EP1029953A1 - Process for surface treatment and for deposition of polyaniline for absorbing light - Google Patents
Process for surface treatment and for deposition of polyaniline for absorbing light Download PDFInfo
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- EP1029953A1 EP1029953A1 EP00400295A EP00400295A EP1029953A1 EP 1029953 A1 EP1029953 A1 EP 1029953A1 EP 00400295 A EP00400295 A EP 00400295A EP 00400295 A EP00400295 A EP 00400295A EP 1029953 A1 EP1029953 A1 EP 1029953A1
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- Prior art keywords
- polyaniline
- titanium
- roughness
- deposition
- minutes
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D13/00—Electrophoretic coating characterised by the process
- C25D13/20—Pretreatment
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/34—Pretreatment of metallic surfaces to be electroplated
- C25D5/38—Pretreatment of metallic surfaces to be electroplated of refractory metals or nickel
Definitions
- the invention lies in the field of devices with an absorbent coating radiation, especially a polyaniline coating absorbing radiation in a band from ultraviolet to infrared. It also concerns a process for preparing the surfaces receiving the deposit.
- a wide variety of surface treatments or surface coatings with only a low specular reflection and having only a weak reflection diffuse is known. These treatments or coatings are sought in particular for applications optical or infrared. They help ensure that mechanical elements such as optical supports input of optical devices do not reflect or little light and so do not increase the ratio signal / noise of the optical or infrared signal picked up by the detectors of these devices.
- black paints we know they tend to crack or crack detach from particularly metallic substrate, due to stresses induced by cycles especially for infrared systems who often work with sensors cooled to the temperature of helium or liquid nitrogen.
- Degassing products can react chemically and damage components microelectronics or to condense on cooled optical surfaces and darken them.
- the method provides a surface treatment by a jet of aluminum oxide with a particle size 100 to 200 mesh. This initial processing is intended to create a roughness of the surface before anodizing.
- the present invention is under a first aspect directed towards such a roughening treatment.
- the applicant has carried out experiments in which a polyaniline was used as absorbent coating.
- Polyaniline was found to have actually good absorbent qualities, however, the total reflection value remains high in the infrared. Adhesion to the substrate is not good. The tendency to laminate the layer is certain.
- the invention relates to a process for preparing the surface of a substrate intended to receive a polyaniline layer, absorbent in the ultraviolet to infrared, characterized in that the surface of the substrate is roughened before the stages of deposition of the polyaniline layer.
- This Ra value can be obtained by example on a titanium substrate by sandblasting with a abrasive. This can be done with corundum with a particle size between 30 and 120 mesh.
- the sandblasting was made with such a corundum, under a pressure of 6 bars at a distance from the surface to be treated of approximately 20 cm.
- a double pass was made with a rate 100% recovery.
- This initial substrate preparation phase is necessary to decrease or even remove the peak specular reflection in the infrared.
- the deposit aniline, according to a second aspect of the invention can be carried out after this preparatory phase relating to obtaining the roughness of the substrate surface. It may also not be performed if the value specular absorption or reflection obtained without this roughening treatment are judged sufficient.
- the acid proportions could be increased and the duration of the bath decreased, or they could be reduced, the duration of the bath remaining equivalent, but the temperature of the bath being increased.
- the part to be processed, in the laboratory is the working electrode of a three cell electrodes (against stainless steel electrode and saturated calomel reference electrode (ECS)).
- ECS saturated calomel reference electrode
- the alloy is polarized at -0.5 V / DHW for 3 min, then then subjected to anodic scanning at the speed of 10 mV / s until the imposed voltage reaches +2 V / DHW. The scanning is then stopped, but the polarization maintained for 20 minutes.
- the indicated voltages are measured between the calomel reference electrode and the job.
- test pieces After electropolymerization, the test pieces can be steamed at a temperature between 40 ° and 160 ° for a period of between 30 min and 2 hours, for example 1 hour at 160 ° C.
- the NaFHF conversion treatment leaves the surface of the alloy a small amount of fluorine than the hydrolysis treatment makes it possible to decrease but not to totally eliminate.
- This hydrolysis treatment seems favor the speed of formation of the deposit of polyaniline.
- the induction time is shorter and the quantity deposited after a given holding time more important.
- the roughness of the surface of the titanium alloy was changed by sandblasting.
- the aim of polyaniline deposition is to to obtain a surface roughness Ra of between 10 and 30 ⁇ m.
- ANNEX 1 Average reflection: 4% Nm R 250 0.03 300 0.03 350 0.03 400 0.03 450 0.03 500 0.03 550 0.03 600 0.03 650 0.03 700 0.03 750 0.03 800 0.03 850 0.04 900 0.04 950 0.04 1000 0.04 1050 0.04 1100 0.04 1150 0.04 1200 0.04 1250 0.04 1300 0.04 1350 0.04 1400 0.04 1450 0.04 1500 0.04 1550 0.04 1600 0.04 1650 0.04 1700 0.04 1750 0.04 1800 0.04 1850 0.04 1900 0.04 1950 0.04 2000 0.04 2050 0.04 2100 0.04 2150 0.04 2200 0.04 2250 0.04 2300 0.04 2350 0.04 2400 0.04 2450 0.04 2500 0.05 APPENDIX 2 Average reflection: 2% Nm R 250 0.01 300 0.01 350 0.01 400 0.01 450 0.01 500 0.01 550 0.01 600 0.01 650 0.01 700 0.01 750 0.02 800 0.02 850 0.02 900 0.02 950 0.02 1000 0.02 1050 0.
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- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
- Chemical Treatment Of Metals (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Investigating Or Analysing Materials By Optical Means (AREA)
- Chemically Coating (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
- Laminated Bodies (AREA)
- ing And Chemical Polishing (AREA)
- Optical Filters (AREA)
- Surface Treatment Of Optical Elements (AREA)
Abstract
Description
L'invention se situe dans le domaine des dispositifs comportant un revêtement absorbant les radiations, en particulier un revêtement de polyaniline absorbant les radiations dans une bande allant de l'ultraviolet à l'infrarouge. Elle concerne aussi un procédé de préparation des surfaces recevant le dépôt.The invention lies in the field of devices with an absorbent coating radiation, especially a polyaniline coating absorbing radiation in a band from ultraviolet to infrared. It also concerns a process for preparing the surfaces receiving the deposit.
Une grande variété de traitements de surface ou de revêtements de surface n'ayant qu'une faible réflexion spéculaire et n'ayant qu'une faible réflexion diffuse est connue. Ces traitements ou revêtements sont recherchés en particulier pour des applications optiques ou infrarouge. Ils contribuent à ce que des éléments mécaniques tels que les supports des optiques d'entrée de dispositifs optiques ne réfléchissent pas ou peu de lumière et ainsi n'augmentent pas le rapport signal/bruit du signal optique ou infrarouge capté par les détecteurs de ces dispositifs.A wide variety of surface treatments or surface coatings with only a low specular reflection and having only a weak reflection diffuse is known. These treatments or coatings are sought in particular for applications optical or infrared. They help ensure that mechanical elements such as optical supports input of optical devices do not reflect or little light and so do not increase the ratio signal / noise of the optical or infrared signal picked up by the detectors of these devices.
Des problèmes connus relativement à ces revêtements et que l'on cherche évidemment toujours à résoudre par des améliorations des procédés de traitement de surface et/ou de dépôt de revêtements sont signalés par exemple dans la colonne 1 du brevet U.S-A-4 589 972 du 20 mai 1986 délivré à Martin Marietta. Les problèmes signalés dans ce brevet et que l'on cherche aussi à résoudre selon la présente invention sont cités ci-après.Known issues with these coatings and that obviously we're always looking to resolve through process improvements surface treatment and / or coating deposition are indicated for example in column 1 of the patent U.S-A-4 589 972 of May 20, 1986 issued to Martin Marietta. The problems reported in this patent and that we also seek to resolve according to the present invention are cited below.
En ce qui concerne les peintures noires, on sait qu'elles ont tendance à se craqueler ou à se détacher du substrat en particulier métallique, en raison des contraintes induites par les cycles thermiques en particulier pour les systèmes infrarouges qui travaillent souvent avec des capteurs refroidis à la température de l'hélium ou de l'azote liquide.Regarding black paints, we know they tend to crack or crack detach from particularly metallic substrate, due to stresses induced by cycles especially for infrared systems who often work with sensors cooled to the temperature of helium or liquid nitrogen.
Ces phénomènes s'aggravent avec l'épaisseur de la couche de peinture, cette épaisseur étant en général croissante avec la longueur d'onde de la radiation que l'on veut absorber.These phenomena worsen with the thickness of the paint layer, this thickness being generally increasing with the wavelength of the radiation that we want to absorb.
Un autre problème que l'on rencontre est dû au dégazage du revêtement, en particulier lorsque le matériau revêtu opère à haute altitude ou dans l'espace. Les produits issus du dégazage peuvent réagir chimiquement et endommager des composants microélectroniques ou encore se condenser sur des surfaces optiques refroidies et les obscurcir.Another problem that we encounter is due to the degassing of the coating, in particular when the coated material operates at high altitude or in space. Degassing products can react chemically and damage components microelectronics or to condense on cooled optical surfaces and darken them.
Ce brevet (4 589 972) de Martin Marietta propose, comme un brevet précédent de Martin Marietta n° 4 111 762 auquel il est fait référence dans le brevet 4 589 972, d'améliorer la solution à ces problèmes de deux façons. Ces deux améliorations sont applicables à des métaux anodisables, préalablement anodisés, en particulier l'aluminium et le béryllium.This patent (4,589,972) by Martin Marietta offers, like a previous patent from Martin Marietta n ° 4 111 762 to which reference is made in the patent 4,589,972, to improve the solution to these problems in two ways. These two improvements are applicable to anodisable metals, previously anodized, in particular aluminum and beryllium.
Le procédé prévoit un traitement de la surface
par un jet d'oxyde d'aluminium de granulométrie 100 à
200 mesh. Ce traitement initial est destiné à créer une
rugosité de la surface avant anodisation.The method provides a surface treatment
by a jet of aluminum oxide with a
Il est indiqué en haut de la colonne 7 de ce brevet, que la rugosité accrue de la surface traitée a un effet significatif sur l'absorption et la réflectivité de la surface. La réflexion spéculaire est réduite et la dispersion du rayonnement incident grâce au relief créé, multiplie les occasions d'absorption.It is indicated at the top of column 7 of this patent, that the increased roughness of the treated surface has a significant effect on absorption and reflectivity of the surface. Specular reflection is reduced and scattering of incident radiation thanks the relief created, multiplies the absorption opportunities.
L'importance de l'état de la rugosité de la surface a été reconnue par la plupart des professionnels. On citera à titre d'exemple complémentaire, les brevets de Johnson US-A-4 233 107 et US-A-4 361 630 qui est une continuation du premier. Dans le procédé décrit dans ce brevet un substrat est tout d'abord traité au moyen d'un placage réalisé dans un alliage de nickel phosphoreux. La surface ainsi revêtue est alors rendue rugueuse au moyen d'un bain dans une solution aqueuse d'acide nitrique qui réalise une attaque acide du placage déposé. Il est ainsi obtenu une très bonne absorption dans la gamme de 320 à 2140 nanomètresThe importance of the roughness state of the surface has been recognized by most professionals. We will cite as an example additional, Johnson's patents US-A-4,233,107 and US-A-4,361,630 which is a continuation of the first. In the process described in this patent a substrate is first treated with a veneer made in a phosphorous nickel alloy. The surface as well coated is then roughened by means of a bath in an aqueous solution of nitric acid which achieves an acid attack on the deposited plating. It is so obtained a very good absorption in the range from 320 to 2140 nanometers
Ainsi on voit qu'il est généralement connu dans l'art qu'un traitement de rugosification de la surface à traiter, avant (cas du brevet Marietta) ou après (cas du brevet Johnson) revêtement ou autre traitement de surface est susceptible d'améliorer les qualités d'absorption. Toutefois, pour chaque gamme de longueur d'onde à absorber et pour chaque traitement et aussi en fonction du substrat, le traitement de rugosification devra être adapté.So we see that it is generally known in the art that a roughening treatment of the surface to be treated, before (case of the Marietta patent) or after (case Johnson patent) coating or other treatment of surface is likely to improve the qualities absorption. However, for each length range wave to be absorbed and for each treatment and also in function of the substrate, the roughening treatment will have to be adapted.
La présente invention est sous un premier aspect dirigé vers un tel traitement de rugosification.The present invention is under a first aspect directed towards such a roughening treatment.
Sous un second aspect elle est dirigée vers un procédé de dépose d'une couche absorbante de polyaniline, ce dépôt étant effectué de préférence après que la surface ait été rugosifiée préalablement aux opérations de pose de la couche de polyaniline. In a second aspect it is directed towards a method of depositing an absorbent layer of polyaniline, this deposition preferably being carried out after the surface has been roughened beforehand during the laying operations of the polyaniline layer.
L'utilisation de la polyaniline comme absorbant de radiations électromagnétiques est en elle-même connue. On citera à ce sujet les brevets de EPSTEIN et Al n° US-A-5 079 334 et quelques unes de ses continuations notamment n° 5 147 968, 5 294 694 et 5 563 182. Dans ces différents brevets EPSTEIN explique les raisons des qualités absorbantes de la polyaniline et les applications possibles. Le brevet 5 294 694 revendique une méthode d'absorption d'ondes électromagnétiques au moyen d'une composition de polyaniline. Ce brevet envisage explicitement notamment le domaine de l'ultraviolet à l'infrarouge.The use of polyaniline as an absorbent electromagnetic radiation is in itself known. In this regard, mention will be made of the patents of EPSTEIN and Al No. US-A-5,079,334 and some of its continuations in particular n ° 5 147 968, 5 294 694 and 5,563,182. In these various patents EPSTEIN explains the reasons for the absorbent qualities of polyaniline and possible applications. Patent 5,294,694 claims a wave absorption method electromagnetic by means of a composition of polyaniline. This patent explicitly contemplates in particular the field of ultraviolet to infrared.
Ce brevet ne mentionne que très fugitivement les traitements à appliquer aux surfaces à revêtir et la méthode de dépose. Ainsi est-il indiqué colonne 7, lignes 55-63 de l'un quelconque de ces brevets que l'aniline peut être appliqué pratiquement par toute méthode connue. Parmi ces méthodes, il cite la déposition électrochimique sur des substrats conducteurs.This patent only very fleetingly mentions the treatments to be applied to the surfaces to be coated and the removal method. Thus it is indicated column 7, lines 55-63 of any of these patents that aniline can be applied practically by any known method. Among these methods, he cites the electrochemical deposition on substrates conductors.
Des dépôts de films minces sont également envisagés en colonne 8, lignes 5-20.Thin film deposits are also envisaged in column 8, lines 5-20.
La demanderesse a effectué des expérimentations dans lesquelles une polyaniline était utilisée comme revêtement absorbant.The applicant has carried out experiments in which a polyaniline was used as absorbent coating.
Il a été constaté que la polyaniline avait effectivement de bonnes qualités absorbantes, toutefois, la valeur de réflexion totale reste élevée dans l'infrarouge. L'adhérence au substrat n'est pas bonne. La tendance au lamellage de la couche est certaine.Polyaniline was found to have actually good absorbent qualities, however, the total reflection value remains high in the infrared. Adhesion to the substrate is not good. The tendency to laminate the layer is certain.
Ces expérimentations ont montré qu'il existait un besoin pour un dépôt d'une couche de polyaniline absorbante de radiations électromagnétiques dans les gammes de l'ultraviolet à l'infrarouge qui adhère bien au substrat et ne présente pas de pic de réflexion dans la gamme infrarouge.These experiments showed that there was a need for deposition of a polyaniline layer absorbing electromagnetic radiation in ranges from ultraviolet to infrared which adheres well to the substrate and has no reflection peak in the infrared range.
A toutes ces fins l'invention est relative à un procédé de préparation de la surface d'un substrat destiné à recevoir une couche de polyaniline, absorbante dans la gamme de l'ultraviolet à l'infrarouge, caractérisé en ce que la surface du substrat est rugosifiée avant que ne soit entamée les étapes de dépôt de la couche de polyaniline.For all these purposes, the invention relates to a process for preparing the surface of a substrate intended to receive a polyaniline layer, absorbent in the ultraviolet to infrared, characterized in that the surface of the substrate is roughened before the stages of deposition of the polyaniline layer.
Il a été constaté que les meilleurs résultats du point de vue de l'absorption était obtenus lorsque la valeur de rugosité de la surface du substrat est comprise entre 10 et 30 µm. Il s'agit là de la valeur quadratique moyenne des écarts entre les points les plus en pointe de la surface et les points les plus profonds corrigé des ondulations lentes de la surface connue sous le nom de rugosité Ra. Avec cette rugosité initiale du substrat on obtient un bon effet de diffusion, en particulier dans la gamme de 0,25 à 16 µm. En outre, cette diffusion favorise l'absorption.It has been found that the best results from the absorption point of view was obtained when the roughness value of the substrate surface is between 10 and 30 µm. This is the value quadratic mean of the differences between the points the farther from the surface and the more points deep corrected for slow surface ripples known as the roughness Ra. With this roughness initial of the substrate we get a good effect of scattering, especially in the range of 0.25 to 16 µm. In addition, this diffusion promotes absorption.
Cette valeur de Ra peut être obtenue par exemple sur un substrat de titane par sablage avec un abrasif. Cette opération peut être réalisée avec du corindon de granulométrie comprise entre 30 et 120 mesh.This Ra value can be obtained by example on a titanium substrate by sandblasting with a abrasive. This can be done with corundum with a particle size between 30 and 120 mesh.
Dans un mode de réalisation, le sablage a été
réalisé avec un tel corindon, sous une pression de 6
bars à une distance de la surface à traiter d'environ
20 cm. Un double passage a été effectué avec un taux
de recouvrement de 100 %.In one embodiment, the sandblasting was
made with such a corundum, under a pressure of 6
bars at a distance from the surface to be treated of approximately
20 cm. A double pass was made with a
Cette phase de préparation initiale du substrat est nécessaire pour diminuer, voire, supprimer le pic spéculaire de réflexion dans l'infrarouge. Le dépôt d'aniline, selon un second aspect de l'invention peut être effectué après cette phase préparatoire relative à l'obtention de la rugosité de la surface du substrat. Il peut aussi ne pas être effectué si la valeur d'absorption ou de réflexion spéculaire obtenu sans ce traitement préalable de rugosification sont jugées suffisantes.This initial substrate preparation phase is necessary to decrease or even remove the peak specular reflection in the infrared. The deposit aniline, according to a second aspect of the invention can be carried out after this preparatory phase relating to obtaining the roughness of the substrate surface. It may also not be performed if the value specular absorption or reflection obtained without this roughening treatment are judged sufficient.
Selon ce second aspect, l'invention est relative à un procédé de dépôt d'une couche de polyaniline sur un substrat de titane ou d'un alliage de titane, caractérisé en ce que la gamme opératoire du dépôt comprend successivement :
- un décapage fluonitrique ;
- un traitement de conversion chimique ;
- une hydrolyse ; et
- un dépôt de polyaniline par électropolymérisation.
- fluonitric stripping;
- chemical conversion treatment;
- hydrolysis; and
- deposition of polyaniline by electropolymerization.
Si le substrat n'est pas dans un état parfait de propreté, il est prudent de prévoir une étape préliminaire de nettoyage (dégraissage alcalin, solvant ou mécanique).If the substrate is not in perfect condition of cleanliness, it is prudent to plan a stage preliminary cleaning (alkaline degreasing, solvent or mechanical).
Un exemple de réalisation d'un revêtement de polyaniline sur un substrat et une description succincte des résultats optiques obtenus sera maintenant en regard des dessins annexés dans lesquels :An example of realization of a coating of polyaniline on a substrate and a description succinct optical results obtained will be now next to the attached drawings in which :
La figure 1 comprend les figures 1a, 1b, 1c, ces figures représentent des vues au microscope électronique à balayage d'une surface d'alliage TA6V revêtue d'un dépôt de polyaniline sous une inclinaison de 30° ;
- figure 1a : avec un grossissement de 40
- figure 1b : avec un grossissement de 400
- figure 1c : avec un grossissement de 2000
- figure 1a: with a magnification of 40
- figure 1b: with a magnification of 400
- figure 1c: with 2000 magnification
La figure 2 comprend les figures 2a, 2b, 2c. Ces figures représentent des vues au microscope électronique à balayage d'une surface d'alliage TA6V revêtue d'un dépôt de polyaniline, la surface ayant été préalablement rugosifié par sablage. (Inclinaison 30°) ;
- figure 2a : avec un grossissement de 40
- figure 2b : avec un grossissement de 400
- figure 2c : avec un grossissement de 2000
- figure 2a: with a magnification of 40
- figure 2b: with a magnification of 400
- figure 2c: with 2000 magnification
Les figures 3 et 4 représentent une courbe donnent une valeur de coefficient de réflexion totale pour des longueurs d'onde allant de 0,25 à 2,5 µm ;
- figure 3 pour de la polyaniline déposée selon le procédé de l'invention sans sablage préalable ;
- figure 4 avec sablage préalable.
- Figure 3 for polyaniline deposited according to the method of the invention without prior sanding;
- Figure 4 with prior sanding.
Un dépôt de polyaniline a été réalisé sur des alliages de titane du type TA6V, les différentes étapes de la gamme opératoire sont les suivantes :Polyaniline deposition was carried out on TA6V type titanium alloys, the different stages of the operating range are as follows:
- Tripolyphosphate de sodium Na5P3O10 : 40 g/lSodium tripolyphosphate Na 5 P 3 O 10 : 40 g / l
- Tétraborate de sodium Na2B4O7, 10 H2O : 40 g/lSodium tetraborate Na 2 B 4 O 7 , 10 H 2 O: 40 g / l
- Tensioactif ref. 631 : 10 ml/lSurfactant ref. 631: 10 ml / l
- Soude NaOH : pH=9NaOH soda: pH = 9
- Température de fonctionnement : 60°COperating temperature: 60 ° C
- Durée : 10 minutesDuration: 10 minutes
- Acide nitrique 41° Bé HNO3 : 141 mlNitric acid 41 ° Be HNO 3 : 141 ml
- Acide fluorhydrique (48%) HF : 50 mlHydrofluoric acid (48%) HF: 50 ml
- Additif F 68 : 1 gAdditive F 68: 1 g
- TA6V (métal) 1,5 gTA6V (metal) 1.5 g
- Eau distillée qsp : 11.Distilled water qs: 11.
- Température de fonctionnement : 20°COperating temperature: 20 ° C
- Durée : 2 mns 15sDuration: 2 mins 15s
- Bifluorure de sodium NaFHF : 13 g/1Sodium bifluoride NaFHF: 13 g / 1
- Température de fonctionnement : 20°COperating temperature: 20 ° C
- Durée 1 min 45sDuration 1 min 45s
- eau déminéraliséeDemineralized Water
- Température de fonctionnement : 90°COperating temperature: 90 ° C
-
Durée 15 minutes
Duration 15 minutes
- Aniline liquide 0,1 mole/litreLiquid aniline 0.1 mole / liter
- Sulfate de sodium Na2SO4, 10 H2O : 0,5 MSodium sulfate Na 2 SO 4 , 10 H 2 O: 0.5 M
- Acide sulfurique H2SO4 qsp pH=1Sulfuric acid H 2 SO 4 qs pH = 1
Les durées, concentrations de produits, et natures de produits qui ont été employées et qui sont citées ci-dessus, peuvent naturellement être modifiées de façon connue dans l'art pour obtenir les mêmes résultats. Les inventeurs n'ont pas expérimenté toutes les gammes de produits utilisables et les durées nécessaires pour les traitements mais ils pensent a priori que par exemple pour le dégraissage alcalin avec les mêmes produits, les proportions ou durées ci-après pourraient être employées. The durations, concentrations of products, and types of products which have been used and which are mentioned above, can of course be modified in a way known in the art to obtain the same results. The inventors have not experienced all ranges of usable products and durations needed for treatments but they think has a priori than for example for alkaline degreasing with the same products, the proportions or durations below could be used.
- Tripolyphosphate de sodium Na5P3O10 : 36 à 44 g/lSodium tripolyphosphate Na 5 P 3 O 10 : 36 to 44 g / l
- Tétraborate de sodium Na2B4O7,10 H2O : 40 g/lSodium tetraborate Na 2 B 4 O 7 , 10 H 2 O: 40 g / l
- Tensioactif ref. 631 : 10 ml/lSurfactant ref. 631: 10 ml / l
- Soude NaOH : pH = 8,5 à 9,5NaOH soda: pH = 8.5 to 9.5
- Température de fonctionnement : 55 à 65°COperating temperature: 55 to 65 ° C
- Durée : 10 à 15 minutesDuration: 10 to 15 minutes
En ce qui concerne le décapage fluonitrique, les proportions d'acide pourraient être augmentées et la durée du bain diminuée, ou encore elles pourraient être diminuées, la durée du bain restant équivalente, mais la température du bain étant augmentée.Regarding the fluonitric stripping, the acid proportions could be increased and the duration of the bath decreased, or they could be reduced, the duration of the bath remaining equivalent, but the temperature of the bath being increased.
Là encore, les durées et proportions pourraient être :Again, the durations and proportions could to be :
- Acide nitrique 41° Bé HNO3 : 100 à 180 mlNitric acid 41 ° Be HNO 3 : 100 to 180 ml
- Acide fluorhydrique (48%) HF : 40 à 60 mlHydrofluoric acid (48%) HF: 40 to 60 ml
- Additif F 68 : 1 gAdditive F 68: 1 g
- TA6V (métal) 1,5 gTA6V (metal) 1.5 g
- Eau distillée qsp : 11.Distilled water qs: 11.
- Température de fonctionnement : 18 à 22°COperating temperature: 18 to 22 ° C
- Durée : 2 à 2,5Duration: 2 to 2.5
Dans le bain d'électropolymérisation, la pièce à traiter, en laboratoire il s'agissait d'éprouvettes, est l'électrode de travail d'une cellule à trois électrodes (contre électrode en acier inoxydable et électrode de référence au calomel saturé (ECS)). L'alliage est polarisé à -0,5 V/ECS pendant 3 min, puis soumis ensuite à un balayage anodique à la vitesse de 10 mV/s jusqu'à ce que la tension imposée atteigne +2 V/ECS. Le balayage est alors stoppé, mais la polarisation maintenue pendant 20 minutes.In the electropolymerization bath, the part to be processed, in the laboratory these were test tubes, is the working electrode of a three cell electrodes (against stainless steel electrode and saturated calomel reference electrode (ECS)). The alloy is polarized at -0.5 V / DHW for 3 min, then then subjected to anodic scanning at the speed of 10 mV / s until the imposed voltage reaches +2 V / DHW. The scanning is then stopped, but the polarization maintained for 20 minutes.
Les tensions indiquées sont mesurées entre l'électrode de référence au calomel et l'électrode de travail.The indicated voltages are measured between the calomel reference electrode and the job.
Après électropolymérisation, les éprouvettes peuvent être étuvées à une température comprise entre 40° et 160° pendant une durée comprise entre 30 min et 2 heures, par exemple 1 heure à 160°C.After electropolymerization, the test pieces can be steamed at a temperature between 40 ° and 160 ° for a period of between 30 min and 2 hours, for example 1 hour at 160 ° C.
Chaque étape de la gamme de préparation a son importance, des essais de polymérisation de polyaniline ont été réalisés après chacune de ces étapes. Il a été mis en évidence :
- qu'après un simple décapage fluonitrique, la polyaniline électropolymérisée n'adhère pas à la surface de l'alliage de titane,
- que le traitement de conversion chimique favorise l'adhérence de la polyaniline, mais la répartition de la couche est hétérogène,
- que le traitement d'hydrolyse est indispensable à la réalisation d'un film adhérent et homogène.
- that after a simple fluonitric pickling, the electropolymerized polyaniline does not adhere to the surface of the titanium alloy,
- that the chemical conversion treatment promotes the adhesion of the polyaniline, but the distribution of the layer is heterogeneous,
- that the hydrolysis treatment is essential for the production of an adherent and homogeneous film.
Le traitement de conversion NaFHF laisse à la surface de l'alliage une faible quantité de fluor que le traitement d'hydrolyse permet de diminuer mais non d'éliminer totalement. Ce traitement d'hydrolyse semble favoriser la vitesse de formation du dépôt de polyaniline. Le temps d'induction est plus court et la quantité déposée au bout d'un temps de maintien donné plus importante.The NaFHF conversion treatment leaves the surface of the alloy a small amount of fluorine than the hydrolysis treatment makes it possible to decrease but not to totally eliminate. This hydrolysis treatment seems favor the speed of formation of the deposit of polyaniline. The induction time is shorter and the quantity deposited after a given holding time more important.
Afin de simplifier la gamme opératoire, des essais complémentaires d'électropolymérisation ont été réalisés sur des éprouvettes en TA6V préalablement anodisées en milieu sulfurique. Il n'a pas été possible de réaliser un film de polymère adhérent.In order to simplify the operating range, additional electropolymerization tests were performed on TA6V test pieces beforehand anodized in sulfuric medium. It was not possible to make an adherent polymer film.
Les essais de caractérisation optique des éprouvettes traitées ont montré de bonnes caractéristiques d'absorption et une faible réflexion spéculaire. Toutefois, il subsistait encore un pic spéculaire pour des longueurs d'onde de 10,6 µm.Optical characterization tests of treated test pieces showed good absorption characteristics and low reflection specular. However, there was still a peak specular for wavelengths of 10.6 µm.
Afin de supprimer ce pic, la rugosité de la surface de l'alliage de titane a été modifiée par sablage.In order to remove this peak, the roughness of the surface of the titanium alloy was changed by sandblasting.
Ce sablage effectué préalablement aux étapes opératoires du dépôt de polyaniline a pour but d'obtenir une rugosité de surface Ra comprise entre 10 et 30 µm.This sanding carried out prior to the steps The aim of polyaniline deposition is to to obtain a surface roughness Ra of between 10 and 30 µm.
Les résultats obtenus en matière d'apparence sont représentés figures 1 et 2.The results obtained in terms of appearance are shown in Figures 1 and 2.
Les coefficients de réflexion hémisphérique font l'objet d'une part, des courbes représentées figures 3 et 4 et, d'autre part, des annexes 1 et 2 qui donnent les valeurs des coefficients de réflexion correspondant aux courbes 3 et 4 respectivement.Hemispheric reflection coefficients on the one hand, the curves represented Figures 3 and 4 and, on the other hand, Annexes 1 and 2 which give the values of the reflection coefficients corresponding to curves 3 and 4 respectively.
Ces courbes correspondent à des longueurs d'onde incidentes comprises entre 0,25 et 2,5 µm.These curves correspond to lengths incident waves between 0.25 and 2.5 µm.
Pour les longueurs d'onde correspondant à
l'infrarouge et à l'infrarouge lointain (jusqu'à
20 µm), on a mesuré des niveaux très faibles, en
particulier, sur les éprouvettes rugosifiées. Par
exemple à 10,6 µm un coefficient de réflexion de 0,03
pour une direction à 25° et de 0,06 pour une direction
de 60°.
Claims (9)
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Application Number | Priority Date | Filing Date | Title |
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FR9901440A FR2789408B1 (en) | 1999-02-08 | 1999-02-08 | METHOD FOR PREPARING SURFACE AND DEPOSITION OF POLYANILINE TO ABSORB LIGHT |
FR9901440 | 1999-02-08 |
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EP1029953A1 true EP1029953A1 (en) | 2000-08-23 |
EP1029953B1 EP1029953B1 (en) | 2003-07-09 |
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EP00400295A Expired - Lifetime EP1029953B1 (en) | 1999-02-08 | 2000-02-03 | Process for surface treatment and for deposition of polyaniline for absorbing light |
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US (1) | US6258242B1 (en) |
EP (1) | EP1029953B1 (en) |
JP (1) | JP2000239894A (en) |
AT (1) | ATE244779T1 (en) |
DE (1) | DE60003734T2 (en) |
DK (1) | DK1029953T3 (en) |
ES (1) | ES2202009T3 (en) |
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WO2003035933A1 (en) * | 2001-10-24 | 2003-05-01 | Fundación Inasmet | Product and method for cleaning titanium surfaces |
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US20050176592A1 (en) * | 2004-02-11 | 2005-08-11 | Tenaris Ag | Method of using intrinsically conductive polymers with inherent lubricating properties, and a composition having an intrinsically conductive polymer, for protecting metal surfaces from galling and corrosion |
JP4628168B2 (en) * | 2005-04-14 | 2011-02-09 | 株式会社ネオス | Method for roughening metal surface |
JP2009249705A (en) * | 2008-04-09 | 2009-10-29 | Japan Carlit Co Ltd:The | Electrode for electrolysis and use thereof |
CN105543924B (en) * | 2015-12-21 | 2017-09-26 | 广东工业大学 | A kind of preparation method of titanium-based conductive hydrogel composite coating material |
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US5294694A (en) * | 1988-05-13 | 1994-03-15 | The Ohio State University Research Foundation | Electromagnetic radiation absorbers and modulators comprising polyaniline |
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US4111762A (en) | 1975-01-31 | 1978-09-05 | Martin Marietta Corporation | Optically black coating and process for forming it |
US4233107A (en) | 1979-04-20 | 1980-11-11 | The United States Of America As Represented By The Secretary Of Commerce | Ultra-black coating due to surface morphology |
US4361630A (en) | 1979-04-20 | 1982-11-30 | The United States Of America As Represented By The Secretary Of The Commerce | Ultra-black coating due to surface morphology |
US4589972A (en) | 1984-07-30 | 1986-05-20 | Martin Marietta Corporation | Optically black coating with improved infrared absorption and process of formation |
-
1999
- 1999-02-08 FR FR9901440A patent/FR2789408B1/en not_active Expired - Fee Related
-
2000
- 2000-02-03 AT AT00400295T patent/ATE244779T1/en not_active IP Right Cessation
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US5294694A (en) * | 1988-05-13 | 1994-03-15 | The Ohio State University Research Foundation | Electromagnetic radiation absorbers and modulators comprising polyaniline |
Non-Patent Citations (3)
Title |
---|
CHEMICAL ABSTRACTS, vol. 117, no. 8, 24 August 1992, Columbus, Ohio, US; abstract no. 78637, GESKIN, V. M.: "Electrodeposition of polyaniline onto non-noble metals. I. Titanium" XP002120668 * |
J. CHIM. PHYS. PHYS.-CHIM. BIOL. (1992), 89(5), 1215-20, 1992 * |
JINGSHUANG Z ET AL: "A NEW PROCESS OF ELECTROPLATING ON TITANIUM AND TITANIUM ALLOY FOR AEROSPACE", TRANSACTIONS OF THE INSTITUTE OF METAL FINISHING, vol. 74, no. PART 01, 1 January 1996 (1996-01-01), pages 25 - 27, XP000551992, ISSN: 0020-2967 * |
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WO2003035933A1 (en) * | 2001-10-24 | 2003-05-01 | Fundación Inasmet | Product and method for cleaning titanium surfaces |
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JP2000239894A (en) | 2000-09-05 |
ES2202009T3 (en) | 2004-04-01 |
DE60003734T2 (en) | 2004-04-15 |
FR2789408B1 (en) | 2001-04-20 |
US6258242B1 (en) | 2001-07-10 |
FR2789408A1 (en) | 2000-08-11 |
DK1029953T3 (en) | 2003-10-27 |
ATE244779T1 (en) | 2003-07-15 |
EP1029953B1 (en) | 2003-07-09 |
DE60003734D1 (en) | 2003-08-14 |
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