EP0088884B1 - Yarns and tows comprising high strength metal coated fibers, process for their production, and uses thereof - Google Patents

Yarns and tows comprising high strength metal coated fibers, process for their production, and uses thereof Download PDF

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Publication number
EP0088884B1
EP0088884B1 EP83101195A EP83101195A EP0088884B1 EP 0088884 B1 EP0088884 B1 EP 0088884B1 EP 83101195 A EP83101195 A EP 83101195A EP 83101195 A EP83101195 A EP 83101195A EP 0088884 B1 EP0088884 B1 EP 0088884B1
Authority
EP
European Patent Office
Prior art keywords
fibers
metal
core
tow
yarn
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP83101195A
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German (de)
English (en)
French (fr)
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EP0088884A1 (en
Inventor
Louis George Morin
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ELECTRO METALLOID Corp
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ELECTRO METALLOID Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by ELECTRO METALLOID Corp filed Critical ELECTRO METALLOID Corp
Priority to AT83101195T priority Critical patent/ATE22121T1/de
Publication of EP0088884A1 publication Critical patent/EP0088884A1/en
Application granted granted Critical
Publication of EP0088884B1 publication Critical patent/EP0088884B1/en
Expired legal-status Critical Current

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    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
    • D02G3/22—Yarns or threads characterised by constructional features, e.g. blending, filament/fibre
    • D02G3/36—Cored or coated yarns or threads
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F41—WEAPONS
    • F41J—TARGETS; TARGET RANGES; BULLET CATCHERS
    • F41J2/00—Reflecting targets, e.g. radar-reflector targets; Active targets transmitting electromagnetic or acoustic waves
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
    • D01F11/10—Chemical after-treatment of artificial filaments or the like during manufacture of carbon
    • D01F11/12—Chemical after-treatment of artificial filaments or the like during manufacture of carbon with inorganic substances ; Intercalation
    • D01F11/127—Metals
    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
    • D02G3/44—Yarns or threads characterised by the purpose for which they are designed
    • D02G3/441—Yarns or threads with antistatic, conductive or radiation-shielding properties

Definitions

  • the present invention relates to a continuous yarn or tow comprising high strength composite fibers according to claim 1 as well as a process for their production and uses thereof.
  • Bundles of high strength fibers of non-metals and semi-metals, such as carbon, boron, silicon carbide, and the like, in the form of filaments, mats, cloths and chopped strands are known to be useful in reinforcing metals and organic polymeric materials.
  • Articles comprising metals or plastics reinforced with such fibers find widespread use in replacing heavier components made of lower strength conventional materials such as aluminum, steel, titanium, vinyl polymers, nylons, polyesters, etc., in aircraft, automobiles, office equipment, sporting goods, and in many other fields.
  • the problem is manifested in a variety of ways: for example, if a length of high strength carbon fiber yarn is enclosed lengthwise in the center of a rod formed from solidified molten lead, and the rod is pulled until broken, the breaking strength will be less than expected from the rule of mixtures, and greater than that of a rod formed from lead alone, due to the mechanical entrapment of the fibers.
  • the lack of reinforcement is entirely due to poor translation of strength between the carbon fibers and the lead.
  • an incompatible high strength fiber is mixed with a plastic material. If some types of carbon fibers, boron fibers, silicon carbide fibers, and the like in the forms of strands, chopped strands, non-woven mats, felts, papers, etc.
  • woven fabrics are mixed with organic polymeric substances, such as phenolics, styrenics, epoxy resins, polycarbonates, and the like, or mixed into molten metals, such as lead, aluminum, titanium, etc., they merely fill them without providing any reinforcement, and in many cases even cause physical properties to deteriorate.
  • organic polymeric substances such as phenolics, styrenics, epoxy resins, polycarbonates, and the like
  • molten metals such as lead, aluminum, titanium, etc.
  • High strength carbon fibers are made by heating polymeric fiber, e.g., acrylonitrile polymers or copolymers, in two stages, one to remove volatiles and carbonize and another to convert amorphous carbon into crystalline carbon. During such procedure, it is known that the carbon changes from amorphous to single crystal then orients into fibrils. If the fibers are stretched during the graphitization, then high strength fibers are formed. This is critical to the formation of the boundary layer, because as the crystals grow, there are formed high surface energies, as exemplified by incomplete bonds, edge-to-edge stresses, differences in morphology, and the like.
  • polymeric fiber e.g., acrylonitrile polymers or copolymers
  • the new carbon fibrils in this form can scavenge nascent oxygen from the air, and even organic materials, to produce non- carbon surface layers which are firmly and chemically bonded thereto, although some can be removed by solvent treating, and there are some gaps or open spaces in the boundary layers.
  • these boundary layers on carbon fibers are mainly responsible forfailure to achieve reinforcement with plastics and metals.
  • Vacuum deposition e.g., of nickel, US-A-4,132 828, made what appears to be a continuous coating, but really isn't because the vacuum deposited metal first touches the fibrils through spaces in the boundary layer, then grows outwardly like a mushroom, then joins away from the surface, as observed under a scanning electron microscope as nodular nucleation. If the fiber is twisted, such a coating will fall off.
  • the low density non-crystalline deposit limits use.
  • Electroless nickel baths have also been employed to plate such fibers but again there is the same problem, the initial nickel or other electroless metal seeds only small spots through holes in the boundary layer, then new metal grows up like a mushroom and joins into what looks like a continuous coating, but it too will fall off when the fiber is twisted.
  • the intermetallic compound is very locally nucleated and this, too limits use.
  • the strength of the metal-to-core bond is always substantially less than one-tenth that of the tensile strength of the metal deposit itself.
  • the metal coating is mechanically stripped, and the reverse side is examined under a high-power microscope, there is either no replica or at best only an incomplete replica of the fibril, the replica defined to the 4 nm resolution of the scanning electron microscope.
  • the latter two observations are strongly suggestive that failure to reinforce the tin matrix was due to poor bonding between the carbon and the nickel plating.
  • the metal to core bond strength is no greater than one-half of the tensile strength on at most 10% of the fibers, and substantially less than one-tenth on the remaining 90%.
  • the composites are distinguishable from any of the prior art because they can be sharply bent without the fibrils slipping through a tube of the metal, as observed with electroless metal or vacuum deposited composites and sharply bending them, especially with nickel, produces neither transverse cracking ("alligatoring") on the compression side of the bend nor breaking and flaking when the elastic limit of the metal is exceeded on the tension side of the bend.
  • the composites of the present invention are distinguishable from those of the prior art because (i) they are continuous, (ii) the majority of the composite fibers are uniformly metal coated; and (iii) the bond strength (metal-to-core) on the majority of fibers is at least about 10 percent of the tensile strength of the metal deposit, preferably not substantially less than about 25 percent, especially preferably not substantially less than about 50 percent. In the most preferred embodiments, the metal-to-core bond strength will be not substantially less than about 90 percent of the tensile strength of the metal deposit. Highest properties will be achieved with yarns or tows of composite fibers in which the metal-to-core bond strength approaches about 99 percent of the tensile strength of the metal, and special mention is made of these.
  • Articles made by adding the yarns or tows of the present invention to a matrix forming material also distinguish from the prior art because they are strongly reinforced.
  • the articles possess other advantages, for example, they dissipate electrical charges and if certain innocuous metals are used in the coatings, e.g., gold and platinum, they will not be rejected when ' implanted into the body.
  • continuous tows or yarns of high strength composite fibers are provided, the majority of which have an electrically conductive core of carbon, boron or silicon carbide and at least one thin, uniform, firmly adherent, electrically conductive layer of at least one electrodeposited metal on said core, wherein the bond strength of said layer to said core in the majority of said fibers is at least sufficient to provide that, when the composite fiber is bent sharply enough to break the coating on the tension side of the bend because its elastic limit is exceeded, the coating on the compression side of the bend will remain bonded to the core and will not crack circumferentially.
  • the present invention contemplates a process for the production of continuous yarns or tows of high strength composite fibers by
  • the plurality of core fibers can comprise a tow of carbon fibers and the product of the process is a tow of composite fibers which can be knotted without separation of the layer of metal or portions thereof from the core fibers.
  • the use of the yarn or tow comprise the steps of weaving or knitting yarns produced by the process into a fabric, laying them up into a non-woven sheet, or chopping them into shortened lengths.
  • Figs. 1 and 1a continuous yarns and tows for use in the core 2 according to the present invention are available from a number of sources commercially.
  • suitable carbon fiber yarns are available from Hercules Company, Hitco, Great Lakes Carbon Company, AVCO Company and similar sources in the United States, and overseas. All are made in general, by procedures described in US-A-3,677,705.
  • the fibers can be long and continuous or they can be short, e.g., 1 to 15 cm. in length.
  • all such carbon fibers will contain a thin, imperfect boundary layer (not shown) of chemically bonded oxygen and chemically or mechanically bonded other materials, such as organics.
  • Metal layer 4 will be of any electrodepositable metal, and it will be electrically continuous. Two layers, or even more, of metal can be applied and metal can be the same or different, as will be shown in the working examples. In any case, the innermost layer will be so firmly bonded to core 2 that sharp bending will neck the metal down as shown in Fig. 3, snapping the fiber core and breaking the metal on the tension side of the bend when its elastic limit is exceeded. This is accomplished without causing the metal to flake off when broken (Fig. 3a) which is a problem in fibers metal coated according to the prior art. As a further distinction from the prior art, the metal layer of the present invention fills interstices and "cracks" in fibers, uniformly and completely, as illustrated in Figs. 2 and 2a.
  • the high strength metal coated fibers of this invention can be assembled by conventional means into composites represented in Fig. 4 in which matrix 6 is a plastic, e.g., epoxy resin, or a metal, e.g., lead, the matrix being reinforced by virtue of the presence of high strength fibrous cores 2.
  • matrix 6 is a plastic, e.g., epoxy resin, or a metal, e.g., lead, the matrix being reinforced by virtue of the presence of high strength fibrous cores 2.
  • Formation of the metal coating layer by the electrodeposition process of this invention can be carried out in a number of ways.
  • a plurality of core fibers can be immersed in an electrolytic bath and through suitable electrical connections the required high external voltage can be applied,
  • a high order of voltage is applied for a short period of time.
  • a pulse generator for example, will send a surge of voltage through the electrolyte, sufficient to push or force the metal ion through the boundary layer into contact with the carbon or other fiber comprising the cathode. The short time elapsing in the pulse will prevent heat from building up in the fiber and burning it up or out.
  • the fibers are so small, e.g., 5 to 10 11m in diameter, and because the innermost fibers are usually surrounded by hundreds or even thousands of others (even though only 0.5 to 2.6 volts are needed to dissociate the electrolytic metal to ions e.g., nickel, gold, silver, copper) depending on the salt used, massive amounts of external voltage are needed, of the order of 5 times the dissociation values, to uniformly nucleate the ions through the bundle of fibers into the innermost fibril and then through the boundary layer.
  • Minimum external voltages e.g., 10 to 50, or even more, volts are used.
  • Electrolytic bath solution 8 is maintained in tank 10. Also included are anode baskets 12 and idler rolls 14 near the bottom of tank 10. Two electrical contact rollers 16 are located above the tank.
  • Tow 24 is pulled by means not shown off feed roll 26, over first contact roller 16 down into the bath under idler rolls 14, up through the bath, over second contact roller 16 and into take up roller 28.
  • the immersed tow length is about 1.8 m.
  • Optional, but very much preferred, is a simple loop comprising pump 18, conduit 20, and feed head 22. This permits recirculating the plating solution at a large flow rate, e.g., 7,6-11,3 I/min. and pumping it onto contact rolls 16. Discharged just above the rolls, the sections of tow 24 and leaving the solution are totally bathed, thus cooling them. At the high current carried by the tow, the 1 2 R heat generated in some cases might destroy them before they reach or after they leave the bath surface without such cooling.
  • the flow of the electrolyte overcomes anisotropy.
  • more than one plating bath can be used in series, and the fibers can be rinsed free of electrolyte solution, treated with other conventional materials and dried, chopped, woven into fabric, all in accordance with conventional procedures.
  • knott- able tows or yarns of the new composite fibers fabrics woven from such yarns, non-woven sheets, mats and papers laid up from such fibers, chopped strands of such fibers and articles comprising such fibers uniformly dispersed in a matrix comprising a metal or an organic polymeric material.
  • coating metals will be nickel, silver, zinc, copper, lead, arsenic, cadmium, tin, cobalt, gold, indium, iridium, iron, palladium, platinum, tellurium, tungsten or a mixture of any of the foregoing, without limitation, preferably in crystalline form.
  • the bond strength of the layer to the core is substantially not less than about 10% of the tensile strength of the metal.
  • the electrolytic bath may be recycled into contact with the fibers.
  • Other preferred features include carrying out the process in an electrolytic bath which is ' recycled into contact with the fibers immediately prior to immersion in the bath so as to provide increased current carrying capacity to the fibers and replenishment of the electrolyte on the surface of the fibers.
  • a bath having the following composition: The bath is heated to 60-70°C and has a pH of 3.8-4.2.
  • the anode baskets are kept filled with electrolytic nickel pellets and 4 tows (fiber bundles) of 12,000 strands each of 7 ⁇ m carbon fibers are continuously drawn through the bath while an external voltage of 30 volts is applied at a current adjusted to give 10 ampere-minutes per 1000 strands total.
  • electrolytic solution is recycled. through a loop into contact with the entering and leaving parts of the tow.
  • the tow is next passed continuously through an identical bath, at a tow speed of 1,5 m/min with 180 amps. current in each bath.
  • the final product is a tow of high strength composite fibers according to this invention comprising a 7 ⁇ m fiber core and about 50% by weight of the composite of crystalline electrodeposited nickel adhered firmly to the core.
  • Example 1 If the procedure of Example 1 is repeated, substituting two baths of the following compositions, in series, and using silver in the anode baskets, silver coated graphite fibers according to this invention will be obtained.
  • the first bath is to be operated at room temperature and 12-36 volts; the second at room temperature and 6-18 volts.
  • Example 2 The procedure of Example 2 can be modified, by substituting nickel plated graphite fibers as prepared in Example 1 for the feed, and the voltage in the first bath is reduced to about 18 volts. There are obtained high strength composite fibers according to this invention in which a silver coating surrounds a nickel coating on a graphite fiber core.
  • Example 1 The procedure of Example 1 can be modified by substituting for the nickel bath a bath of the following composition, using zinc in the anode baskets, and zinc coated graphite fibers according to this invention will be obtained:
  • the bath is run at 38°C and 18 volts are externally applied.
  • Example 1 The procedure of Example 1 can be modified by substituting for the nickel bath a bath of the following composition, using copper in the anode baskets, and copper coated graphite fibers according to this invention will be obtained:
  • the bath is run at 60°C and 18 volts are externally applied.
  • the copper plated fibers should be washed with sodium dichromate solution immediately after plating to prevent tarnishing. If the procedure of Example 3 is repeated, substituting the copper bath of this example for the silver bath, there will be obtained high strength composite fibers according to this invention in which a copper coating surrounds a nickel coating on a graphite fiber core.
  • Example 1 The procedure of Example 1 can be modified by substituting for the nickel bath two baths of the following composition, using standard 80% cu/ 20% zinc anodes, and brass coated graphite fibers according to this invention will be obtained:
  • Both baths are run at 43-49°C. Since one-third of the brass is plated in the first bath, at 24 volts, and two-thirds in the second at 15 volts, the current is proportioned accordingly. Following two water rinses, the brass plated fibers are washed with a solution of sodium dichromate, to prevent tarnishing, and then rinsed twice again with water.
  • Example 1 The procedure of Example 1 can be modified by substituting for the nickel bath a bath of the following composition, using solid lead bars in the anode baskets, and lead coated graphite fibers according to this invention will be obtained:
  • Silicon carbide filaments and boron fibers are coated with nickel by placing them in cathodic contact with a nickel plating bath of Example 1 and applying an external voltage of about 30 volts.
  • a composition is prepared by chopping the composite fibers of Example 1 into short lengths 3-25 mm long, then thoroughly mixing with thermoplastic nylon polyamide in an extruder, and chopping the extrudate into molding pellets in accordance with conventional procedures.
  • the pellets are injection molded into plaques 10 cmx20 cmx0,3 cm in size.
  • the plaque is reinforced by the composite fibers. By virtue of the metal content, it also does not build up static charge, and it can act as an electrical shield in electronic assemblies.
  • Bundles of nickel plated graphite fibers of about 25,4 mm in length prepared according to the procedure of Example 1 are mixed with 1:9 with uncoated graphite fibers and laid up into a non woven mat, at 33 g/m 2 .
  • the mat has a metal content of about 5% by weight of nickel and can be impregnated with thermosetting resin varnishes and consolided under heat and pressure into reinforced laminates having high strength and excellent electrical dissipation properties.
  • aluminum can be deposited from ethereal solutions.
  • Metals e.g., tungsten
  • molten salt solutions e.g., sodium tungstenate.
  • the tow can be treated to remove metal from sections thereof, and thereby segmented structures are provided which have utility, for example, as electrical resistors.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Remote Sensing (AREA)
  • Radar, Positioning & Navigation (AREA)
  • Electromagnetism (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Engineering & Computer Science (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
  • Nonwoven Fabrics (AREA)
  • Woven Fabrics (AREA)
  • Knitting Of Fabric (AREA)
  • Manufacture Of Alloys Or Alloy Compounds (AREA)
  • Laminated Bodies (AREA)
  • Ropes Or Cables (AREA)
EP83101195A 1982-03-16 1983-02-08 Yarns and tows comprising high strength metal coated fibers, process for their production, and uses thereof Expired EP0088884B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT83101195T ATE22121T1 (de) 1982-03-16 1983-02-08 Metallisierte fasern enthaltende garne und seile, verfahren zu deren herstellung und deren verwendung.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US35863782A 1982-03-16 1982-03-16
US358637 1982-03-16

Publications (2)

Publication Number Publication Date
EP0088884A1 EP0088884A1 (en) 1983-09-21
EP0088884B1 true EP0088884B1 (en) 1986-09-10

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EP83101195A Expired EP0088884B1 (en) 1982-03-16 1983-02-08 Yarns and tows comprising high strength metal coated fibers, process for their production, and uses thereof

Country Status (17)

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EP (1) EP0088884B1 (es)
JP (1) JPS58169532A (es)
KR (1) KR880000477B1 (es)
AR (1) AR240342A1 (es)
AT (1) ATE22121T1 (es)
AU (2) AU561667B2 (es)
BR (1) BR8301227A (es)
CA (1) CA1256052A (es)
DE (1) DE3365941D1 (es)
DK (1) DK158159C (es)
ES (1) ES520574A0 (es)
FI (1) FI75876C (es)
HK (1) HK14491A (es)
IL (1) IL67867A (es)
IN (1) IN158302B (es)
MX (1) MX159077A (es)
NO (1) NO164996C (es)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0088884B1 (en) * 1982-03-16 1986-09-10 Electro Metalloid Corporation Yarns and tows comprising high strength metal coated fibers, process for their production, and uses thereof
EP0137912B1 (en) * 1983-06-24 1990-05-16 American Cyanamid Company Apparatus and process for continuously plating fiber
EP0129845B1 (en) * 1983-06-24 1988-10-26 American Cyanamid Company Electrodes, electro-chemical cells containing said electrodes, and process for forming and utilizing such electrodes
EP0149763A3 (en) * 1983-11-29 1985-08-21 Toho Beslon Co., Ltd. Electroplating method for carbon fibers and apparatus therefor
FR2562101B1 (fr) * 1984-03-27 1987-03-06 Brochier Sa Materiau a base de fibres inorganiques, carbure de silicium notamment, utilisable pour la realisation de structures composites
EP0269850A1 (en) * 1986-10-31 1988-06-08 American Cyanamid Company Copper coated fibers
ES2037959T3 (es) * 1988-10-12 1993-07-01 Johnson Matthey Public Limited Company Telas metalicas.
CA2125378A1 (en) * 1993-06-09 1994-12-10 James A. E. Bell Composition for lightning strike protection and improved electrical conductivity
JP2002180372A (ja) * 2000-12-15 2002-06-26 Toho Tenax Co Ltd 金属酸化物被覆炭素繊維、及びその製造方法
JP7032348B2 (ja) * 2019-03-26 2022-03-08 矢崎総業株式会社 金属めっき炭素素材及びその製造方法

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1215002A (en) * 1967-02-02 1970-12-09 Courtaulds Ltd Coating carbon with metal
FR1535660A (fr) * 1967-06-28 1968-08-09 Thomson Houston Comp Francaise Perfectionnements aux procédés de fabrication des matériaux composites et produits obtenus
EP0088884B1 (en) * 1982-03-16 1986-09-10 Electro Metalloid Corporation Yarns and tows comprising high strength metal coated fibers, process for their production, and uses thereof

Also Published As

Publication number Publication date
DK158159B (da) 1990-04-02
AU7108187A (en) 1987-07-23
CA1256052A (en) 1989-06-20
DK120683A (da) 1983-09-17
IL67867A (en) 1987-10-30
BR8301227A (pt) 1983-11-22
ATE22121T1 (de) 1986-09-15
FI75876B (fi) 1988-04-29
DE3365941D1 (en) 1986-10-16
ES8406576A1 (es) 1984-08-01
JPS58169532A (ja) 1983-10-06
NO164996B (no) 1990-08-27
ES520574A0 (es) 1984-08-01
IN158302B (es) 1986-10-11
FI830854L (fi) 1983-09-17
DK120683D0 (da) 1983-03-15
AU561667B2 (en) 1987-05-14
AR240342A1 (es) 1990-03-30
MX159077A (es) 1989-04-14
KR840004193A (ko) 1984-10-10
FI830854A0 (fi) 1983-03-15
AU1245083A (en) 1983-09-22
DK158159C (da) 1990-08-27
NO830897L (no) 1983-09-19
NO164996C (no) 1990-12-05
AU588991B2 (en) 1989-09-28
HK14491A (en) 1991-03-08
EP0088884A1 (en) 1983-09-21
IL67867A0 (en) 1983-06-15
FI75876C (fi) 1988-08-08
KR880000477B1 (ko) 1988-04-07

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