EP0273806B1 - Procédé électrochimique de traitement de fibres de carbone, et fibres traitées par ce procédé - Google Patents

Procédé électrochimique de traitement de fibres de carbone, et fibres traitées par ce procédé Download PDF

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Publication number
EP0273806B1
EP0273806B1 EP87402719A EP87402719A EP0273806B1 EP 0273806 B1 EP0273806 B1 EP 0273806B1 EP 87402719 A EP87402719 A EP 87402719A EP 87402719 A EP87402719 A EP 87402719A EP 0273806 B1 EP0273806 B1 EP 0273806B1
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Prior art keywords
carbon
fibers
treatment
process according
potential
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EP87402719A
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German (de)
English (en)
French (fr)
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EP0273806A1 (fr
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Manuel Sanchez
Georges Desarmot
Blandine Barbier
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Office National dEtudes et de Recherches Aerospatiales ONERA
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Office National dEtudes et de Recherches Aerospatiales ONERA
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    • 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
    • D01F11/16—Chemical after-treatment of artificial filaments or the like during manufacture of carbon by physicochemical methods
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/22—Nonparticulate element embedded or inlaid in substrate and visible
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2918—Rod, strand, filament or fiber including free carbon or carbide or therewith [not as steel]

Definitions

  • the invention relates to an electrochemical process for the surface treatment of carbonaceous materials. It applies in particular to the surface treatment of carbon fibers in order to improve the adhesion of the fibers to the resin in a composite material formed of carbon fibers embedded in a matrix of synthetic resin.
  • Electrochemical treatments of this type are for example described in the oppositionde of French patent No. 2,477,593. They essentially consist in immersing the fibers in an electrolyte solution by polarizing them positively with respect to a cathode. In particular, good adhesion is obtained by using ammonium and sodium sulfates and bisulfates as electrolytes, which are strong saline electrolytes.
  • the potential applied between the anode made of carbon fibers and the cathode is sufficient to cause the decomposition of water and the appearance of a gaseous release of oxygen, phenomena well known in electrochemistry.
  • the electrolyte then includes reactive species which attack the carbon of the fibers to form oxygenated surface groups which promote fiber-matrix adhesion.
  • the potential V o of decomposition of water with release of oxygen is close to +1.7 volts relative to a reference electrode with saturated calomel, but can be lowered by certain electrolytes.
  • French Patent No. 2,564,489 in the name of the Applicant describes a process for treating carbon fibers allowing the grafting of nitrogenous functions.
  • the fibers are immersed in an aqueous solution of an amino compound which dissociates little water, so as to avoid an excessive reduction in V o .
  • the object of the invention is to provide an electrochemical process leading to the grafting of nitrogenous groups to the surface of carbon fibers, avoiding the limitations linked to the use of an aqueous solution, in particular with regard to the speed of the electrochemical reaction. .
  • Another object of the invention is to graft nitrogen groups onto carbon in a form other than that of fibers, in particular in a divided form, with a view to catalytic use for example.
  • the subject of the invention is an electrochemical carbon treatment process in which the carbon is brought into contact with a solution of an amino compound in a dipolar solvent by polarizing it positively with respect to a cathode, characterized in that the solvent is an organic compound with high anodic oxidation potential, the solution being practically free of water.
  • the solvent is an aprotic dipolar solvent.
  • the first condition is that the surface reactivity of the carbon is sufficient, which is the case of microporous carbons, graphitable carbons of low temperature and carbons with activated surface.
  • La and Le denote the dimensions of the basic textual unit, respectively parallel and perpendicular to the aromatic layers.
  • the size of the micropores is of the order of a few tens of nanometers; The rest remains low whatever the heat treatment temperature, the torsion of the layers being non-reducible.
  • the carbon of the "high resistance” fibers has a microtexture constituted by an assembly of basic textural units (UTB) formed by a turbostratic stack of two or three aromatic layers of small dimension [approximately 1 nm (10 A)].
  • the UTB are connected to each other by sp 3 type chemical bonds forming a joint with bending and twisting disorientations.
  • a "high resistance” fiber is made up of UTB aggregates whose average orientation is that of the axis of the fiber.
  • the surface of these fibers has a high density of sp 3 type bonds capable of being attacked electrochemically.
  • the “intermediate fibers” have UTBs slightly larger in size than those of the "high resistance”fibers; the density of surface bonds type S p 3 remains high, although less.
  • the carbon of "high modulus" fibers is analogous to a non-graphitable pyrocarbon with large La, but it remains microporous. This type of carbon is not suitable for the treatment according to the invention, unless it is previously activated.
  • the "high modulus” fibers comprise UTBs of very different sizes, because they have undergone a "graphitation" stage between 2000 and 3000 ° C.
  • the UTB are turbostratic stacks of several tens of aromatic layers providing reaching or exceeding, in particular on the surface, a size of 100 nm (1000 ⁇ ). Consequently, the density of joints between UTB is much lower than for "high strength" fibers, which gives "high modulus” fibers a surface reactivity very attenuated by the bonds between carbon atoms engaged in aromatic rings are very stable.
  • the action of a nitrogen plasma on the surface of these fibers increases their reactivity by the ejection of carbon atoms from the aromatic surface layers and consequently allows the treatment according to the invention.
  • Graphitable carbons are characterized by a Le higher than La below about 1500 ° C, but their La increases above 1500 ° C and especially 2000 ° C (observation by high resolution electron microscopy in network fringes) in developing a three-dimensional periodic structure (graphitation).
  • Low temperature graphitable carbons ( ⁇ ⁇ 1500 ° C) therefore have a microtexture which makes them sensitive to the action of an electrochemical treatment.
  • High temperature graphitable carbons only become graphitable if their surface has been previously activated.
  • the second condition allowing grafting is that the working potential V t is less than the decomposition potential V SOL of the solvent or of the solvent + support electrolyte pair.
  • the organic solvent used in the treatment can be, in particular, acetonitrile, dimethylformamide, dimethyl sulfoxide. It is advantageous to add to the solution a support electrolyte also having a high anodic oxidation potential V es , which depends on the nature of the organic solvent, such as lithium perchlorate, tetraethylammonium perchlorate or, for example, tetrafluoroborates, alkaline tetrafluorophosphates or quaternary ammoniums.
  • V es anodic oxidation potential
  • the working potential V t is limited by the oxidation potential of the support electrolyte, which varies with the solvent used, which leads to setting a potential V SOL for a couple considered.
  • the table below lists the V SOL values observed for various solvents and supporting electrolytes.
  • V t must be greater than the redox potential V E of the amino compound or, if the amino compound has several amine functions, V t must be greater than the redox potential the weaker.
  • V t In order for the electrochemical reactions to occur quickly, we must make sure that the difference V t ⁇ V E is high with V t ⁇ V SOL . It is also desirable that V t is not too close to V SOL , since we could then see parasitic electrochemical phenomena such as the passivation of the anode resulting from an accumulation of amine oxidation products forming a film on the electrode which may possibly remain on the surface.
  • amino compound it is also possible to use the amino 6 methyl 2 pyridine, tetramethylbenzidine, or any other compound having at least one redox potential lower than V SOL .
  • the treatment is carried out under insufficient polarization to cause the decomposition of the solvent and of the support electrolyte.
  • V t 1.3 volts is located at the start of the ohmic regime of the polarization curve.
  • the invention also relates to a carbon, in particular in the form of fibers, treated by the process which has just been defined, as well as a composite material.
  • the carbons treated according to the invention can also be powdered or divided carbons, provided that they also belong to the categories of microporous carbons and graphitable carbons of low temperature or that their surface has been activated.
  • a tank 1 contains an electrolyte solution 2 in which is immersed a bundle of monofilaments or carbon fibers 3 forming an anode and coated in an insulating support 4.
  • the anode thus that a platinum cathode 5 and a reference electrode 6 -at saturated calomel for treatments in an aqueous medium; a 0.01 M Ag / Ag + system in acetonitrile for treatment in a non-aqueous medium - which also immerse in solution 2, are connected to a potentiostat 7 which maintains a potential between the anode and the reference electrode of predetermined value, chosen so as to avoid the release of oxygen by electrolysis in an aqueous medium or the decomposition of the mixture of solvent and of the support electrolyte (LiCl0 4 ) in a non-aqueous medium.
  • Argon is bubbled into the bath, supplied by a tube 8 which opens below the fibers 3. This avoids the presence of dissolved oxygen in the bath.
  • the electrolytic bath 2 is either an aqueous solution of an amino compound, or a solution of an amino compound and a support electrolyte in a dipolar organic solvent. electrochemical reactions occurring at the interface of the solution and the fibers result in the grafting by nitrogen of nitrogen groups or molecules of the amino compound on the surface of the fibers.
  • the curve of FIG. 2 shows the evolution of the current 1 passing through the anode as a function of the potential V of the latter relative to the reference electrode.
  • V the potential of the current
  • the working potential V is chosen at a maximum value but less than a value V o for which the release of oxygen begins to manifest in an aqueous medium (examples 1, 2 and 3) or below the ohmic regime in the medium non-aqueous (Example 4).
  • V o is generally of the order of +1.7 volts (relative to the saturated calomel electrode) if the compound does not dissociate the water well and a potential of work V t close to +1.5 volts.
  • the working potential V t is of the order of +1.3 volts (relative to the reference electrode Ag / Ag + ) in a non-aqueous medium (example 4), this value being close to the start of the ohmic regime. It is not advantageous to choose a lower value for V t , which would slow down the electrochemical process.
  • the organic solvent for example acetonitrile
  • the organic solvent must be free of water and dehydrated beforehand if it contains it. Another characteristic is that it must have a dipolar character in order to dissolve the support electrolyte, the nature of which does not matter, insofar as it does not intervene in the electrochemical processes (decomposition potential clearly greater than the potential V t ).
  • the solvent is aprotic, it promotes the deprotonation of a cation radical.
  • the choice of the dipolar solvent is based solely on the consideration that its decomposition potential is also clearly greater than V t .
  • the curve of FIG. 2 does not generally show an oxidation-reduction peak of the amino compound, because the geometry of the electric field lines is complex in the vicinity of a multifilament electrode.
  • FIG. 3 An installation for the continuous treatment of fibers is shown diagrammatically in FIG. 3.
  • the roller 15 (and possibly other rollers) is rotated by means not shown so as to advance the wire 10 continuously.
  • Rollers 11 and 15 are connected to a positive output terminal of a potentiostat 16, a negative terminal of which is connected to a cathode 17 made of stainless steel immersed in the solution 12, so as to positively polarize the wire 10 relative to the cathode.
  • a reference electrode 18 to the calomel is connected to a control terminal 19 of the potentiostat 16, which makes it possible to set the potential of the anode relative to the reference electrode to a desired value. This installation makes it possible to carry out the same type of treatment as the device in FIG. 1, but continuously.
  • FIG. 4 An installation for the treatment of divided carbon is shown diagrammatically in FIG. 4.
  • a bed of divided carbon 20 is retained by a fine platinum grid 21 acting as an anode, itself resting on a porous disc 22 obstructing a cylindrical column vertical 23 in glass.
  • a second platinum grid 24 disposed above the carbon bed 20 constitutes the cathode.
  • a reference electrode 25 plunges into the carbon bed 20.
  • the enclosure 23 is filled with electrolyte 26 whose circulation in the cathode-anode direction is ensured by a pump 27 (the elements of the pump in contact with the electrolyte are chemically inert).
  • the anode 21, the cathode 24 and the reference electrode 25 are connected to a potentiostatic device 28.
  • One end of a fragment of an insulated fiber is introduced into the movable jaw of a traction machine, shrinking it with a drop of tin solder, and the other end is coated in the resin over a length low enough that the force required to tear the fiber from the resin is less than the breaking force of the fiber.
  • the breakout force F d is measured by means of the traction machine; the perimeter p of the section of the filament and the length implanted in the resin 1 are determined by means of a scanning electron microscope calibrated in magnification.
  • Greszozuk established a theory of the pull-out test. It shows that the shear stress T fiber-matrix is maximum at the embedding of the filament and that it decreases as one moves away from the embedding.
  • T reaches ⁇ d , fiber-matrix decohesion constraint.
  • ⁇ d is given by the formula: where a is a coefficient taking into account the geometry of the embedding of the filament and the Young's moduli of the fiber and shear of the resin.
  • the experiment gives access to the average decohesion constraint T given by the formula: So :
  • Examples 1 to 3 below are taken from the aforementioned French Patent No. 2,564,489, but the values of ⁇ d given there have been corrected for the effect of embedding length of the filament as indicated above, whereas the results indicated in the Patent did not take this correction into account.
  • the effect of this is to slightly increase the values of Td which are thus closer to reality, allowing a more precise comparison between the corresponding results and those provided by the present invention, reported in Example 4. All the values of ⁇ d given below are corrected and the error on T d is estimated with a confidence interval of 68%.
  • the processing temperature is 20 ° C.
  • Figure 6 combines ESCA and SIMS spectra performed on untreated COURTAULDS HT fibers (a, b, c) then on treated fibers 10 minutes (d, e, f) and 60 minutes (g, h, i) .
  • a detail of the peaks Cls and Nls (ESCA) is given in Figure 7.
  • a spectrum in SIMS shows peaks corresponding to the various species of ions torn from the surface by the primary argon ion beam, in the composition of which enter the elements present on the surface of the fibers over a thickness of about 0.5 nm (5 ⁇ ).
  • the peak at mass 24 (secondary ions CC-) is characteristic of the carbonaceous substrate and serves as a reference.
  • the peaks at masses 25 and 26 correspond to CCH - and CCH 2 - ions for the untreated fiber which contains very little nitrogen.
  • the peak at mass 26 contains CCH 2 ions - and CN ions - originating from the nitrogenous surface groups.
  • R (N) defined as follows:
  • R (O) is defined analogously from the peaks at masses 16 and 17 (0- and OH - ). Table II groups together the analyzes carried out.
  • FIG. 7 shows the photoelectron peaks Cls in Nls corresponding.
  • the peaks Cls Figures 7c and 7e respectively
  • the peaks Cls Figures 7c and 7e respectively
  • Figure 7a shows that the carbon is partly bound with more electronegative elements than him, especially nitrogen
  • the Nls peaks FIGS. 7b, d and f respectively for 0.10 and 60 minutes
  • Treatments were carried out using the amino 6 methyl 2 pyridine (primary amine) as the electrolyte.
  • the processing temperature is 20 ° C.
  • FIG. 13b corresponding to Table III represents the evolution of ⁇ d as a function of the processing time. This curve has a maximum around 10 minutes of treatment and the value of ⁇ d obtained for this time is very comparable to that of Example 1 for the same duration.
  • This body is an aminoamide comprising two amine groups.
  • FIG. 13c corresponding to Table IV shows the evolution of Td as a function of the duration of the treatment.
  • the electrolyte is ethylenediamine (primary amine comprising two amine functions) in solution in dehydrated acetonitrile at the rate of 12 g per liter.
  • a supporting electrolyte is added, lithium perchlorate at a rate of 21 g per liter of solution.
  • the potential of the COURTAULDS HT fibers is +1.3 volts compared to a 0.01 M Ag / Ag + reference electrode containing acetonitrile.
  • the temperature is 20 ° C., the experimental treatment device is that of FIG. 1.
  • the procedure of Example 1 is also reproduced for the measurements of Td .
  • FIG. 14a shows the evolution of Td as a function of the duration of the treatment for a fiber coated in the Araldite LY 556 + HT 972 resin.
  • FIG. 14b shows the result obtained using the NARMCO 5208 resin, a resin sold by the company NARMCO and composed mainly of tetraglycidylmethylenedianiline and diaminodiphenylsulfone acting as hardener.
  • the surface analyzes corresponding to the 5 nm treatment provide: in ESCA: in SIMS:
  • the peak Cls (FIG. 10d) has a very large shoulder attesting that a large part of the surface carbon is covalently linked to atoms more electronegative than it, in particular to nitrogen since R (N) and the concentration d are very high.
  • nitrogen is located on the surface: R (N) »R (O).
  • the oxygen - which can come from traces of water in the solution - is located below the surface.
  • SIMS positive Figure 10c
  • ⁇ d for the NARMCO 5208 resin is worth 60.9 MPa for the untreated fibers against 28.1 MPa with the CIBA GEIGY LY 556 resin. This can be explained by considering that the NARMCO 5208 resin is more reactive that the CIBA GEIGY LY 556 resin vis-à-vis the bare surface of the untreated fibers and that direct fiber bonding can be established without surface grouping. Likewise, NARMCO 5208 resin reacts more easily with grafted surface groups, since practically maximum adhesion is reached around 2.5 minutes.
  • the electrolyte is the amino 6 methyl 2 pyridine in solution in dehydrated acetonitrile at a rate of 45 g per liter, without supporting electrolyte.
  • the potential of COURTAULDS HT fibers is +1 Volt compared to a reference electrode Ag / Ag + 0.01 M in acetonitrile.
  • the temperature is 20 ° C., the treatment device is that of FIG. 1.
  • the duration of the treatment is three minutes.
  • FIG. 11a shows the peak Cls of the fibers thus treated
  • FIG. 11b the peak Nls
  • FIG. 11 c the spectrum in negative SIMS
  • FIG. 11d the spectrum in SIMS positive.
  • the shoulder of the Cls peak shows that the carbon is linked to more electronegative atoms than it.
  • the electrolyte is ethylene diamine in solution in dehydrated dimethylformamide at the rate of 12 g / liter.
  • a supporting electrolyte is added, lithium perchlorate at a rate of 21 g per liter of solution.
  • the potential of the COURTAULDS HT fibers is, that is +1.45 Volt compared to a saturated calomel reference electrode (ECS) (equivalent to +1.15 Volt compared to an Ag / Ag reference electrode + 0.01 M in acetonitrile), ie +1.6 Volt with respect to this same electrode (equivalent to +1.3 Volt with respect to Ag / Ag + ).
  • ECS saturated calomel reference electrode
  • the processing temperature is 20 ° C, the processing time 5 minutes; the experimental treatment device is that of FIG. 1.
  • the corresponding surface spectroscopic analyzes (Table VI) were carried out with a device different from that used in Examples 1 to 5, 7 and 8. This second device was the subject of a calibration so that we can compare the results obtained in the present example with those cited in the other examples.
  • the photoelectron energy scale (ESCA) is taken here in relation to the Mg Ka radiation and represents their kinetic energy while in the other examples the abscissa represents the EB binding energy of the photoelectrons with their emitting atom.
  • a broad shoulder towards low kinetic energies strong bond energies in the atom attests that carbon is chemically linked to atoms more electronegative than it.
  • Figures 12c and 12d are the negative and positive SIMS spectra.
  • Figures 12g and 12h show the negative and positive SIMS spectra.
  • the decohesion stress measured according to the procedure of Example 1 with the NARMCO 5208 resin is: since oxygen cannot participate significantly in adhesion since R (O) is only worth 0.21.
  • a segment 5 cm in length 31 is disposed on a graphite support 32 placed inside a cylindrical envelope 33 cooled by circulation of water.
  • Two external annular electrodes 34 are connected to a high frequency generator 35.
  • a pump 36 maintains a nitrogen pressure close to 15 Pa in the enclosure thanks to a controlled nitrogen micro-leak 37.
  • the power dissipated in the nitrogen plasma is approximately 100 watts.
  • Plasma treatment can be carried out continuously on a carbon wire by means of a suitable installation, not shown.
  • FIG. 15a represents the peak Cls (ESCA) of the non-triaturated COURTAULDS HT fibers.
  • FIG. 15b represents the Cls peak after the treatment with hexamethylene tretramine in an aqueous medium after one hour.
  • FIG. 15c represents the peak Cls for the fibers not treated and subjected to the action of epichlorohydrin.
  • FIG. 15d shows the peak Cls of the fibers having undergone the surface treatment with hexamethylene tetramine and the action of epichlorohydrin.
  • Figures 15a and 15c show that the untreated fibers do not bind epichlorohydrin, unlike the treated fibers ( Figures 15b and 15d).
  • the carbon atoms involved in these reactions are surface atoms of a fiber.
  • the cation can have a certain stability in the organic solvent and react with the carbon of the fibers. Reactions involving C 'radicals and oxygen will remain in the minority as soon as the solvent has been suitably dehydrated.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Chemical Treatment Of Fibers During Manufacturing Processes (AREA)
  • Reinforced Plastic Materials (AREA)
  • Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
  • Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
EP87402719A 1986-12-02 1987-12-01 Procédé électrochimique de traitement de fibres de carbone, et fibres traitées par ce procédé Expired - Lifetime EP0273806B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8616841 1986-12-02
FR8616841A FR2607528B1 (fr) 1986-12-02 1986-12-02 Procede electrochimique de traitement de surface de carbone; carbone, notamment fibres de carbone, traite par ce procede et materiau composite comportant de telles fibres

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EP0273806A1 EP0273806A1 (fr) 1988-07-06
EP0273806B1 true EP0273806B1 (fr) 1991-02-06

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US (1) US4844781A (enrdf_load_stackoverflow)
EP (1) EP0273806B1 (enrdf_load_stackoverflow)
JP (1) JPH01500133A (enrdf_load_stackoverflow)
CA (1) CA1324978C (enrdf_load_stackoverflow)
DE (1) DE3767992D1 (enrdf_load_stackoverflow)
FR (1) FR2607528B1 (enrdf_load_stackoverflow)
WO (1) WO1988004336A2 (enrdf_load_stackoverflow)

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CN111600087B (zh) * 2020-05-29 2022-10-04 重庆长安新能源汽车科技有限公司 锂离子电池检测用参比电极和三电极系统及制备方法
CN113322678B (zh) * 2021-05-10 2022-06-28 北京化工大学 表面改性碳纤维及其改性方法

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GB1433712A (en) * 1974-06-06 1976-04-28 Hercules Inc Electrolytic treatment of graphite fibres
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JPH0621420B2 (ja) * 1985-08-20 1994-03-23 東燃株式会社 炭素繊維の表面処理法

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JPH01500133A (ja) 1989-01-19
FR2607528B1 (fr) 1989-03-17
WO1988004336A3 (fr) 1988-07-14
FR2607528A1 (fr) 1988-06-03
CA1324978C (en) 1993-12-07
US4844781A (en) 1989-07-04
JPH0353245B2 (enrdf_load_stackoverflow) 1991-08-14
WO1988004336A2 (fr) 1988-06-16
EP0273806A1 (fr) 1988-07-06
DE3767992D1 (de) 1991-03-14

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