EP0197981B1 - Katalytische polymerelektrode für katodischen schutz und diese elektrode enthaltendes kathodisches schutzsystem - Google Patents

Katalytische polymerelektrode für katodischen schutz und diese elektrode enthaltendes kathodisches schutzsystem Download PDF

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Publication number
EP0197981B1
EP0197981B1 EP19850904921 EP85904921A EP0197981B1 EP 0197981 B1 EP0197981 B1 EP 0197981B1 EP 19850904921 EP19850904921 EP 19850904921 EP 85904921 A EP85904921 A EP 85904921A EP 0197981 B1 EP0197981 B1 EP 0197981B1
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Prior art keywords
anode
catalytic
polymer
valve metal
particles
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Expired
Application number
EP19850904921
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English (en)
French (fr)
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EP0197981A1 (de
Inventor
John E. Bennett
Donald S. Novak
Thomas A. Mitchell
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Eltech Systems Corp
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Eltech Systems Corp
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Priority to AT85904921T priority Critical patent/ATE50603T1/de
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F13/00—Inhibiting corrosion of metals by anodic or cathodic protection
    • C23F13/02—Inhibiting corrosion of metals by anodic or cathodic protection cathodic; Selection of conditions, parameters or procedures for cathodic protection, e.g. of electrical conditions
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F2201/00—Type of materials to be protected by cathodic protection
    • C23F2201/02—Concrete, e.g. reinforced

Definitions

  • the present invention relates to anodes of impressed-current cathodic protection systems comprising a body of current-conducting polymer in the surface of which are fixed electrochemically active elements, and a method of making such catalytic polymer anodes.
  • cathodic protection is effective to prevent corrosion of reinforcing steel in concrete bridge decks, support structures and parking garages, which are subject to extensive damage by corrosion of the steel reinforcement due to the presence of salt and moisture in the normally alkaline concrete environment.
  • Such damage of reinforced concrete by corrosion results more particularly from the practice of spreading large amounts of salt on roads in winter, while coastal structures are attacked by seawater and salt spray.
  • a known type of polymer anode commercially available for use in impressed-current cathodic protection systems consists of a carbon loaded, current conducting polymer body with a copper core and operates at a current density limited to a maximum of about 0.02 A/m 2 to avoid causing damage to the polymer anode surface.
  • Another type of anode which is used for cathodic protection of reinforcing steel consists of carbon fibers which are placed in a groove in the concrete, the groove then being filled with a grout of electronically conductive carbon-loaded backfill.
  • carbon presents serious limitations, since this material is subject to high operating voltages and therefore a limited lifetime as an anode. This is a serious limitation since replacement of anodes embedded in concrete is very difficult.
  • This type of anode also has a high electronic resistivity, so that current can be carried longitudinally only over very short distances through the carbon fibers.
  • anodes which are traditionally used for impressed current cathodic protection are constructed of platinized titanium or platinized tantalum with a more electronically conductive copper core. Such electrodes are often used for cathodic protection of underground pipelines, well casings, ship hulls, jetties, drilling rigs, and oil platforms. These electrodes are expensive and must therefore be used at a higher current density, up to 1000 A/m 2 in some cases. The expense of such platinized titanium or tantalum electrodes entails special design problems since a very low current density must be applied to the structure being cathodically protected. This results in a mismatch of current density between anode and cathode. Various system designs attempt to accommodate this mismatch, usually by installation of small anodes at certain locations which are intended to protect large structures over great distances. Unfortunately, this often leads to unforeseen current density disparities and inadequate protection of more distant parts of the structure.
  • composite electrodes which comprise a polymer material combined with a dispersed conductive filler, or an electrocatalyst, or both.
  • the state of the art relating to such composite electrodes may be illustrated for example by U.S. Patents No. 3,629,007; 3,751,301; 4,118,294; 4,473,450 and European Patent Application No. 0 067 679.
  • European Patent Application No. 0 122 785 for instance proposed and claimed in article which is suitable for use as an anode in a method for protecting an electrically conductive substrate from corrosion and which comprises: a first element which provides part of the electrochemically active surface of the article, and is composed of a conductive polymer; and a plurality of second elements which provide part of the electrochemically active surface of the article, are partially embedded in, and project from the surface of, the first element, and are composed of a material such that, when the article is used as an anode in a method for protecting an electrically conductive substrate from corrosion, the electrochemical reactions at the anode take place preferentially on the second elements rather than the first element.
  • these second elements were carbon fibres or graphite fibres, typically in the form of multifilament yarn.
  • European Patent Application No. 0 046 727 described and claimed an anode for oxygen evolution in an acid electrolyte, comprising a base of lead or lead alloy, having catalytic particles comprising at least one catalyst for oxygen evolution fixed to a support particle consisting of a valve metal. These particles were partly embedded in the lead or lead alloy base and uniformly distributed at the surface of the base, so that the particles were firmly anchored and electrically connected to the base while a substantial non-embedded part of the particles remained projecting from the surface of the base for contact with the acid electrolyte.
  • Oxygen could thereby be evolved on the surface of the particles at a reduced potential at which the underlying lead or lead alloy base essentially served as a current conducting support for the catalytic particles.
  • Such anodes were useful as replacement of the conventional lead or lead alloy anodes without catalytic particles.
  • An object of the invention is to provide a catalytic polymeric anode with a long service life which is particularly suitable for the cathodic protection of reinforced concrete structures, such as bridge decks, parking garages, and coastal structures exposed to seawater and salt spray, as well as the cathodic protection of underground pipelines, well casings, ship hulls, jetties, drilling rigs, oil platforms, and the like.
  • an anode of an impressed-current cathodic protection system comprising a body of current conducting polymer in the surface of which are fixed electrochemically active elements, wherein these active elements are catalytic particles of valve metal surface-coated with an electrocatalyst.
  • the anode according to the invention may comprise any suitable current conducting polymer body. Carbon loaded polymers are advantageous.
  • the current conducting body may be made from thermoplastic polymer compounds.
  • the preferred thermoplastic resins include: polyolefins such as polymers of ethylene and/or propylene; halocarbon polymers such as polyvinyl chloride, polyvinylidene fluoride and halogen substituted olefinic polymers; styrenic polymers such as polystyrene, and copolymers of styrene with acrylonitrile, etc; polyamides such as polycaprolactam; thermoplastic polyesters; and acrylic resins such as polyacrylates and polymethacrylates.
  • higher strength thermoplastics including polyimides; polyarylene resins, such as polycarbonates, polysulfones and polyphenylene. oxides and sulfides; and various heterocyclic resins may also be used.
  • the invention provides a particularly simple method of manufacturing such a catalytic polymer anode with an extended service life.
  • the polymer anode is made by heating a cable of thermoplastic polymer so as to produce a softened external layer of the thermoplastic polymer and pressing catalytic valve metal particles onto said softened external layer of the polymer cable.
  • the catalytic valve metal particles may advantageously be heated before pressing, the pressing being carried out so that upon cooling a uniform outer layer of catalytic valve metal particles is anchored to the surface of the electrode base.
  • the amount of fibers may be as high as 50 weight %, the best results are obtained when the amount of fibers in the carbon loaded polymer is kept in the range of 5 to 30% by weight of the polymer. This is based on the finding that the polymer body made with more than 50% of fibers loses its mechanical properties and when the amount of fibers is kept below 5% the conductivity of the polymer body is not adequate.
  • Various conductive fibers may be employed e.g. carbon, glassy carbon, nickel, copper, aluminium or stainless steel fibers.
  • thermoplastic polymer is particularly advantageous in that it allows a catalytic polymer anode to be produced according to the invention by this extremely simple and reproducible method, while ensuring an excellent fixation and electrical connection of said catalytic particles to the surface of the polymer body.
  • the anode according to the invention may be produced in a highly simplified manner in the form of a continuous electrode of any suitable cross-section, for example in the form of a wire, rod, strip, or sheet.
  • the body formed of current conducting, carbon-loaded polymer will advantageously comprise an internal metallic reinforcing core, preferably a copper core, which is embedded in the carbon loaded polymer body, in order to allow the catalytic polymer electrode to conduct a sufficiently high electrical current while avoiding an excessive voltage drop within the electrode.
  • the catalytic particles used in the invention advantageously consist of one of the valve metals titanium, niobium, tantalum, zirconium, or an alloy thereof which exhibits substantially the same anodic film-forming properties as these valve metals.
  • Catalytic particles of titanium sponge which have an irregular size and shape and are readily deformable may be advantageously pressed into a coherent layer adhering to the surface of a current conducting polymer body.
  • catalytic valve metal particles are advantageously activated with an electrocatalyst which provides a reduced oxygen potential and which may comprise at least one precious metal selected from ruthenium, palladium, iridium, platinum, and rhodium in the metallic state or, preferably, as an oxide.
  • a very small amount of precious metal may be applied to the valve metal particles and the proportion of precious metal applied may advantageously be at most in the order of 1 % by weight of the valve metal particles, and advantageously considerably below 1%.
  • This proportion of precious metal applied may preferably lie in the range from 0.1% to about 1.0% but may if necessary amount up to about 5%.
  • the particle loading of the catalysed valve metal particles may advantageously be in the range 10 to 100 grams per square meter of the electrode base surface to which they are applied, but this loading may amount to up to 500 grams per square meter or more in some cases.
  • the catalytic particles employed according to the invention may be prepared in any suitable manner, for example by a process as described in U.S. Patent No. 4,454,169, or in U.S. Patent No. 4,425,217.
  • the catalytic particles may be simply applied, fixed, and electrically connected by pressing them onto the surface of a heated thermoplastic polymer body forming the anode base. These particles may thus be applied by means of rollers, or by drawing the polymer body through a die. An electronically conductive glue or adhesive may likewise be used for their electrical connection.
  • the impressed-current anodes for cathodic protection systems according to the invention are used at current densities that do not exceed 500 Alm 2 and are preferably between 10 and 350 A/ m 2 .
  • the catalytic polymer anode of the invention is particularly effective in protecting buried or submerged steel structures such as gas and oil pipelines.
  • the catalytic anode according to the invention may thus be expected to exhibit a long service life in cathodic protection systems due to the fact that it can operate at a much lower potential and can thereby protect the current conducting polymer body from damage by oxidation during operation at a relatively high anode current density.
  • the activated polymer anode of the invention may be in the form of cable, sheet, wire, perforated plate or any other convenient form.
  • the active catalytic material e.g. Ru0 2
  • the preferred form is the cable.
  • a catalytic polymer anode was made by applying catalytic titanium particles to an anode base consisting of a conventional current conducting polymer anode of carbon loaded polyolefin with a copper core, which is a conventional, wire-shaped polymer anode (diameter 1 cm) commercially available for impressed-current cathodic protection.
  • the polymer anode body was heated to 120°C for 10 minutes and catalytic titanium particles were then pressed with a roller onto the softened anode surface, which provided good adherence of the catalytic particles to the anode surface.
  • the catalytic particles thus applied consisted of activated titanium sponge with a particle size in the range from 300 to 840 micrometers. These sponge particles were activated by impregnation with an activating solution comprising 2.38 g RuCI 3 - aq. (40 wt% Ru), and 3.36 g tetra-ortho- butyl titanate dissolved in 3.2 ml concentrated HCI and 80 ml butylalcohol, then drying at 100°C in air for 120 minutes, and heat treating the dried particles in air at 300°C for 30 minutes, at 425°C for 30 minutes, and finally at 500°C for 10 minutes. This activating treatment qas carried out 2 times and the catalytic particles thus obtained contained 1% Ru by weight of Ti.
  • an activating solution comprising 2.38 g RuCI 3 - aq. (40 wt% Ru), and 3.36 g tetra-ortho- butyl titanate dissolved in 3.2 ml concentrated HCI and 80 ml but
  • the total loading of the catalytic particles applied as described corresponded to 100 g/m 2 of the polymer anode surface.
  • the catalytic anode thus obtained was tested in a concrete block containing a steel reinforcement bar, and compared with a conventional polymer anode (without catalyst) as described above.
  • the catalytic anode and the conventional polymer anode were symmetrically positioned in the same vertical plane and on opposite sides of a vertical steel reinforcement bar (at 5 cm from the steel bar), and each anode was provided with a reference electrode (Ag/AgCI) for measuring its single electrode potential (S.E.P).
  • a block of concrete (9x13x30 cm) containing 8.8 kg/m 3 of NaCI was then cast around the anodes and the steel bar so that they were embedded while their top ends projected from the concrete block for connection to a D.C. supply source.
  • An impressed current corresponding to an anode current density of 0.11 A/m 2 was passed through the concrete block between the steel bar connected to the negative terminal of the D.C. source and the anodes connected to the positive terminal, while the anode potentials were measured over a test period of 1 month.
  • the described catalytic anode operated for 30 days at a constant potential of 0.390 V vs. CSE (Copper Sulfate Electrode).
  • CSE Copper Sulfate Electrode
  • the conventional polymer anode exhibited a potential which rose from about 1 V to about 2 V vs. CSE in the first 8 days, decreased slightly to 1.8 V after 20 days, then increased slowly once more to 2.0 V after 30 days.
  • the catalytic anode thus operated at a constant potential up to about 1.6 V lower than the non- catalytic anode, while it may be noted that the anode current density applied in this test is several times higher than that at which the described conventional polymer anode can be operated with a satisfactory service life.
  • the catalytic anode according to the invention may thus be expected to exhibit a long service life in cathodic protection systems, due to the fact that it can operate at a much lower potential, and can thereby protect the current conducting polymer body from damage by oxidation during operation at a relatively high anode current density.
  • the catalytic anode according to the invention may be expected to be functional up to about 500 A/m2.
  • a catalytic polymer anode 150 meters long was made by applying catalytic particles to an anode base consisting of a carbon loaded polyolefin with a copper core.
  • the anode base was first prepared by extruding a conductive thermoplastic compound around a conductive copper core of 1.50 mm diameter wire.
  • Catalyst was prepared by activating 500 grams of titanium sponge with a particle size in the range of 300 to 840 micrometers. After rinsing in acetone and drying at 120°C, the titanium particles were activated by mixing with an activating solution comprising 17.31 grams RuC1 3 aq. (43 wt.% Ru) in 250 ml acetone, drying for 2 hours, prebaking at 340°C for 30 minutes, and postbak- ing at 400°C for 40 minutes. This activating treatment was carried out two times and the catalytic particles thus obtained contained 3% Ru by weight of titanium.
  • Catalyst was then continuously applied in a separate step by passing the anode base through a tube furnace at about 385°C to rapidly heat the polymer surface, passing through a fixed bed of heated catalyst particles, and passing through a series of rollers to press the catalyst particles onto the surface of the anode base.
  • the anode thus prepared was catalyzed with 330 grams of said particles per square meter of anode surface.
  • a catalytic polymer anode 100 meters long was made by applying catalytic particles to an anode base consisting of carbon loaded polyolefin with a copper core.
  • the anode base was first prepared by extruding a conductive thermoplatic compound around a conductive copper core of 3.73 mm diameter wire.
  • Catalyst particles were prepared and were applied to the anode base as described in Example II. An anode thus prepared was catalyzed with 300 grams of said particles per square meter of anode surface.
  • a catalytic polymer anode was prepared by applying catalytic particles to an anode base consisting of a modified carbon loaded polyolefin with a copper core.
  • the anode base was prepared by extruding a mixture of a conductive thermoplastic compound with 15% by weight of added carbon fibers around a conductive copper core of 3.73 mm diameter wire. Addition of the carbon fibers had the effect of lowering the volumetric resistivity of the polymeric phase from 20 ohm-centimeters to 0.20 ohm-centimeters making possible operation at higher current density.
  • Catalytic particles containing 3% Ru by weight of titanium were prepared as described in Example II, and were then applied to the surface of the anode base by heating the anode base to 120°C for 10 minutes and rolling the catalytic titanium particles onto the softened anode surface.
  • the anode thus prepared contained 380 grams of said particles per square meter of anode surface.
  • Catalytic polymer anodes of impressed-current cathodic protection systems are especially suitable to prevent corrosion damage of reinforced concrete structures such as bridge decks, support members and parking garages, or buried or submerged steel structures such as gas and oil pipelines, offshore production platforms, fuel storage tanks and well casings.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Prevention Of Electric Corrosion (AREA)
  • Catalysts (AREA)

Claims (15)

1. Anode für ein kathodisches Schutzsystem mit aufgezwungenem Strom, wobei die Anode einen Körper aus stromleitendem Polymer aufweist, in dessen Oberfläche elektrochemisch aktive Elemente gebunden sind, dadurch gekennzeichnet, daß die aktiven Elemente katalytische Teilchen aus mit einem Elektrokatalysator oberflächenbeschichtetem Ventilmetall sind.
2. Anode nach Anspruch 1, bei der der Körper aus einem kohlenstoffbelandenen Polymer gebildet ist.
3. Anode nach Anspruch 1 oder 2, bei der der stromleitende Polymerkörper bis zu 50 Gew.% in ihm dispergierte Kohlenstoff- oder Metallfasern enthält.
4. Anode nach Anspruch 1, 2 oder 3, bei der das Polymer ein thermoplastisches Polymer ist.
5. Anode nach Anspruch 4, bei der das thermoplastische Polymer aus Polyolefinen, Halogenkohlenwasserstoffpolymeren, styrolartigen Polymeren, Polyamiden, thermolastischen Polyestern, Acrylharzen und deren Mischungen ausgewählt ist.
6. Anode nach Anspruche 1, 2 oder 3, bei der ein metallischer Kern innerhalb des stromleitenden Polymerkörpers eingebettet ist.
7. Anode nach Anspruch 1 oder 2, bei der das Ventilmetall aus Titan, Tantal, Niob und Zirkonium ausgewählt ist.
8. Anode nach Anspruch 1 oder 7, bei der der Elektrokatalysator mindestens ein Edelmetall ausgewählt aus Ruthenium, Palladium, Rhodium, Iridium und Platin entweder als Metall oder als deren Oxid enthält.
9. Anode nach Anspruch 8, bei der die katalytischen Teilchen das Edelmetall in einer Menge von 0,1 bis 5% bezogen auf das Gewicht des Ventilmetalles enthalten.
10. Anode nach Anspruch 1, bei der die katalytischen Ventilmetallteilchen in einer Menge auf die Oberfläche des stromleitenden Polymerkörpers aufgebracht sind, die einer Beladung von etwa 10 bis etwa 500 g der katalytischen Teilchen pro Quadratmeter der Oberfläche entspricht.
11. Anode nach einem der Ansprüche 1 bis 10, bei der das Ventilmetall Titan ist und der Elektrokatalysator Rutheniumoxid enthält.
12. Anode nach einem der Ansprüche 1 bis 11, bei der der Polymerkörper in Form eines Kabels vorliegt.
13. Verfahren zur Herstellung einer Anode nach Anspruch 12, bei dem
(a) das Kabel aus einem thermoplastischen Polymer erwärmt wird, um eine weichgemachte äußere Schicht des thermoplastischen Polymer herzustellen, und
(b) die katalytischen Ventilmetallteilchen auf die weichgemachte äußere Shicht des thermoplastischen Polymer aufgedrückt werden, um beim Abkühlen eine einheitliche äußere Schicht der katalytischen Ventilmetallteilchen zu erhalten, die an der Oberfläche des Kabels aus thermoplastischem Polymer verankert sind.
14. Verfahren nach Anspruch 14, bei dem die katalytischen Ventilmetallteilchen erwärmt werden, bevor sie auf die weichgemachte äußere Schicht des thermoplastischen Polymer aufgedrückt werden.
15. Verwendung der Anode nach einem der Ansprüche 1 bis 12 als Anode mit aufgezwungenem Strom in einem kathodischen Schutzsystem zur Verhinderung der Korrosion von Armierungsstahl in Beton oder eingegrabenen oder im Wasser versenkten Stahlstrukturen bei einer Anodenstromdichte bis zu 500 A/m2.
EP19850904921 1984-10-01 1985-09-19 Katalytische polymerelektrode für katodischen schutz und diese elektrode enthaltendes kathodisches schutzsystem Expired EP0197981B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT85904921T ATE50603T1 (de) 1984-10-01 1985-09-19 Katalytische polymerelektrode fuer katodischen schutz und diese elektrode enthaltendes kathodisches schutzsystem.

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US65663484A 1984-10-01 1984-10-01
US77244385A 1985-09-06 1985-09-06
US772443 1985-09-06
US656634 2000-09-07

Publications (2)

Publication Number Publication Date
EP0197981A1 EP0197981A1 (de) 1986-10-22
EP0197981B1 true EP0197981B1 (de) 1990-02-28

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EP19850904921 Expired EP0197981B1 (de) 1984-10-01 1985-09-19 Katalytische polymerelektrode für katodischen schutz und diese elektrode enthaltendes kathodisches schutzsystem

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EP (1) EP0197981B1 (de)
AU (1) AU4960285A (de)
BR (1) BR8506959A (de)
CA (1) CA1278775C (de)
DE (1) DE3576174D1 (de)
WO (1) WO1986002106A1 (de)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4957612A (en) * 1987-02-09 1990-09-18 Raychem Corporation Electrodes for use in electrochemical processes
GB9115184D0 (en) * 1991-07-12 1991-08-28 Jennings Winch Foundry Co Ltd Anodes for cathodic protection
WO1997044505A1 (fr) * 1996-05-22 1997-11-27 Delektorsky Alexandr Alexeevic Anode de mise a la terre, composition pour cette anode et procede de fabrication de cette composition

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4381983A (en) * 1980-06-02 1983-05-03 Ppg Industries, Inc. Solid polymer electrolyte cell
GB2085031B (en) * 1980-08-18 1983-11-16 Diamond Shamrock Techn Modified lead electrode for electrowinning metals
DE3036066A1 (de) * 1980-09-25 1982-05-06 Hoechst Ag, 6000 Frankfurt Verfahren zur herstellung eines elektroden-membran-verbundsystems
US4473450A (en) * 1983-04-15 1984-09-25 Raychem Corporation Electrochemical method and apparatus

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CA1278775C (en) 1991-01-08
EP0197981A1 (de) 1986-10-22
WO1986002106A1 (en) 1986-04-10
AU4960285A (en) 1986-04-17
BR8506959A (pt) 1986-12-23
DE3576174D1 (de) 1990-04-05

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