EP0721194A2 - Polymères électroconducteurs désagglomérés et leurs précurseurs - Google Patents

Polymères électroconducteurs désagglomérés et leurs précurseurs Download PDF

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EP0721194A2
EP0721194A2 EP95120081A EP95120081A EP0721194A2 EP 0721194 A2 EP0721194 A2 EP 0721194A2 EP 95120081 A EP95120081 A EP 95120081A EP 95120081 A EP95120081 A EP 95120081A EP 0721194 A2 EP0721194 A2 EP 0721194A2
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group
acid
polyaniline
electrically conductive
salts
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German (de)
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EP0721194A3 (fr
EP0721194B1 (fr
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Marie Angelopoulos
Bruce K. Furman
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International Business Machines Corp
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International Business Machines Corp
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Priority claimed from US08/370,127 external-priority patent/US5804100A/en
Priority claimed from US08/370,128 external-priority patent/US6087472A/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H01B1/124—Intrinsically conductive polymers
    • H01B1/128—Intrinsically conductive polymers comprising six-membered aromatic rings in the main chain, e.g. polyanilines, polyphenylenes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H01B1/124—Intrinsically conductive polymers
    • H01B1/127—Intrinsically conductive polymers comprising five-membered aromatic rings in the main chain, e.g. polypyrroles, polythiophenes

Definitions

  • the present invention is directed to methods of fabrication of electrically conducting polymers having enhanced electrical conductivity.
  • the present invention is directed to methods to deaggregate electrically conductive polymers and precursors thereof.
  • Electrically conductive organic polymers have been of scientific and technological interest since the late 1970's. These relatively new materials exhibit the electronic and magnetic properties characteristic of metals while retaining the physical and mechanical properties associated with conventional organic polymers.
  • Intra-molecular conformation refers to the conformation of a single molecule or a single polymer chain in which the molecular chain is coiled around itself.
  • inter-molecular structure refers to the structural arrangement of more than one molecule or polymer chain in which the molecules or chains are bonded together or coiled around each other forming aggregates. These aggregates are then comprised of many polymer chains intertwined or entangled. MacDiarmid et al. teaches that the secondary dopant causes a intra-molecular conformational change, i.e., the molecule or the chain unravels and assumes an expanded coil conformation.
  • a film of this expanded coil polyaniline has enhanced electrical conductivity because of an increase in the crystallinity of the material formed from the aggregated straightened molecules.
  • the polyaniline which has been doped has electrically conductive regions or islands which are of the order of 20-30 nm (200-300 ⁇ ). The spaces between these regions are significantly less electrically conductive.
  • a broad aspect of the present invention is an electrically conductive polymer having electrically conductive regions having a dimension greater than about 300 ⁇ .
  • Another broad aspect of the present invention is a precursor to an electrically conductive polymer containing a deaggregating agent, such as a complexing agent.
  • a deaggregating agent such as a complexing agent.
  • the dimension of the electrically conductive regions are enhanced by a deaggregating agent.
  • Another broad aspect of the present invention is a body of material containing precursor molecules to electrically conductive molecules wherein the body of material has regions of aggregated precursor molecules of less than about 100 nm.
  • Another broad aspect of the present invention is a method for fabricating electrically conducting polymers, the electrical conductivity of which is enhanced by deaggregating the polymer either prior to being doped to the electrically conducting state or after being doped to the electrically conducting state.
  • a more specific aspect of a method of the present invention is deaggregating the precursor polymer or electrically conducting polymer either in solution or in the solid state, such as by using complexing agents.
  • Another more specific aspect of a method of the present invention includes steps of providing a first admixture of an additive in a solvent; forming a second admixture by dissolving in the first admixture precursor polymers to electrically conduct ing polymers wherein the additive deaggregates the precursor molecules and either adding a dopant to the second admixture to dope the precursor to the electrically conductive polymer or forming a film of the second admixture and the n doping the film in the solid state.
  • Another more specific aspect of a method of the present invention includes providing aniline molecules which are oxidatively polymerized in an acid solution in the presence of a deaggregating agent to result in a deaggregated polyaniline.
  • Another more specific aspect of a method of the present invention includes the steps of providing aniline molecules which are oxidatively polymerized in an acid solution to form an electrically conducting polyaniline salt which is then neutralized to the base non-doped form and deaggregated upon exposure to a deaggregating agent.
  • Another more specific aspect of a method according to the present invention includes neutralizing a polyaniline salt to the base form in the presence of a deaggregating agent.
  • Another broad aspect of the present invention is a method of causing a doped electrically conductive polymer in a compact coil conformation to undergo a conformational change from a compact coil to an expanded coil conformation by exposing the doped polymer to salts and surfactants.
  • the present invention is directed to enhancing the electrical conductivity of polymer materials, which when doped, are electrically conducting.
  • polymers which can be used to practice the present invention are of substituted and unsubstituted polyparaphenylenes, polyparaphenylevevinylenes, polyanilines, polyazines, polythiophenes, poly-p-phenylene sulfides, polyfuranes, polypyrroles, polyselenophenes, polyacetylenes formed from soluble precursors and combinations thereof and copolymers of monomers thereof.
  • each R can be H or any organic or inorganic radical; each R can be the same or different; wherein each R 1 can be H or any organic or inorganic radical, each R 1 can be the same or different; x ⁇ 1; preferably x ⁇ 2 and y has a value from 0 to 1.
  • organic radicals are alkyl or aryl radicals.
  • inorganic radicals are Si and Ge. This list is exemplary only and not limiting. The most preferred embodiment is emeraldine base form of the polyaniline wherein y has a value of approximately 0.5.
  • Fig. 4.1 polyaniline is shown doped with a dopant. If the polyaniline base is exposed to cationic species QA, the nitrogen atoms of the imine part of the polymer becomes substituted with the Q+ cation to form an emeraldine salt as shown in Fig. 4.1.
  • Q+ can be selected from H+ and organic or inorganic cations, for example, ⁇ è an alkyl group or a metal.
  • QA can be a protic acid where Q is hydrogen.
  • a protic acid HA is used to dope the polyaniline, the nitrogen atoms of the imine part of the polyaniline are protonated.
  • the emeraldine base form is greatly stabilized by resonance ⁇ effects.
  • the charges distribute through the nitrogen atoms and aromatic rings making the imine and amine nitrogens ⁇ indistinguishable.
  • the actual structure of the doped form is a delocalized polysemiquinone radical cation as shown in Fig. 4.2.
  • the emeraldine base form of polyaniline is soluble in various organic solvents and in various aqueous acid solutions.
  • organic solvents are dimethylsulfoxide (DMSO), dimethylformamide (DMF) and N-methylpyrrolidinone (NMP). This list is exemplary only and not limiting.
  • aqueous acid solutions is 80% acetic acid and 60-88% formic acid. This list is exemplary only and not limiting.
  • Fig. 1 shows a GPC (gel permeation chromatograph) of polyaniline in the base form dissolved in 100% solvent N-methylpyrrolidinone (NMP).
  • NMP N-methylpyrrolidinone
  • the vertical axis is the ultraviolet visible (UV VIS) detector response and the horizontal axis is the peak retention time in minutes.
  • Two peaks are evident in Fig. 1, peak 2 which corresponds to a weight average molecular weight of approximately 371,700 and peak 4 which corresponds to a weight average molecular weight of approximately 29,500.
  • Fig. 2 shows the GPC of polyaniline in the base form in NMP/.5 wt % lithium chloride (LiCl) which shows a single peak 6 corresponding to a weight average molecular weight of approximately 45,500. It is evident in comparing Fig. 1 to Fig. 2 that the high molecular weight peak 2 of Fig. 1 has disappeared and that the molecular weight of ⁇ the major peak is higher than that in NMP, corresponding to a higher hydrodynamic volume.
  • Fig. 5 is a plot of a first run of a dynamic mechanical thermal analysis (DMTA) plot of an undoped polyaniline base film cast from 100% NMP. The as-cast film contains approximately 21% ⁇ è NMP which is determined from thermo gravimmetric analysis. The dashed line in Fig. 5 which is the plot of tan( ⁇ ) shows several transitions of which some are related to the residual solvent.
  • DMTA dynamic mechanical thermal analysis
  • Fig. 6 shows a plot of a DMTA (second run) of the same material as for Fig. 5. The solvent is substantially driven off in the first run.
  • the single peak of the dashed curve which corresponds to the tan ( ⁇ ) measurement shows that the polyaniline base has a glass transition temperature ( T g ) of 251°C.
  • Fig. 7 shows a plot of a DMTA (second run) for polyaniline base, cast from 100 wt% NMP, which has been doped in 1N HCl and subsequently undoped with .1M NH 4 OH. Most of the NMP was removed in the process. It has been determined from thermogravimmetric analysis (TGA) that there is only 2.8% NMP remaining in the film. The glass transition temperature of this sample is 256 ⁇ degree C, relatively the same as that measured for the sample of Fig. 6.
  • TGA thermogravimmetric analysis
  • Fig. 8 shows a plot of a DMTA (second run) of polyaniline base cast from 99.5 wt% NMP/.5 wt% lithium chloride. The peak in the tan( ⁇ ) curve gives a T g of 180°C. Table I summarizes the results of Figs. 5-8 and also gives additional results for films cast from combinations of NMP and m-cresol and a surfactant nonylphenol.
  • the drop in glass transition temperature of the polyaniline base upon exposure to an additive such as m-cresol, LiCl and nonylphenol indicates that there is a drop in the crosslink density of the polyaniline base material as a result of deaggregation of the polyaniline base molecules. While applicant's do not want to be limited to a particular theory, this cross-link is believed to be in the form of inter-chain or intermolecular hydrogen bonding.
  • Fig. 9 shows two polyaniline base molecules wherein a hydrogen atom from an amine site on one molecule is hydrogen bonded as represented by the dashed line to an imine nitrogen on an adjacent molecule.
  • Fig. 10 shows the effect of adding lithium chloride to the arrangement shown in Fig. 9.
  • the lithium chloride can complex with the imine nitrogen lone pairs as shown in the Fig. 10 thereby disrupting the interchain hydrogen bonding between polyaniline chains.
  • Fig. 11 is a schematic diagram showing three polyaniline molecules 20, 22 and 24 wherein there are a plurality of hydrogen bonds 26 interlocking each of the three polyaniline molecules shown.
  • the aggregated polyaniline molecules are deaggregated by the methods according to the present invention, the polyaniline molecules will be more effectively doped when contacted with a dopant.
  • the size of the metallic islands may in turn be increased above 20-30 nm (200-300 &angstrom) thereby enhancing the mobility of the carriers, and in turn the electrical conductivity. It may be possible to ultimately eliminate the formation of islands by more uniform doping; in this fashion the material would be more homogeneous and hopping through less conducting regions to go from metallic island to metallic island would thereby be eliminated.
  • An exemplary list of solvents useful to practice the present invention is:
  • NMP N-methyl pyrrolidinone
  • DMSO dimethyl sulfoxide
  • DMF dimethyl formamide
  • DMPU dimethyl propylene urea
  • the deaggregating agent When deaggregation is done in solution the deaggregating agent is present in an amount less than about 25 wt%.
  • the salt When deaggregation is done in solution using a salt as the deaggregation agent, the salt is preferably present in an amount from about 0.00001 wt% to about 5 wt%, more preferably from about 0.0001 wt% to about 2.5 wt%; most preferably from about 0.001 wt% to about 1 wt%.
  • the surfactant is preferably present in an amount from about 0.0001 wt% to about 10 wt%; more preferably from about 0.001 wt% to about 5 wt%; most preferably from about 0.01 wt% to about 2.5 wt%.
  • the acidic additive is preferably present in an amount from about 0.0001 wt% to about 25 wt%; preferably from about 0.001 wt% to about 15 wt%; most preferably from about 0.01 wt% to about 10 wt%.
  • Fig. 15, 16, 17, 18, 19 and 20 are atomic force micrographs each having a dimension of 1000 nm X 1000 nm.
  • Fig. 15 is for polyaniline base cast from 100% NMP;
  • Fig. 16 is for polyaniline cast from 100% NMP and subsequently exposed to m-cresol; and
  • Fig. 15 shows aggregated ⁇ regions ⁇ è of the order of 100 nm.
  • Fig. 16 shows the substantial elimination of the aggregated regions caused by exposure to the deaggregating agent, m-cresol, which remains when the m-cresol is removed. Therefore, the deaggregated structure is locked or remains without the deaggregating agent.
  • Fig. 15 shows bundles of aggregated regions which are not present in Fig. 16 and 17.
  • Figs. 18, 19 and 20 show similar results for treatment with nonylphenol and triton surfactant.
  • the level of deaggregation is not as complete as in Fig. 16 but shows the onset of deaggregation.
  • the unsubstituted polyaniline is synthesized by the chemical oxidative polymerization of aniline in 1N HCL using ammonium peroxydisulfate as an oxidizer.
  • Polyaniline can also be oxidatively polymerized electrochemically as taught by W.Huang, B. Humphrey, and A.G. Macdiarmid, J. Chem. Soc., Faraday Trans. 1, 82, 2385, 1986.
  • the conducting polyaniline:hydrochloride salt precipitates from solution. The polymerization is allowed to proceed for several hours after which the powder is filtered, washed with excess 1N hydrochloric acid.
  • the polyaniline:hydrochloride is then converted to the non-conducting or non-doped polyaniline base by reaction with 0.1M ammonium hydroxide.
  • the polyaniline base is then filtered, washed with ammonium hydroxide, then washed with methanol and dried.
  • the polymer in this stage is in the undoped base form as a powder.
  • the polymer is generally processed by taking the polyaniline base powder and dissolving it in organic solvents, most commonly N-methylpyrrolidinone. This solution can be used to spin-coat thin films of the base polymer or can be used to solution cast thick films or can be used to fabricate structural parts of the polyaniline base.
  • the substituted polyaniline derivatives are made by the oxidative polymerization of the appropriate substituted aniline monomer. Copolymers can also be made by the oxidative polymerization of one or more monomers. In addition different acids other than hydrochloric acid can be used in the synthesis.
  • Doping generally involves reaction with most commonly protonic acids. Other electrophiles can also be used as dopants, for example alkylating agents, etc.
  • the doping can be done in solution or it can be done heterogeneously in the solid state.
  • the NMP solution of the polyaniline base can be used to spin-coat films of the polyaniline base. These films can be doped or made conducting by dipping into a solution of the appropriate acid such as 1N HCL, or aqueous toluene sulfonic acid or the vapor of the acid.
  • the polyaniline base powder can also be doped by stirring in an aqueous solution of the dopant.
  • the doping can also be carried out in solution which is generally preferred as it allows the conducting form to be processable.
  • the appropriate dopant for example camphorsulfonic acid.
  • the acid reacts with the polyaniline base to form the conducting polyaniline salt.
  • Any ⁇ other acid or electrophile can be used in the same manner.
  • the conducting salt will either precipitate or remain in solution depending on the particular dopant used. If it stays in solution, the conducting solution can then be used to fabricate films of the conducting polyaniline by spin-coating, dip coating, spray-coating, etc. or fabricated into some structural components.
  • the present invention uses additives in the starting solvent, eg. NMP.
  • the starting solvent eg. NMP.
  • LiCl LiCl
  • the salt is allowed to dissolve in the NMP.
  • the polyaniline base powder is added to this solvent.
  • the polyaniline base is filtered through a 0.2 micron millipore filter and then to the filtered solution is added the dopant.
  • Dopants used in this study include toluenesulfonic acid, camphor sulfonic acid, acrylamidopropanesulfonic acid, hydrochloric acid.
  • the conductivity of the polyaniline salt is found to depend on the processing conditions. Generally polyaniline doped heterogeneously with aqueous 1N HCL gives conductivity on the order of approx. 1 S/cm. Doping in NMP generally gives much lower conductivity (approx. .1 S/cm). A great deal of variation in conductivity has been observed depending on the solvent system used for doping.
  • a polyaniline base is doped in NMP with an organic sulfonic acid a localized polaron peak is observed on the ultraviolet-visible near IR spectrum. When this film is exposed to m-cresol ⁇ è a highly delocalized polaron peak is observed extending out to 2500 nm with the conductivity increasing to hundreds of S/cm.
  • Conductivity of .2 S/cm is attained when an NMP solution of the polyaniline base is reacted with camphorsulfonic acid or acrylamidopropanesulfonic acid.
  • the uv/visible/near IR spectrum for the polyaniline doped with acrylamidopropane sufonic acid is shown in Fig. 12.
  • a localized polaron peak 10 is attained.
  • a delocalized polaron peak 12 (Fig. 13) is attained and with 1 wt. % LiCl a highly delocalized polaron peak is attained (Fig. 14).
  • This delocalized polaron is indicative of higher conductivity as a result of more highly delocalized carriers.
  • an NNP/additive (e.g. LiCl) solvent system was used to spin-coat the polyaniline base films.
  • the UV of the base also shows a red shift to longer wavelengths with the incorporation of additives as compared to films cast from 100% NMP. This red shift is indicative of an extension of the conjugation length.
  • the films which include the lithium chloride show a more highly delocalized polaron peak as compared to the NMP film alone.
  • the additives can also be surfactants such as nonylphenol or the tritons.
  • the triton for example is dissolved in the NMP prior to the addition of the pani base as described above. This solution was used to cast thick films of the pani base. Upon doping of the thick films with hydrochloric acid, the conductivity of the film was 11 S/cm for the triton containing film; 40 S/cm for the nonylphenol containing film; and only 1 S/cm for the NMP only film.
  • Films processed according to the present invention can give rise to enhanced stretch orientation and a corresponding increase in electrical conductivity.
  • Fig. 21 schematically shows an undoped deaggregated film 20 held at end 22 and end 24 by clamps 26 and 28 respectively. Ends 22 and 24 are pulled apart as indicated by arrows 30 and 32, respectively. The molecules in the deaggregated film are unravelled and therefore when film 20 is stretched there is increased propensity for alignment of the molecules in the stretch direction and thereby enhanced electrical conductivity in the stretch direction.
  • Solutions processed according to the present invention exhibit enhanced shelf life stability.
  • Polyaniline solutions in general tend to gel over time. The time for gelling to occur is dependent on solvent and concentration of solids in solution. For example, a solution of polyaniline base in NMP made to 5% solids be weight tends to gel within days. Solutions higher in solids content gel within minutes. Gellation limits the full use of the polyaniline solutions for many applications. Gellation occurs because of interactions between chains, most probably hydrogen bonding. As the hydrogen bonding between chains increase, chain entanglements increase. As this entangled or highly aggregated structure is less soluble than the non-aggregated structure, the solutions of the aggregated structure in turn gel.
  • salts such as lithium chloride, for example, breaks the interchain hydrogen bonds and in turn prevents the solution from gelling thereby enhancing the long term shelf life stability of the polyaniline solutions.
  • use of these additives allows higher solids polyaniline solutions to be made (higher than can normally be made without the additives) with good shelf life stability.
EP19950120081 1995-01-09 1995-12-19 Polymères électroconducteurs désagglomérés et leurs précurseurs Expired - Lifetime EP0721194B1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US370128 1995-01-09
US08/370,127 US5804100A (en) 1995-01-09 1995-01-09 Deaggregated electrically conductive polymers and precursors thereof
US370127 1995-01-09
US08/370,128 US6087472A (en) 1995-01-09 1995-01-09 Methods of fabrication of deaggregated electrically conductive polymers and precursors thereof

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EP0721194A2 true EP0721194A2 (fr) 1996-07-10
EP0721194A3 EP0721194A3 (fr) 1997-03-05
EP0721194B1 EP0721194B1 (fr) 2004-03-10

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0797218A2 (fr) * 1996-03-22 1997-09-24 International Business Machines Corporation Polymères électroconducteurs
WO1998005043A1 (fr) * 1996-07-25 1998-02-05 International Business Machines Corporation Procedes vibratoires de desagregation de polymeres electriquement conducteurs et de precurseurs de ces polymeres
DE19631563A1 (de) * 1996-07-26 1998-02-26 Frank Dr Ing Lux Reine oder funktionalisierte oder ferromagnetisch funktionalisierte elektronisch leitfähige Polymermaterialien und ihre Bestandteile, deren Herstellung und deren Verwendung
WO2002059907A1 (fr) * 2001-01-23 2002-08-01 Panipol Oy Composition plastifiante electroconductrice et son procede de preparation
CN114349143A (zh) * 2021-12-23 2022-04-15 扬州大学 一种复合物凝聚相体系及其制备方法和应用

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1988006064A1 (fr) * 1987-02-11 1988-08-25 Lockheed Corporation Fabrication de dispositifs electroniques par dopage selectif d'un polymere non conducteur
EP0399299A2 (fr) * 1989-05-26 1990-11-28 International Business Machines Corporation Matériaux polymères électroconducteurs et leurs utilisations
US4994783A (en) * 1989-01-26 1991-02-19 Lockheed Corporation Electronic device fabrication on non-conductive polymer substrate
FR2699542A1 (fr) * 1992-12-21 1994-06-24 Thomson Csf Procédé d'obtention de polymères conducteurs de type polyarylène vinylène.

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1988006064A1 (fr) * 1987-02-11 1988-08-25 Lockheed Corporation Fabrication de dispositifs electroniques par dopage selectif d'un polymere non conducteur
US4994783A (en) * 1989-01-26 1991-02-19 Lockheed Corporation Electronic device fabrication on non-conductive polymer substrate
EP0399299A2 (fr) * 1989-05-26 1990-11-28 International Business Machines Corporation Matériaux polymères électroconducteurs et leurs utilisations
FR2699542A1 (fr) * 1992-12-21 1994-06-24 Thomson Csf Procédé d'obtention de polymères conducteurs de type polyarylène vinylène.

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0797218A2 (fr) * 1996-03-22 1997-09-24 International Business Machines Corporation Polymères électroconducteurs
EP0797218A3 (fr) * 1996-03-22 1998-03-18 International Business Machines Corporation Polymères électroconducteurs
WO1998005043A1 (fr) * 1996-07-25 1998-02-05 International Business Machines Corporation Procedes vibratoires de desagregation de polymeres electriquement conducteurs et de precurseurs de ces polymeres
WO1998005044A1 (fr) * 1996-07-25 1998-02-05 International Business Machines Corporation Procedes oxydo-reducteurs de desagregation de polymeres electriquement conducteurs, precurseurs de ces polymeres et procedes de fabrication d'articles a partir de tels polymeres
DE19631563A1 (de) * 1996-07-26 1998-02-26 Frank Dr Ing Lux Reine oder funktionalisierte oder ferromagnetisch funktionalisierte elektronisch leitfähige Polymermaterialien und ihre Bestandteile, deren Herstellung und deren Verwendung
WO2002059907A1 (fr) * 2001-01-23 2002-08-01 Panipol Oy Composition plastifiante electroconductrice et son procede de preparation
CN114349143A (zh) * 2021-12-23 2022-04-15 扬州大学 一种复合物凝聚相体系及其制备方法和应用
CN114349143B (zh) * 2021-12-23 2023-04-14 扬州大学 一种复合物凝聚相体系及其制备方法和应用

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EP0721194B1 (fr) 2004-03-10
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