EP1180552B1 - Method for surface treatment of mechanical pieces subjected to wear and corrosion - Google Patents
Method for surface treatment of mechanical pieces subjected to wear and corrosion Download PDFInfo
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- EP1180552B1 EP1180552B1 EP01402028A EP01402028A EP1180552B1 EP 1180552 B1 EP1180552 B1 EP 1180552B1 EP 01402028 A EP01402028 A EP 01402028A EP 01402028 A EP01402028 A EP 01402028A EP 1180552 B1 EP1180552 B1 EP 1180552B1
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- nitriding
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- oxidation
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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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/40—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using liquids, e.g. salt baths, liquid suspensions
- C23C8/42—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using liquids, e.g. salt baths, liquid suspensions only one element being applied
- C23C8/48—Nitriding
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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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/40—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using liquids, e.g. salt baths, liquid suspensions
- C23C8/58—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using liquids, e.g. salt baths, liquid suspensions more than one element being applied in more than one step
Definitions
- the present invention relates to a method of surface treatment of mechanical parts subjected to both wear and corrosion. More particularly, the invention relates to a method of surface treatment of mechanical parts subjected to both wear and corrosion to impart to said parts a high resistance to wear and corrosion and a roughness conducive to lubrication. More specifically, the invention relates to a method of surface treatment of mechanical parts whose lubrication must be controlled accurately, and which must therefore control the roughness in a narrow range.
- the thickness of the oil film on the surface of a part depends a lot on the roughness of its surface: a perfectly polished part may not be wetted by the oil, whereas at the Conversely, a very rough piece will be covered with a film whose thickness will be less than the height of the microreliefs, it will result in high risk of seizure.
- the parts that can be advantageously treated according to the present invention include for example the cylinder rods and the thermal engine valves.
- a cylinder rod the thickness of the oil film on its surface must be perfectly controlled; too weak, the rod-seal contact is no longer lubricated and there is wear; too high, the resulting leakage of lubricant alters the performance of the cylinder.
- the oil film provides both lubrication and dynamic sealing functions in the valve stem / valve guide contact; too polished a piece will provide a thin film of oil and the lubrication will be random, while a high roughness will cause a high oil consumption and a loss of efficiency of the engine.
- Another commonly used solution consists of nitriding the parts and then oxidizing them; these two operations are often followed by a step of impregnating the surface porosity with a product further improving the corrosion resistance.
- These operations are conducted successively, either in a bath of salts as taught for example by French patents FR-A-2 672 059 or FR-A-2,679,258 , either in a gaseous atmosphere as for example the European patent 0217420 .
- polishing-oxidation This increase in roughness has led those skilled in the art to complete these processes with one or more polishing phases that are more or less advanced so that the result is sequences such as nitriding-oxidation-polishing, or even nitriding-oxidation. polishing-oxidation.
- Such methods make it possible to effectively fulfill the lubrication function, but are difficult to apply industrially because they impose a combination of different technologies (thermochemical and mechanical) which makes them both very expensive and of limited use, it is indeed difficult to polishing the roughness on a piece of complex shape.
- the Applicant has demonstrated that it is possible to obtain both a high resistance to wear and corrosion and a roughness conducive to lubrication by conducting the nitriding and oxidation operations in special baths.
- the present invention provides a method of surface treatment of mechanical parts, making it possible to give the said parts a high resistance to wear and corrosion as well as a roughness conducive to lubrication in which consecutively nitriding said piece followed by oxidation of said piece, characterized in that said nitriding is carried out by immersing said piece in a bath of nitriding molten salts free of sulfur species, at a temperature between 500 ° C and 700 ° C, and in that said oxidation is carried out in an aqueous oxidizing solution at a temperature below 200 ° C.
- the process must respect both the consecutive association of nitriding and oxidation, the two operations being conducted in the liquid phase under the conditions specified above.
- the aqueous oxidizing solution additionally contains 0.6 to 1.0% by weight of S 2 O 3 2- thiosulfate ions.
- the immersion time of the parts in the oxidation bath is advantageously between 5 and 45 minutes.
- a part treated by the above process is characterized in that its roughness has a Ra value of less than about 0.5 ⁇ m and that its surface is free of "tables".
- Parallelepiped test pieces measuring 30 x 18 x 8 mm as well as 35 mm diameter rings, both in unalloyed steel with 0.35% carbon and an initial roughness Rmax 0.6 ⁇ m, were treated first. in a bath of nitriding salts containing by mass 19% of cyanate ions, 37% of carbonate ions and 3.5% lithium ions, the rest being sodium and potassium ions. The pieces were immersed for 40 minutes at a temperature of 630 ° C.
- test pieces were characterized on the one hand in roughness and on the other hand in friction tests.
- the roughness measurements made on the parts thus treated are grouped in Table II and compared with those obtained with the conventional methods listed, N1, N2, 0x1 and 0x2 corresponding for N1 to a nitriding according to FR 2,171,993 , N2 at a nitriding according to (TF1), 0x1 at an oxidation according to FR 2 708 941 and 02 to an oxidation according to FR 2,306,268 .
- the morphological parameters of the roughness patterns used to qualify the surface states are: AR (arithmetic mean of length) and R (arithmetic mean of depth).
- the method according to the invention makes it possible to obtain roughness equivalent to that of conventional processes followed by polishing.
- Cylinders of high-alloy steel containing 0.45% carbon, 9% chromium and 3% silicon are treated in a nitriding bath of identical composition to that of Example 1.
- the pieces are immersed for 30 minutes in the bath maintained at a temperature of 590 ° C and then quenched in cold water. Once washed, they are oxidized in the brine described in Example 1 for 10 minutes at 130 ° C. and then again washed with hot water.
- the roughnesses obtained with the standard nitrocarburizing oxidation or oxidized sulfonitrocarburation processes are relatively high because of the poor quality of the surface layers obtained (very porous layers and poorly adhering powdery oxides).
- the Rz is usually of the order of 10 microns and it is often necessary to carry out a polishing operation, or even micro-grinding, to bring the roughness Rz in the vicinity of 2 microns.
- test pieces treated according to the range described in this example have a Rz between 2 and 2.5 microns without it was necessary to resort to polishing or microbilling.
- Rz average of the roughness depths according to the NF ISO 4287 standard of 1997 corrected 1998.
- the nitriding step was carried out either, according to FR 72 05498 at 570 ° C in a salt bath consisting of 37% cyanate ions and 17% carbonate ions, the remainder being alkali K +, Na + and Li + cations, plus 10-15 ppm S 2 - ions, under the same conditions as those of Example 1.
- the oxidation step was conducted either according to FR 9309814 at 475 ° C. in a bath of salts based on 13.1% of carbonate ions, 36.5% of nitrate ions, 11.3% of hydroxide ions and 0.1% of dichromate ions; the remainder being alkaline K +, Na + and Li + cations, either under the conditions described in Examples 1 and 2.
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)
- Chemical Treatment Of Metals (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
- Forging (AREA)
- Cleaning Implements For Floors, Carpets, Furniture, Walls, And The Like (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
Description
La présente invention concerne un procédé de traitement superficiel de pièces mécaniques soumises à la fois à l'usure et à la corrosion. Plus particulièrement, l'invention se rapporte à un procédé de traitement superficiel de pièces mécaniques soumises à la fois à l'usure et à la corrosion permettant de conférer aux dites pièces une résistance élevée à l'usure et à la corrosion ainsi qu'une rugosité propice à la lubrification. Plus précisément encore, l'invention a trait à un procédé de traitement superficiel de pièces mécaniques dont la lubrification doit être contrôlée de façon précise, et dont il faut par conséquent maîtriser la rugosité dans une fourchette étroite.The present invention relates to a method of surface treatment of mechanical parts subjected to both wear and corrosion. More particularly, the invention relates to a method of surface treatment of mechanical parts subjected to both wear and corrosion to impart to said parts a high resistance to wear and corrosion and a roughness conducive to lubrication. More specifically, the invention relates to a method of surface treatment of mechanical parts whose lubrication must be controlled accurately, and which must therefore control the roughness in a narrow range.
Il est bien connu que l'épaisseur du film d'huile à la surface d'une pièce dépend beaucoup de la rugosité de sa surface : une pièce parfaitement polie risquera de ne pas être mouillée par l'huile, alors que, à l'inverse, une pièce très rugueuse sera recouverte d'un film dont l'épaisseur sera inférieure à la hauteur des microreliefs, il en résultera des risques de grippage élevés.It is well known that the thickness of the oil film on the surface of a part depends a lot on the roughness of its surface: a perfectly polished part may not be wetted by the oil, whereas at the Conversely, a very rough piece will be covered with a film whose thickness will be less than the height of the microreliefs, it will result in high risk of seizure.
Parmi les pièces qui pourront avantageusement être traitées selon la présente invention, on peut citer par exemple les tiges de vérins et les soupapes de moteurs thermiques. En ce qui concerne une tige de vérin, l'épaisseur du film d'huile à sa surface doit être parfaitement contrôlée ; trop faible, le contact tige-joint n'est plus lubrifié et il y a usure ; trop élevé, la fuite de lubrifiant qui en résulte altère les performances du vérin. En ce qui concerne une soupape de moteur thermique, le film d'huile assure à la fois les fonctions de lubrification et d'étanchéité dynamique dans le contact queue de soupape / guide de soupape ; une pièce trop polie fournira un film d'huile de faible épaisseur et la lubrification sera aléatoire, tandis qu'une rugosité élevée entraînera une consommation d'huile élevée et une perte de rendement du moteur.Among the parts that can be advantageously treated according to the present invention include for example the cylinder rods and the thermal engine valves. With regard to a cylinder rod, the thickness of the oil film on its surface must be perfectly controlled; too weak, the rod-seal contact is no longer lubricated and there is wear; too high, the resulting leakage of lubricant alters the performance of the cylinder. With regard to a thermal engine valve, the oil film provides both lubrication and dynamic sealing functions in the valve stem / valve guide contact; too polished a piece will provide a thin film of oil and the lubrication will be random, while a high roughness will cause a high oil consumption and a loss of efficiency of the engine.
De nombreuse solutions s'offrent à l'homme du métier quand il est en présence d'un organe qui doit à la fois résister à l'usure et à la corrosion. Il est ainsi courant d'utiliser des dépôts épais de «chrome dur» microfissurés. Ceux-ci présentent toutefois des inconvénients. Sur le plan technique, la présence d'une interface entre l'acier-et le chrome peut être à l'origine d'écaillages dramatiques pour les fonctions recherchées, par ailleurs, dans le cas de pièces qui fonctionnent par intermittence comme certains vérins, il y a risque d'élimination du film résiduel de lubrifiant par les intempéries et donc corrosion. Sur le plan économique, ce procédé nécessite un dépôt suivi d'un usinage, ce qui en fait une solution onéreuse. Sur le plan de l'environnement enfin, le chromage est encore très largement réalisé à l'aide de bains contenant du chrome VI qui est un polluant majeur.Many solutions are available to the skilled person when it is in the presence of an organ that must both withstand wear and corrosion. It is thus common to use thick deposits of "hard chrome" microfissured. These, however, have disadvantages. From the technical point of view, the presence of an interface between the steel and the chromium can be at the origin of dramatic flaking for the functions sought, moreover, in the case of parts that operate intermittently as some jacks, there is a risk of the residual film of lubricant being removed by bad weather and thus corrosion. Economically, this process requires a deposit followed by machining, which makes it an expensive solution. Finally, in terms of the environment, chromium plating is still largely achieved using baths containing chromium VI, which is a major pollutant.
Une autre solution couramment utilisée consiste à nitrurer les pièces, puis à les oxyder ; ces deux opérations sont souvent suivies d'une étape d'imprégnation de la porosité superficielle avec un produit améliorant encore la résistance à la corrosion. Ces opérations sont conduites successivement, soit dans un bain de sels comme l'enseignent par exemple les brevets français
Cette opération combinée de nitruration et d'oxydation confère généralement une très bonne résistance à l'usure et à la corrosion, cependant, elle conduit systématiquement à une augmentation de la rugosité de la pièce, l'amenant à un niveau incompatible avec ce qui est requis par les applications relevant du champ de l'invention.This combined operation of nitriding and oxidation generally gives very good resistance to wear and corrosion, however, it systematically leads to an increase in the roughness of the part, bringing it to a level incompatible with what is required by the applications falling within the scope of the invention.
Cette augmentation de rugosité a conduit l'homme du métier à compléter ces procédés par une ou des phases de polissage plus ou moins poussées de sorte que l'on aboutit à des séquences telles que nitruration-oxydation-polissage, ou même nitruration-oxydation-polissage-oxydation. De tels procédés permettent de remplir efficacement la fonction lubrification, mais sont difficiles à appliquer industriellement car ils imposent une combinaison de technologies différentes (thermochimique et mécanique) qui les rend à la fois très onéreux et d'usage limité, il est en effet difficile de maîtriser par polissage la rugosité sur une pièce de forme complexe.This increase in roughness has led those skilled in the art to complete these processes with one or more polishing phases that are more or less advanced so that the result is sequences such as nitriding-oxidation-polishing, or even nitriding-oxidation. polishing-oxidation. Such methods make it possible to effectively fulfill the lubrication function, but are difficult to apply industrially because they impose a combination of different technologies (thermochemical and mechanical) which makes them both very expensive and of limited use, it is indeed difficult to polishing the roughness on a piece of complex shape.
De façon surprenante, la Demanderesse a mis en évidence qu'il était possible d'obtenir à la fois une résistance élevée à l'usure et à la corrosion et une rugosité propice à la lubrification en conduisant les opérations de nitruration et d'oxydation dans des bains particuliers.Surprisingly, the Applicant has demonstrated that it is possible to obtain both a high resistance to wear and corrosion and a roughness conducive to lubrication by conducting the nitriding and oxidation operations in special baths.
Les objets définis plus haut sont satisfaits par la présente invention qui fournit un procédé de traitement superficiel de pièces mécaniques, permettant de conférer aux dites pièces une résistance élevée à l'usure et à la corrosion ainsi qu'une rugosité propice à la lubrification dans lequel on effectue consécutivement une nitruration de ladite pièce suivie d'une oxydation de ladite pièce, caractérisé en ce que ladite nitruration est mise en oeuvre par l'immersion de ladite pièce dans un bain de nitruration de sels fondus exempt d'espèces soufrées, à une température comprise entre 500°C et 700°C, et en ce que ladite oxydation est mise en oeuvre dans une solution aqueuse oxydante à une température inférieure à 200°C.The objects defined above are satisfied by the present invention which provides a method of surface treatment of mechanical parts, making it possible to give the said parts a high resistance to wear and corrosion as well as a roughness conducive to lubrication in which consecutively nitriding said piece followed by oxidation of said piece, characterized in that said nitriding is carried out by immersing said piece in a bath of nitriding molten salts free of sulfur species, at a temperature between 500 ° C and 700 ° C, and in that said oxidation is carried out in an aqueous oxidizing solution at a temperature below 200 ° C.
Pour être conforme à l'invention, le procédé doit respecter à la fois l'association consécutive d'une nitruration et d'une oxydation, les deux opérations étant conduites en phase liquide dans les conditions spécifiées ci-dessus.To be in accordance with the invention, the process must respect both the consecutive association of nitriding and oxidation, the two operations being conducted in the liquid phase under the conditions specified above.
Il ne s'agit cependant pas de l'association consécutive d'un procédé de nitruration particulier et d'un procédé d'oxydation particulier, mais bien d'un ensemble indissociable car, dans le cas du procédé conforme à l'invention, il existe une interaction très forte entre les deux.However, it is not a question of the consecutive association of a particular nitriding process and of a particular oxidation process, but rather of an indissociable set because, in the case of the process according to the invention, it There is a very strong interaction between the two.
Les deux étapes du procédé, à savoir l'étape de nitruration et l'étape d'oxydation, doivent répondre aux conditions suivantes :
- (1) L'opération de nitruration préalable (première étape) doit être exécutée dans un bain fondu exempt d'espèces soufrées.
La température du bain est comprise entre 500°C et 700°C, par exemple à une température comprise entre 590°C et 650°C.
Avantageusement, le bain comporte des cyanates et des carbonates alcalins et a la composition suivante:- Li+ =0,2 à 10%
- Na+ = 10 à 30 %
- K+ = 10à30%
- CO3 2- = 25 à 45 %
- CNO- = 10 à 40%
- CN- < 0,5 %
- en poids
Par exemple, le bain de nitruration de sels fondus contient les ions suivants, en pourcentage en poids :- Li+ = 2,8 à 4,2
- Na+ = 16,0 à 19,0
- K+ = 20,0 à 23,0
- CO3 2- = 38,0 à 43,0
- CNO- = 12,0 à 17,0
Une agitation par de l'air comprimé sera avantageusement prévue.
Avantageusement, la durée d'immersion des pièces est au moins d'environ 10 minutes; elle peut aller jusqu'à plusieurs heures selon les besoins. Habituellement, la durée d'immersion des pièces est comprise entre 30 et 60 minutes. - (2) L'opération d'oxydation (deuxième étape) qui fait suite à la nitruration doit être conduite à une température inférieure à 200°C. La température du bain d'oxydation est de préférence comprise entre 110°C et 160°C. Mieux encore, la température du bain d'oxydation est comprise entre 125°C et 135°C.
- (1) The preliminary nitriding operation (first step) must be carried out in a molten bath free of sulfur species.
The bath temperature is between 500 ° C and 700 ° C, for example at a temperature between 590 ° C and 650 ° C.
Advantageously, the bath comprises alkaline cyanates and carbonates and has the following composition:- Li + = 0.2 to 10%
- Na + = 10 to 30%
- K + = 10 to 30%
- CO 3 2- = 25 to 45%
- NOC - = 10 to 40%
- CN - <0.5%
- in weight
For example, the bath of molten salt nitriding contains the following ions, in percentage by weight:- Li + = 2.8 to 4.2
- Na + = 16.0 to 19.0
- K + = 20.0 to 23.0
- CO 3 2- = 38.0 to 43.0
- NOC - = 12.0 to 17.0
Stirring with compressed air will advantageously be provided.
Advantageously, the immersion time of the pieces is at least about 10 minutes; it can go up to several hours as needed. Usually, the immersion time of the pieces is between 30 and 60 minutes. - (2) The oxidation operation (second step) following nitriding shall be conducted at a temperature below 200 ° C. The temperature of the oxidation bath is preferably between 110 ° C and 160 ° C. More preferably, the temperature of the oxidation bath is between 125 ° C and 135 ° C.
La composition du bain est avantageusement la suivante :
- HO- = 10,0 à 22%
- NO3 - = 1,8 à 11,8%
- NO2 = 0 à 5,3%
- S2O3 2- = 0,1 à 1,9%
- Cl- = 0 à 1,0%
- Na+ = 1,0 à 38%
- HO - = 10.0 to 22%
- NO 3 - = 1.8 to 11.8%
- NO 2 = 0 to 5.3%
- S 2 O 3 2- = 0.1 to 1.9%
- Cl - = 0 to 1.0%
- Na + = 1.0 to 38%
Par exemple, la solution aqueuse oxydante contient les ions suivants, en pourcentage en poids :
- OH-= 17 à 18,5
- NO3 - = 4,0 à 5,5
- NO2 - = 1,0 à 2,5
- Cl- = 0,25 à 0,35
- Na+ = 25 à 29.
- OH - = 17 to 18.5
- NO 3 - = 4.0 to 5.5
- NO 2 - = 1.0 to 2.5
- Cl - = 0.25 to 0.35
- Na + = 25 to 29.
Par exemple, la solution aqueuse oxydante contient en outre 0,6 à 1,0 % en poids d'ions thiosulfate S2O3 2-.For example, the aqueous oxidizing solution additionally contains 0.6 to 1.0% by weight of S 2 O 3 2- thiosulfate ions.
La durée d'immersion des pièces dans le bain d'oxydation est avantageusement comprise entre 5 et 45 minutes.The immersion time of the parts in the oxidation bath is advantageously between 5 and 45 minutes.
Il est remarquable de constater que, après avoir été nitrurées puis oxydées conformément à l'invention, les pièces traitées peuvent ensuite subir une opération d'imprégnation avec la même efficacité que dans l'art antérieur. Bien que la rugosité finale soit nettement plus faible, l'affinité de la couche pour les produits d'imprégnation est au moins aussi élevée. Ce fait surprenant n'est encore pas expliqué scientifiquement à ce jour.It is remarkable to note that, after having been nitrided and then oxidized in accordance with the invention, the treated parts can then undergo an impregnation operation with the same efficiency as in the prior art. Although the final roughness is significantly lower, the affinity of the layer for the impregnating products is at least as high. This surprising fact is still not explained scientifically to date.
Une pièce traitée par le procédé ci-dessus est caractérisée en ce que sa rugosité a une valeur Ra inférieure à environ 0,5 µm et en ce que sa surface est exempte de "tables".A part treated by the above process is characterized in that its roughness has a Ra value of less than about 0.5 μm and that its surface is free of "tables".
L'invention sera à présent décrite plus en détail dans les exemples non limitatifs suivants.The invention will now be described in more detail in the following non-limiting examples.
Des éprouvettes parallélépipédiques de dimensions 30 x 18 x 8 mm ainsi que des bagues de diamètre 35 mm, toutes deux en acier non allié à 0,35 % de carbone et de rugosité initiale Rmax = 0,6 µm, ont été traitées en premier lieu dans un bain de sels de nitruration contenant en masse 19 % d'ions cyanates, 37 % d'ions carbonates et 3,5 % d'ions lithium, le reste étant des ions sodium et potassium. Les pièces ont été immergées pendant 40 minutes à la température de 630°C.Parallelepiped test pieces measuring 30 x 18 x 8 mm as well as 35 mm diameter rings, both in unalloyed steel with 0.35% carbon and an initial roughness Rmax = 0.6 μm, were treated first. in a bath of nitriding salts containing by mass 19% of cyanate ions, 37% of carbonate ions and 3.5% lithium ions, the rest being sodium and potassium ions. The pieces were immersed for 40 minutes at a temperature of 630 ° C.
A leur sortie du bain, les pièces ont été refroidies dans une cuve d'eau puis lavées avant d'être immergées 15 minutes dans une saumure oxydante à 135°C constituée à raison de 85 kg du mélange de sels suivants (Tableau I) en % en poids pour 75 litres d'eau:
Les éprouvettes ont été caractérisées d'une part en rugosité et d'autre part en essais de frottement.The test pieces were characterized on the one hand in roughness and on the other hand in friction tests.
Les mesures de rugosité réalisées sur les pièces ainsi traitées sont regroupées dans le Tableau II et comparées à celles obtenues avec les procédés classiques répertoriés, N1, N2, 0x1 et 0x2 correspondant pour N1 à une nitruration selon
(µm)
(µm)
(µm)
(µm)
(Microns)
(Microns)
(Microns)
(Microns)
On notera que le procédé selon l'invention permet d'obtenir une rugosité équivalente à celle des procédés classiques suivis d'un polissage.It will be noted that the method according to the invention makes it possible to obtain roughness equivalent to that of conventional processes followed by polishing.
Pour les essais de frottement, la bague est appuyée contre la grande face de la plaquette avec une charge régulièrement croissante depuis la valeur initiale de 5 daN et avec une vitesse de glissement constante de 0,55 m/s. La surface frottante de la plaquette est huilée avant l'essai. Les résultats sont regroupés dans le Tableau III.
Des cylindres en acier fortement allié contenant 0,45 % de carbone, 9 % de chrome et 3 % de silicium, sont traités dans un bain de nitruration de composition identique à celui de l'Exemple 1.Cylinders of high-alloy steel containing 0.45% carbon, 9% chromium and 3% silicon are treated in a nitriding bath of identical composition to that of Example 1.
Les pièces sont immergées pendant 30 minutes dans le bain maintenu à une température de 590°C puis trempées dans l'eau froide. Une fois lavées, elles sont oxydées dans la saumure décrite à l'Exemple 1 pendant 10 minutes à 130°C puis à nouveau lavées à l'eau chaude.The pieces are immersed for 30 minutes in the bath maintained at a temperature of 590 ° C and then quenched in cold water. Once washed, they are oxidized in the brine described in Example 1 for 10 minutes at 130 ° C. and then again washed with hot water.
Habituellement, sur ce type d'aciers, les rugosités obtenues avec les procédés standard de nitrocarburation oxydation ou de sulfo-nitrocarburation oxydée sont relativement élevées à cause de la mauvaise qualité des couches superficielles obtenues (couches très poreuses et oxydes pulvérulents peu adhérents). A titre indicatif, le Rz est habituellement de l'ordre de 10 µm et il est souvent nécessaire de réaliser une opération de polissage, voire de microbillage, pour amener la rugosité Rz au voisinage de 2 µm.Usually, on this type of steel, the roughnesses obtained with the standard nitrocarburizing oxidation or oxidized sulfonitrocarburation processes are relatively high because of the poor quality of the surface layers obtained (very porous layers and poorly adhering powdery oxides). As an indication, the Rz is usually of the order of 10 microns and it is often necessary to carry out a polishing operation, or even micro-grinding, to bring the roughness Rz in the vicinity of 2 microns.
Les éprouvettes traitées selon la gamme décrite dans cet exemple, présentent un Rz compris entre 2 et 2,5 µm sans qu'on ai eu besoin de recourir à un polissage ou à un microbillage.The test pieces treated according to the range described in this example, have a Rz between 2 and 2.5 microns without it was necessary to resort to polishing or microbilling.
Nota : Rz = moyenne des profondeurs de rugosité selon la norme NF ISO 4287 de 1997 corrigée 1998.Note: Rz = average of the roughness depths according to the NF ISO 4287 standard of 1997 corrected 1998.
Des essais ont été conduits pour montrer dans quelle mesure le procédé conforme à l'invention est un ensemble indissociable. Dans ce cadre, des éprouvettes cylindriques en acier non allié à 0,35 % en masse de carbone ont été traitées en associant différents procédés de nitruration avec les procédés d'oxydation usuels, y compris celui cité dans les Exemples 1 et 2.Tests have been conducted to show to what extent the process according to the invention is an indissociable whole. In this context, cylindrical specimens of unalloyed steel with 0.35% by weight of carbon were treated by combining different nitriding processes with the usual oxidation processes, including that mentioned in Examples 1 and 2.
L'étape de nitruration a été réalisée soit, selon
L'étape d'oxydation a été conduite soit selon
Les résultats obtenus en rugosité sont regroupés dans le Tableau IV ci-après, sachant que la rugosité de départ pour toutes les éprouvettes est de 0,3 µm Ra.
Claims (14)
- A surface treatment process for mechanical parts, for conferring on said parts a high resistance to wear and corrosion and a roughness propitious to lubrication, in which process nitriding of said part is followed consecutively by oxidation of said part, characterised in that said nitriding is applied by immersing said part in a molten salt nitriding bath free of sulphur-containing species at a temperature from 500°C to 700°C, and in that said oxidation is carried out in an oxidising aqueous solution at a temperature less than 200°C.
- A process according to claim 1, characterised in that the molten salt nitriding bath contains the following ions:Li+ = 0.2 - 10 wt%Na+ = 10 - 30 wt%K+ = 10 - 30 wt%CO3 2- = 25 - 45 wt%CNO- = 10 - 40 wt%with a quantity of CN- ions not greater than 0.5 wt%.
- A process according to claim 2, characterised in that the molten salt nitriding bath contains the following ions:Li+ = 2.8 - 4.2 wit%Na+ = 16.0 - 19.0 wt%K+ = 20.0 - 23.0 wt%CO3 2- = 38.0 - 43.0 wit%CNO- = 12.0 - 17.0 wit%with a quantity of CN- ions not greater than 0.5 wt%.
- A process according to any of claims 1 to 3, characterised in that the mechanical part is immersed in the nitriding bath for at least 10 minutes.
- A process according to claim 4, characterised in that the mechanical part is immersed in the nitriding bath for from 30 minutes to 60 minutes.
- A process according to any of claims 1 to 5, characterised in that the nitriding bath is agitated with compressed air.
- A process according to any of claims 1 to 6, characterised in that the oxidising aqueous solution contains the following ions:OH- = 10.0 - 22.0 wt%NO3 - = 1.8 -11.8 wt%NO2 - = 0 - 5.3 wt%Cl- = 0 - 1.0 wit%Na+ = 1.0 - 38 wt%
- A process according to claim 7, characterised in that the oxidising aqueous solution contains the following ions:OH- 17 - 18.5 wt%NO3 - = 4 . 0 - 5.5 wt%NO2 - = 1.0 - 2.5 wt%Cl- = 0.25 -0.35 wt%Na+ = 25 - 29 wit%
- A process according to any of claims 1 to 8, characterised in that the oxidising aqueous solution further contains 0.1 to 1.9 wt% of thiosulphate ions S2O3 2-.
- A process according to claim 9, characterised in that the oxidising aqueous solution further contains 0.6 to 1.0 wt% of thiosulphate ions S2O3 2-.
- A process according to any of claims 1 to 10, characterised in that the nitriding is carried out at a temperature from 590°C to 650°C.
- A process according to any of claims 1 to 11, characterised in that the oxidation is carried out at a temperature from 110°C to 160°C.
- A process according to claim 12, characterised in that the oxidation is carried out at a temperature from 125°C to 135°C.
- A process according to any of claims 1 to 13, characterised in that the part is immersed in the oxidising bath for from 5 minutes to 45 minutes.
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FR0010633A FR2812888B1 (en) | 2000-08-14 | 2000-08-14 | PROCESS FOR THE SURFACE TREATMENT OF MECHANICAL PARTS SUBJECT TO BOTH WEAR AND CORROSION |
FR0010633 | 2000-08-14 |
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EP1180552A1 EP1180552A1 (en) | 2002-02-20 |
EP1180552B1 true EP1180552B1 (en) | 2011-02-16 |
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EP01402028A Expired - Lifetime EP1180552B1 (en) | 2000-08-14 | 2001-07-26 | Method for surface treatment of mechanical pieces subjected to wear and corrosion |
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US (1) | US6645315B2 (en) |
EP (1) | EP1180552B1 (en) |
JP (1) | JP3809082B2 (en) |
KR (1) | KR100458663B1 (en) |
CN (1) | CN1231611C (en) |
AT (1) | ATE498704T1 (en) |
AU (1) | AU774372B2 (en) |
BR (1) | BR0103350B1 (en) |
CA (1) | CA2355479C (en) |
DE (1) | DE60144039D1 (en) |
ES (1) | ES2356807T3 (en) |
FR (1) | FR2812888B1 (en) |
MX (1) | MXPA01008184A (en) |
MY (1) | MY130608A (en) |
SG (1) | SG98452A1 (en) |
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Families Citing this family (14)
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JP2004003599A (en) * | 2002-03-29 | 2004-01-08 | Denso Corp | Electromagnetic drive device |
KR100679326B1 (en) | 2005-05-26 | 2007-02-07 | 주식회사 삼락열처리 | Heat treatment method |
DE102007060085B4 (en) * | 2007-12-13 | 2012-03-15 | Durferrit Gmbh | Process for producing corrosion-resistant surfaces of nitrided or nitrocarburised steel components and nitrocarburised or nitrided steel components with oxidised surfaces |
FR2942241B1 (en) | 2009-02-18 | 2011-10-21 | Hydromecanique & Frottement | METHOD FOR PROCESSING PIECES FOR KITCHEN UTENSILS |
CN102251211A (en) * | 2010-05-18 | 2011-11-23 | 上海江凯金属表面处理技术有限公司 | Formula of salt bath in salt bath nitridation treatment for stainless steel intake/exhaust valve and treatment method |
CN103276345B (en) * | 2012-12-28 | 2015-07-22 | 上海尚职纳米科技有限公司 | QPQ salt bath composite strengthening and modifying high and new technology applied to automobile component metal surface |
FR3001231B1 (en) * | 2013-01-24 | 2016-05-06 | Renault Sa | THERMOCHEMICAL DIFFUSION PROCESSING METHOD FOR A MECHANICAL ELEMENT, AND CORRESPONDING MECHANICAL ELEMENT |
JP6111126B2 (en) * | 2013-04-12 | 2017-04-05 | パーカー熱処理工業株式会社 | Salt bath soft nitriding method |
FR3030578B1 (en) | 2014-12-23 | 2017-02-10 | Hydromecanique & Frottement | PROCESS FOR SUPERFICIAL TREATMENT OF A STEEL PART BY NITRURATION OR NITROCARBURING, OXIDATION THEN IMPREGNATION |
CN106319438A (en) * | 2015-07-01 | 2017-01-11 | 杭州巨星科技股份有限公司 | Rare earth catalytic permeation QPQ composition and method for manufacturing high-speed cutting tool by QPQ process |
CN108359785B (en) * | 2018-03-19 | 2019-12-17 | 盐城工学院 | Strengthening and toughening treatment method for W6Mo5Cr4V2 high-speed steel broach |
FR3096419B1 (en) * | 2019-05-22 | 2021-04-23 | Hydromecanique & Frottement | Guide member, mechanical system comprising such a guide member, and method of manufacturing such a guide member |
CN113073287A (en) * | 2021-03-19 | 2021-07-06 | 北京航天瑞泰液压技术有限公司 | Method for improving air tightness of inner cylinder barrel of hydro-pneumatic spring |
FR3133394A1 (en) | 2022-03-14 | 2023-09-15 | Hydromecanique Et Frottement | METHOD FOR TREATING AN IRON ALLOY PART TO IMPROVE ITS CORROSION RESISTANCE |
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DE1149035B (en) * | 1959-04-10 | 1963-05-22 | Degussa | Process and device for nitriding metals, in particular iron alloys, in salt baths containing alkali cyanide and alkali cyanate |
BE795015A (en) * | 1972-02-18 | 1973-05-29 | Stephanois Rech Mec | PROCESS FOR TREATING FERROUS METAL PARTS TO INCREASE THEIR RESISTANCE TO WEAR AND SEIZURE |
JPS57152461A (en) * | 1981-03-16 | 1982-09-20 | Parker Netsushiyori Kogyo Kk | Surface treatment of iron member for increasing corrosion and wear resistance |
JPS599166A (en) * | 1982-07-06 | 1984-01-18 | Parker Netsushiyori Kogyo Kk | Surface hardening and nitriding method of steel material |
DE4119820C1 (en) * | 1991-06-15 | 1992-09-03 | Goetz Dr. 5400 Koblenz De Baum | Treatment of iron@ (alloys) on same support - comprises nitriding in molten alkali metal cyanate and quenching in hot aq. salt bath |
FR2679258B1 (en) * | 1991-07-16 | 1993-11-19 | Centre Stephanois Recherc Meca | PROCESS FOR TREATING FERROUS METAL PARTS TO SIMULTANEOUSLY IMPROVE CORROSION RESISTANCE AND FRICTION PROPERTIES THEREOF. |
FR2708623B1 (en) * | 1993-08-06 | 1995-10-20 | Stephanois Rech Mec | Nitriding process for ferrous metal parts, with improved corrosion resistance. |
US5576066A (en) * | 1993-08-10 | 1996-11-19 | Centre Stephanois De Recherches Mecaniques Hydromecanique Et Frottement | Method of improving the wear and corrosion resistance of ferrous metal parts |
JPH0820877A (en) * | 1994-07-07 | 1996-01-23 | Nippon Parkerizing Co Ltd | Production of ferrous metal matrix composite material excellent in corrosion resistance |
FR2731232B1 (en) * | 1995-03-01 | 1997-05-16 | Stephanois Rech | PROCESS FOR TREATING FERROUS SURFACES SUBJECT TO HIGH FRICTION STRESS |
DE69838575T2 (en) * | 1997-11-28 | 2008-07-24 | Maizuru Corp. | Method of surface treatment of iron material and salt bath oven used therefor |
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Also Published As
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KR20020013797A (en) | 2002-02-21 |
ATE498704T1 (en) | 2011-03-15 |
MXPA01008184A (en) | 2004-10-29 |
DE60144039D1 (en) | 2011-03-31 |
BR0103350A (en) | 2002-05-28 |
CN1231611C (en) | 2005-12-14 |
MY130608A (en) | 2007-07-31 |
JP2002060925A (en) | 2002-02-28 |
BR0103350B1 (en) | 2012-02-07 |
FR2812888B1 (en) | 2003-09-05 |
TWI230745B (en) | 2005-04-11 |
US6645315B2 (en) | 2003-11-11 |
KR100458663B1 (en) | 2004-12-03 |
CA2355479C (en) | 2004-06-29 |
US20020038679A1 (en) | 2002-04-04 |
AU5798401A (en) | 2002-02-21 |
SG98452A1 (en) | 2003-09-19 |
JP3809082B2 (en) | 2006-08-16 |
CA2355479A1 (en) | 2002-02-14 |
ES2356807T3 (en) | 2011-04-13 |
FR2812888A1 (en) | 2002-02-15 |
AU774372B2 (en) | 2004-06-24 |
CN1338529A (en) | 2002-03-06 |
EP1180552A1 (en) | 2002-02-20 |
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