ball milling, FIG 3 is a process schematic representing a state-of-the-art process for preparing polyimide foam, and FIG 4 is a process schematic representing a process for the preparation of hollow polyimide microspheres accordmg to the present mvention Descnption of the Preferred Embodiments Shaped articles accordmg to the present invention are composed of an aromatic polyimide and have a density accordmg to ASTM D-3574A of between about 1 and about 6 pounds/ft 3 , and they exhibit a volume change between about 0% and about 20% by a pressure treatment of 30 psi for 10 minutes at room temperature Shaped articles accordmg to the present invention also have a thermal stability of from 0 to about 1% weight loss at 204°C as determined by thermogravimetπc analysis (TGA) The aromatic polyimide which advantageously composes the shaped articles according to the present mvention has repeatmg units represented by formula (I) wherein R is a tetravalent aromatic radical having 1 to 5 benzenoid-unsaturated nngs of 6 carbon atoms, the four carbonyl groups being directly bonded to different carbon atoms in a benzene ring of the R radical, each pair of carbonyl groups being bonded to adjacent carbon atoms m the benzene ring of the R radical, and R' is a divalent aromatic radical having 1 to 5 benzenoid-unsaturated nngs of 6 carbon atoms, the ammo groups being directly bonded to different carbon atoms m a benzene ring of the R' radical As used herein, the following abbreviations are understood to mean ODPA = 4,4'-oxydιphthalιc anhydnde ODP-TA = 4,4'-oxydιphthalιc acid (a tetraacid) BPDA = 3,3',4,4'-bιphenyl tetracarboxyhc dianhydnde BTDA = 3,3'4,4'-benzophenone tetracarboxyhc dianhydnde DSDA = tetracarboxyhc dianhydnde PMDA = pyromelhtic dianhydnde BPADA = 2,2-bιs(4-(3,4-carboxyphenyl))propane dianhydnde 3,4' ODA = 3,4'-oxydιanιlιne 4,4' ODA = 4,4'-oxydιanιhne APB = l,3-bιs(3-amιnophenox7)benzene BPB = 1, 3 -bιs(4-amιnophenoxy) benzene m-PDA = m-phenylenediamine p-PDA = p-phenylenedianune 3,3 'DDS = 3,3'-dιammodιphenylsulfone 4,4'DDS = 4,4'-dιamιnodιphenylsulfone 4,4 BAPS = bιs(4-(4-aιmnophenoxy)phenyl)sulfone 4,3 BAPS = bιs(4-(3-ammophenoxy)phenyl)sulfone 3 BAPB = 4,4'-bιs(3-amιnophenoxy)bιphenyl 4 BAPB = 4,4'-bιs(4-amιnophenoxy)bιphenyl BAPP = 2,2'-bιs(4-(4-amιnophenoxy)phenyl)propane Shaped articles accordmg to the present mvention are composed of any aromatic polyimide, and preferably an aromatic polyimide havmg repeatmg units represented by formula (I) above Shaped articles accordmg to the present mvention have been found to be especially beneficial if the aromatic polyimide of which they are composed is prepared by reacting at least one denvative of a dianhydnde selected from the group consisting of ODPA, BPDA, BTDA, DSDA, PMDA and BPADA with at least one denvative of a diamine selected from the group consistmg of 3.4'ODA, 4,4'ODA, APB, BPB, m-PDA, p-PDA, 3,3 'DDS. 4,4'DDS, 4.4BAPS, 4,3BAPS, 3BAPB, 4BAPB and BAPP Equally beneficial results are obtained if the aromatic polyimide is an admixture of two or more different polyimides prepared by reactmg at least one denvative of a dianhydnde selected from the group consistmg of ODPA, BPDA, BTDA, DSDA, PMDA and BPADA with at least one denvative of a diamine selected from the group consisting of 3,4'ODA, 4,4'ODA, APB, BPB, m-PDA, p-PDA, 3,3'DDS. 4,4'DDS, 4,4BAPS, 4,3BAPS. 3BAPB, 4 BAPB and BAPP Also beneficial are shaped articles denved from copolyiπude synthesized from the aromatic dianhydnde denvatives and aromatic diamine denvatives listed above The combination of particle size, density and resistance to pressure, along with the chemical and thermal properties of aromatic polyimides, provides shaped articles accordmg to the present mvention with the potential for use in many applications in the aeronautics, aerospace, and mantime mdustnes Shaped articles accordmg to the present invention are advantageously prepared by the following process ( 1 ) providmg an aromatic polyimide precursor solid residuum, which is an admixture of an aromatic compound (A), which is an aromatic dianhydnde or a denvative of an aromatic dianhydnde, and an aromatic compound (B), which is an aromatic diamine or a denvative of an aromatic diamine, plus a complexing agent (C), which is complexed with the admixture by hydrogen bondmg, the complexing agent (C) being present m an amount sufficient to provide from about 1 to about 15 % by weight, based on the total weight of the polyimide precursor solid residuum Especially beneficial results are obtained if the aromatic polyimide precursor solid residuum is prepared from an admixture of an aromatic compound (A) ( A ) and an aromatic compound (B) wherein n is an integer from 0 to 3, and Ri is hydrogen or an alkyl group, and R 2 is a tetravalent aromatic radical havmg 1 to 5 benzenoid-unsaturated nngs of 6 carbon atoms, R 3 is a divalent aromatic radical havmg 1 to 5 benzenoid-unsaturated nngs of 6 carbon atoms, plus a complexmg agent (C) which is complexed with the admixture by hydrogen bondmg and which has a boiling temperature of less than 200°C, the complexing agent (C) being present m an amount sufficient to provide from about 1 to about 15% by weight, based on the total weight of the aromatic polyimide precursor solid residuum which is formed by heating the complexed admixture to remove any excess complexmg agent and volatile byproducts Outstanding results are obtained if the aromatic compound (A) and the aromatic compound (B) as specified above are present in the admixture m approximately equimolar amounts , (2) charging the aromatic polyimide precursor solid residuum mto a non-confined vessel, (3) heating the aromatic polyimide precursor solid residuum in the non-confined vessel to a temperature between about 100°C and 200°C to produce a multiphcity of shaped articles from the aromatic polyimide precursor solid residuum in the non-confined vessel, (4) heating the multiphcity of shaped articles to a temperature between about 200°C and 300°C to produce a multiplicity of thermally lnudized shaped articles, and (5) cooling the multiplicity of thermally limdized shaped articles for subsequent utilization Although not required m the practice of this process, conventional additives may be added to the above descnbed solution or to the resulting polyimide precursor solid residuum if desired Examples of such additives are surface active agents (SH190,8H193 - Toray/Dow Corning silicone, Zonyl FSC - DuPont, L550, L5430 - Union Carbide), pigments, fibrous fillers, and the like In another aspect thereof the present mvention is a syntactic foam, which is made up of a multiplicity of shaped articles according to the present invention, which shaped articles are bonded together by a matnx resin to form an mtegral composite structure Tlus structure has a density accordmg to ASTM D-3574A of between about 3 and about 30 pounds/ft 3 and a compression strength accordmg to ASTM D- 3574C of between about 100 and about 1400 pounds/in 2 Advantageously the matnx resin employed is a thermosetting resin, such as an epoxy resm, a thermosetting polyimide resin, or a phenolic resin, all of which have afforded syntactic foams havmg excellent properties Equally beneficial results are obtained if the matnx resm is a thermoplastic resm Especially preferred thermoplastic resins are polyamides, polyarylene sulfones, polyarylene ketones, polyarylene ether ketones, polyarylene ether sulfones, polyarylene sulfides, polyphenylene oxides, and polyimides Syntactic foams accordmg to this aspect of the present mvention have excellent high temperature and solvent resistance, flame resistance, high modulus, and excellent chemical and hot water resistance They have found significant application as structural foam, where substantial stiffness and large weight reduction are required EXAMPLES The following Examples are illustrative of the present invention and are not mtended to limit its scope I. Preparation of an Aromatic Polyimide Precursor Solid Residuum 1 756 g (2 4 mol) of ODPA was dispersed in a mixture of 480 g of THF and 280g of MeOH at room temperature This solution was treated at 70 °C for 6 hours m order to convert the ODPA into ODPA- DADA complexed with THF by hydrogen bondmg 488g (2 4 mol) of 3,4'ODA was added to the resulting solution of ODPA-DAD A and stirred for 2 hours to yield a homogenous polyimide precursor solution The resultmg polyimide precursor solution had a solids content of 70 wt % and a viscosity of 20 poise at 20°C The solution was then charged to a stainless-steel vat and treated at 70°C for 14 hours m order to evaporate the solvent (THF and MeOH) The resulting matenal was crushed into a fine powder (2 to 500 μm) (These powders are sieved usmg a mesh, if needed ) The polyimide precursor powders were then treated for an additional amount of time (0 to 300 minutes) at 80°C to further reduce the residual solvents to about 1-10 wt % depending on the final density desired Residual amounts of THF were determined by measuring proton NMR spectra of the solid residua 2 The procedure of Example 1 was repeated except that BTDA and 4,4'ODA were used m replacement of ODPA and 3,4'ODA respectively 3 The procedure of Example 2 was repeated except that 4,3BAPS was used in replacement of 4,4'ODA 4 The procedure of Example 1 was repeated except that BPDA and a mixture of 3,4'ODA and APB (85/15 mol ratio) were employed mstead of ODPA and 3,4'ODA 5 227g (1 lmol) of 3,4'ODA was dissolved in a mixture of 1120 g of THF and 280g of MeOH at room temperature To the stirrmg 3,4'ODA solution, 176g (0 57mol) of ODPA was added gradually at 15°C over 40 mm The resulting mixture was stured for 2 hr at 15°C to yield a homogenous solution To this solution, 197g (0 57mol) of ODP A-tetraacid was added gradually and the mixture was stured for 24 hr at 30°C to yield a homogenous precursor solution Solid content and viscosity of the resulting solution were 30 wt % and 0 2 poise, respectively From this solution, polyimide precursor powders were prepared m a similar manner to Example 1 6 336g (0 78mol) of 4,4BAPS was dissolved in a mixture of 1120g of THF and 280g of MeOH at room temperature To the stirrmg 4,4BAPS solution, 125g (0 39mol) of BTDA was added gradually at 15°C over 40 mm The resultmg mixture was stirred for 2 hr at 15°C to yield a homogenous solution To this solution, 139 g (0 39mol) of BPDA-tetraacid was added gradually and the mixture was stured for 24 hr at 30°C to yield a homogenous precursor solution Solid content and viscosity of the resulting solution were 30 wt % and 0 2 poise, respectively From this solution, polyimide precursor powders were prepared m a manner similar to Example 1 7 The procedure of Example 6 was repeated except that 4,3BAPS was used m replacement of 4,4BAPS 8 The procedure of Example 6 was repeated except that BAPP was used in replacement of 4,4BAPS 9 The procedure of Example 6 was repeated except that a mixture of 4,4'DDS and 3,3'DDS (80/20 mol ratio) was used m replacement of 4,4BAPS 10 The procedure of Example 5 was repeated except that a mixture of 3,4'ODA and APB (85/15 mol ratio) and BPDA were used in replacement of 3,4'ODA and ODPA, respectively In Table 1 below, properties of the polyimide precursor solid residuum of the above examples are summarized Table 1 Properties of Polyimide Precursor Solid Residuum II Preparation of Hollow Polyimide Microspheres An appropnate amount of a polyimide precursor solid residuum which is designated (A), (B), (C). (D). (E). (F), (G), (H), (I), (J) in Table 1 above was individually charged into a separate open stainless steel container The contamers were place in an oven set at 100°C, and the precursor powders were held at tlus temperature for approximately 2 hours Following this, the temperature of the oven was increased to 200°C. and this temperature was maintained for 15 hours The containers were then returned to ambient conditions, and hollow polyimide microspheres were removed therefrom for testmg Basic properties of these hollow polyimide microspheres are summanzed in Table 2 below Table 2 Properties of Hollow Polyimide Microshperes * The pressure treatment is descnbed as follows Three grams of hollow polyimide microspheres were charged into a closed container, and the volume thereof was measured Nitrogen gas at a pressure of 30 psi was then applied to the microspheres for 10 minutes at room temperature Following this, the pressure was released and the volume of the microspheres in the container was measured The volume change in percent was recorded IH. Preparation of Syntactic Foams 1 50 g of the precursor (B) from Table 1 above was blended uniformly with 50 g of 3% offsetting ODPA-3,4'ODA polyimide powder which is commercially available The resulting mixture was charged mto an open stainless steel container, which was placed m an oven at 170 C C, and held up to 120 minutes at this temperature Once the hold was completed, the container was returned to ambient conditions to obtain lightly sintered flake made of polyimide powder and BTDA-4.4ODA polyimide microspheres The apparent density of the resulting flake was 11 pcf 2 The procedure of Example 1 was repeated except that 200 g of the precursor (B) was used The apparent density of the resulting flake was 9 pcf 3 An appropnate amount of the flake obtamed by the procedure of examples 1 and 2, respectively, was individually charged into a separate metal mold The mold was then pressed at 310°C for 30 mm under a pressure of less than 5 kg/cm" Following this, the mold was cooled to room temperature and opened to obtain a molded product Properties of the resulting syntactic foam are summarized in Table 3 below Table 3 Properties of Syntactic Foams As seen from Table 3, syntactic foams having a density of less than 30 pound/ft 3 are provided according to the present of a dry unconsolidated composition via dr> process in contrast to the processes of the art wluch include the conventional wet process and the unconsolidated composition via wet process

Claims: We claim 1 A shaped article compnsmg an aromatic polyimide and having a hollow, essentially sphencal structure and a particle size of from about 100 to about 1500μm 2 A shaped article accordmg to claim 1, which has a density accordmg to ASTM D-3574A of from about 1 to about 6 pounds/ft 3 3 A shaped article accordmg to claim 2, which exhibits a volume change of from about 0% to about 20% by a pressure treatment of 30 psi for ten minutes at room temperature 4 A shaped article accordmg to claim 3, which has a thermal stability of from 0 to about 1% weight loss at 204°C by thermogravimetnc analyzer (TGA) 5 The shaped article of claim 1, wherem the aromatic polyimide has repeating units represented by formula (I) wherein R is a tetravalent aromatic radical having 1 to 5 benzenoid-unsaturated nngs of 6 carbon atoms, the four carbonyl groups being directly bonded to different carbon atoms in a benzene ring of the R radical, each pair of carbonyl groups being bonded to adjacent carbon atoms m the benzene ring of the R radical, and R' is a divalent aromatic radical havmg 1 to 5 benzenoid-unsaturated nngs of 6 carbon atoms, the ammo groups being directly bonded to different carbon atoms in a benzene ring of the R' radical 6 The shaped article of claim 5, wherein the aromatic polyimide having repeating units represented by formula (I) is prepared by reacting at least one denvative of a dianhydnde selected from the group consistmg of ODPA, BPDA, BTDA, DSDA, PMDA and BPADA with at least one denvative of a diamme selected from the group consisting of 3,4' ODA, 4,4' ODA, APB, BPB, m-PDA, p-PDA, 3,3' DDS, 4,4' DDS, 4,4 BAPS, 4,3 BAPS, 3 BAPB, 4 BAPB and BAPP The shaped article of claim 1, wherem the aromatic polyimide is an admixture of two or more different polyimides prepared by reacting at least one denvative of a dianhydnde selected from the group consisting of ODPA, BPDA, BTDA, DSDA, PMDA and BPADA with at least one denvative of a diamme selected from the group consisting of 3,4' ODA, 4,4' ODA, APB, BPB, m-PDA, p-PDA, 3,3' DDS, 4,4' DDS, 4,4 BAPS, 4,3 BAPS, 3 BAPB, 4 BAPB and BAPP The shaped article of claim 6, wherem the aromatic polyimide is a copolyinude A process for prepaπng a multiplicity of shaped articles according to claim 1, which process compnses (1) providmg an aromatic polyimide precursor solid residuum, which is an admixture of an aromatic compound (A), which is an aromatic dianhydnde or a denvative of an aromatic dianhydnde, and an aromatic compound (B), which is an aromatic diamine or a denvative of an aromatic diamine. plus a complexmg agent (C), which is complexed with the admixture by hydrogen bonding, the complexing agent (C) bemg present m an amount sufficient to provide from about 1 to about 15 % by weight, based on the total weight of the polyimide precursor solid residuum, (2) charging the aromatic polyimide precursor solid residuum mto a non-confined vessel, (3) heating the aromatic polyimide precursor solid residuum in the non-confined vessel to a temperature between about 100°C and 200°C to produce a multiplicity of shaped articles from the aromatic polyimide precursor solid residuum m the non-confined vessel, (4) heating the multiphcity of shaped articles to a temperature between about 200°C and 300°C to produce a multiphcity of thermally lπudized shaped articles, and (5) cooling the multiplicity of thermally lπudized shaped articles for subsequent utilization 10 A process for preparing a multiphcity of shaped articles according to claim 1, which process comprises: (1) providing an aromatic polyimide precursor solid residuum, which is prepared from an admixture comprising an aromatic compound (A) ( A ) and an aromatic compound (B) wherein n is an integer from 0 to 3, and Ri is hydrogen or an alkyl group, and R 2 is a tetravalent aromatic radical having 1 to 5 benzenoid-unsaturated rings of 6 carbon atoms, R 3 is a divalent aromatic radical having 1 to 5 benzenoid-unsaturated rings of 6 carbon atoms; plus a complexing agent (C), which is complexed with the admixture by hydrogen bonding and which has a boiling temperature of less than 200°C, the compound (C) being present in an amount sufficient to provide from about 1 to about 15% by weight, based on the total weight of the aromatic polyimide precursor solid residuum which is formed by heating the complexed admixture to remove any excess complexing agent and volatile by-products; (2) charging the aromatic polyimide precursor solid residuum into a non-confined vessel; (3) heating the aromatic polyimide precursor solid residuum in the non-confined vessel to a temperature between about 100°C and 200°C to produce a multiplicity of shaped articles from the aromatic polyimide precursor solid residuum in the non-confined vessel; (4) heating the multiphcity of shaped articles to a temperature between about 200°C and 300°C to produce a multiphcity of thermally imidized shaped articles; and (5) cooling the multiplicity of thermally imidized shaped articles for subsequent utilization. 11. The process of claim 10, wherein the aromatic compound (A) and the aromatic compound (B) are present in an approximately equimolar admixture. 12. A syntactic foam comprising a multiplicity of shaped articles according to claim 1 which are bonded together by a matrix resin to form an integral composite structure having a density according to ASTM D- 3574A of from about 3 to about 30 pounds/ft 3 and a compression strength according to ASTM D-3574C of from about 100 to about 1400 pounds/in 2 13. A syntactic foam according to claim 12, wherein the matrix resin is a thermosetting resin. 14. A syntactic foam according to claim 13, wherein the thermosetting resin is a member selected from the group consisting of epoxy resin, thermosetting polyimide resin and phenolic resin. 15. A syntactic foam according to claim 12, wherein the matrix resin is a thermoplastic resin. 16. A syntactic foam according to claim 15, wherein the thermoplastic resin is a member selected from the group consisting of polyamide, polyarylene sulfone, polyarylene ketone, polyarylene ether ketone, polyarylene ether sulfone, polyarylene sulfide, polyphenylene oxide, and polyimide.

Inventors: ECHIGO YOSHIAKI, KANESHIRO HISAYASU, ST CLAIR TERRY, WEISER ERIK, ECHIGO, YOSHIAKI, KANESHIRO, HISAYASU, ST. CLAIR, TERRY, WEISER, ERIK
Applicants: NASA, UNITIKA LTD, THE GOVERNMENT OF THE UNITED STATES OF AMERICA AS REPRESENTED BY THE ADMINISTRATOR OF THE NATIONAL AERONAUTICS AND SPACE ADMINISTRATION (NASA), UNITIKA, LTD
Application year: 1999
Main classification: C08G73
IPC codes: B01J13, C08J9