Title of Invention

"PASSIVATING MEANS, SURFACE TREATMENT MEANS, SURFACE TREATMENT SPRAY MEANS AND METHOD FOR TREATING METALLIC SURFACES OF WORK PIECES OR CAST MOLDS"

Abstract Passivating by phosphating is a known method. Prior to passivation, there are usually performed various cleaning steps when a surface treatment is to be performed on casting molds or workpieces. According to the invention, it is proposed that the passivating agent comprising an aqueous phosphate solution with metal ions, is additionally provided with a gelatin. Further proposed are surface treatment agents and spray-type surface treatment agents which comprise such a passivating agent as well as non-ionic surface-active agents, lactic acid and a citric acid monohydrate, and optionally a thickening agent. Thereby, preceding cleaning steps can be avoided. Further, there is proposed a corresponding method wherein these surface treatment agents are used. The proposed agents and methods reduce the energy consumption and, in comparison with known agents, allow for a better effect with regard to adhesive strength, promotion of adhesion and thermal shock resistance.
Full Text DESCRIPTION
Passivating agent, surface treatment agent, spray-type surface treatment agent, and method for treating metallic surfaces of workpieces or casting molds
The present invention relates to a passivating agent provided for metallic surfaces of workpieces or casting molds and comprising an aqueous phosphate solution with metal ions, and further to a surface treatment agent and a spray-type surface treatment agent provided for cleaning and passivating metallic surfaces of workpieces or casting molds and comprising such a passivating agent, and to a method for the treatment of metallic surfaces of workpieces or casting molds by use of such a surface treatment agent or such a spray-type surface treatment agent.
Casting molds as used in low-pressure casting, gravity casting, squeeze casting or pressure-die casting, are usually made of hot-work steels because the recrystallization and/or transformation temperatures of these steels are distinctly above those of the molten light metal materials. In the casting processes, in order to obtain smooth surfaces on the cast components to be produced, it is required that the liquid melt, e.g. in the form of a light metal alloy, particularly an aluminum alloy, will not adhere to the surface of the casting mold. For this purpose, the surfaces of the casting molds are provided with release agents or with facings for preventing that the molten metal might stick to the casting mold.
To ensure that the release agents and respectively the facings adhere to the tool surfaces, the latter first have to be cleaned and, in the given case, be passivated.
By the passivating, a non-metallic protective layer is generated on the metallic material in order to slow down the corrosion or to prevent corrosion as largely as
possible. In this regard, passivating by phosphating is of special importance. Phosphating is a widespread method of surface technology wherein, by a chemical reaction between the metallic surface of the workpiece and an aqueous phosphate solution, there is formed a conversion layer of tightly adhering metal phosphates. Phosphating serves for protection from corrosion and generates a diffusion barrier. Additionally, it is thus possible to enhance the adhesion, e.g. in case of subsequently applied layers, and to reduce wear.
For phosphating, use is made both of phosphate baths and of phosphate spray systems. In both cases, it is required to clean the surface of the casting mold or of the workpiece prior to phosphating.
The cleaning process is performed e.g. by use of a high-pressure water jet which, via a rotating nozzle, is directed onto the workpiece at a pressure ranging from 1750 to 3000 bar. Herein, it is disadvantageous that the water contact of the cleaned workpiece will cause corrosion and that organic and inorganic residues from the jet water will remain on the surface. The high pressures will lead to massive wear of the pistons and valves of the water-jet system and will cause high costs.
For this reason, also cleaning processes performed at lower pressures of e.g. 200 bar are known. Although these processes can be carried out with reduced wear, the cleaning effect will deteriorate correspondingly.
Further, it is known to perform the cleaning of pressure die casting molds by uses of granulates which are blasted under pressure onto the workpiece. Herein, use is made of nutshells or glass pearls, for instance. For the cleaning of low-pressure casting molds or gravity casting molds, the granulate used can also be provided in the form of steel, corundum or ceramics. Apart from an additional increase of mechanical wear of the surface, undercut portions of the treated component will be partly inaccessible. This gives rise to dimensional inaccuracies in subsequent casting processes and to impurities on the surface of the mold due to coating with foreign particles from the cycle.
When depositing a facing e.g. with sodium silicate binders subsequent to such a cleaning process, the surfaces, which for the above mentioned reasons have been insufficiently cleaned and passivated, will cause adhesion problems, giving rise to lattice defects on the surface of the facing after deposition. Particularly during a subsequent thermal treatment, a danger exists that the facing will peel off from the treated surface, or in casting molds, during subsequent casting processes, there is a danger of intermetallic welding on the lattice defects so that the mold cannot be accurately separated from the cast workpiece.
Further, when using known cooling/separating agent systems for pressure die casting molds, problems exist in the wetting of insufficiently cleaned surfaces or corroded surfaces of the mold. In the casting process, also this will cause intermetallic connections on the surface of the mold.
To avoid these advantages, it is thus necessary to perform a post-cleaning on the surface of the mold to obtain a metallurgically pure surface.
Known methods for cleaning and passivating are usually carried out in baths or by spraying treatment.
When the treatment is performed in a bath, the casting mold or the workpiece will, after the jet treatment, first be immersed into a pickling bath for removal of organic residues and oxides at temperatures from 40°-90° by means of inorganic acids and suitable surface-active agents. This process is followed by a deep cleaning process in the bath by ultrasonic means, whereupon the workpiece or the casting mold will be immersed into a further bath for rinsing and neutralizing. Subsequently, the workpiece has to be dried and, in a further process step, be activated in the bath, before the phosphating will be performed e.g. by means of zinc phosphate at 40-70°C or manganese phosphate at 70-90°C. Thereafter, the workpiece or the casting mold will be neutralized and dried. A disadvantage of these processes consists in the required long dwelling times in the baths, especially in case of large components such as pressure die casting tools. In
correspondence thereto, large amounts of energy are needed for reaching and maintaining the required temperatures. Also keeping up the clean condition of the bath for maintaining the necessary bath parameters is very bothersome because, between the individual baths, impurities will be generated, making it necessary to remove accumulating residues. Depending on the dimensioning of the components, also the size of the base may have to be adapted.
In spray treatment, the pickling bath is followed by a high-pressure cleaning process and then by rinsing and neutralizing with a suitable spray solution. After the subsequent drying and heating of the component, a spray activation is carried out at increased temperature before the phosphating will be performed by means of a heated spray solution at 40-70°C in case of zinc phosphate, and at 70-90°C in case of manganese phosphate. Also here, this is followed by the further steps of neutralizing and drying the workpiece or the casting mold. Similar to the treatment in a bath, also the spray treatment entails a relatively high energy consumption for reaching the required temperatures, particularly in case of correspondingly high mass ratios, so that the method is economically disadvantageous. Further, there exists a high logistic expenditure in the treatment cycle of the components to be treated.
Further still, the components treated with known passivating agents often suffer from an insufficient thermal shock resistance which is caused particularly by lattice defects in the structure of the passivating layer.
To improve the above situation, DE-34 03 660 Al describes a passivating agent consisting of an aqueous solution of aluminum hydrogen phosphate and organic polymers which under thermal influence will form a film. As organic polymers, use is made herein of acrylic or epoxy resins. When heated, however, these lacquers will lose their organic components. A special disadvantage of this agent resides in that, in case of several casting processes, lattice defects will be caused, entailing the risk of welding connections to a cast component. Further, the thermal shock resistance is still insufficient.
Thus, it is an object of the invention to provide a passivating agent which is adapted to achieve a long durability of the phosphate layer while avoiding lattice defects to the largest possible extent, and, according to a further embodiment of the invention, to provide a surface treatment agent and a spray-type surface treatment agent comprising such a passivating agent, by which the bothersome cleaning process can be simplified. Further, it is an object of the invention to provide a correspondingly simplified method for treatment of surfaces by such agents.
The above object is achieved by a passivating agent which, according to the invention, comprises a gelatin. While the phosphates have the effect, in the known manner, that iron phosphate generated along with the basic material, in combination with the metallic ions of the phosphate system on the free lattice sites and respectively grain boundaries, will form - during the treatment of components or casting molds of steel - a protective layer on the surface that will act as a corrosion protection and adhesive for the layers to be applied, the gelatin in such an agent will act as a dispersion agent and as a potential equalization system and will improve the diffusion barrier in a previously unknown manner. The electrochemical reaction is influenced by the gelatin in such a manner that the phosphating takes place at room temperature. Thereby, the energy demand for phosphating is considerably lowered.
Particularly preferred are gelatins whose redox potential has been set to the effect that the gold number of the gelatin is smaller than 50 µmol Au/g of gelatin. It has become evident that the use of such gelatins makes it possible to reach particularly good results with regard to the adhesion of the passivating layer and the thermal shock resistance of a component treated therewith.
Preferably, the aqueous phosphate solution with the metal ions should be an aqueous orthophosphate solution, wherein the orthophosphates comprise one or a plurality of the compounds zinc phosphate, aluminum phosphate, manganese phosphate, titanium phosphate, calcium phosphate, boron phosphate or iron
phosphate. In phosphating, these compounds have been found to be particularly useful for achieving smooth surfaces.
According to a preferred embodiment, the passivating agent has the following composition: 0.1 % by weight to 5 % by weight of gelatin, 5 % by weight to 50 % by weight of orthophosphates, the rest being water. With such a composition, there is obtained an optimal balance and potential equalization between the individual elements of the system so that, already with small quantities of the individual substances used, particularly good results can be reached in passivation.
The above object of simplifying the presently known cleaning and passivating methods is also achieved by a surface treatment agent comprising such a passivating agent which additionally includes non-ionic surface-active agents, lactic acid and a citric acid monohydrate. When using such a surface treatment agent, preparatory cleaning steps can be completely or at least partly omitted since it is already at room temperature that rust and organic components, such as e.g. grease, dirt, cracked organics etc., will be detached from the surface. The non-ionic surface-active agents included in the surface treatment agent is effective to reduce the surface tension and, in combination with the organic acids, to undermine the impurities on the surface so that these impurities will be detached and respectively dissolved, which allows for an especially good and largely faultless binding of the phosphate system to the metallic surface. The agent can be applied by immersion of the workpiece or the casting mold into a corresponding bath at room temperature.
The surface treatment agent preferably has the following composition:
0.1 to 5 % by weight, preferably 0.41 to 1 % by weight of gelatin
5 to 50 % by weight, preferably 5 to 10 % by weight of orthophosphates
0.5 to 5 % by weight, preferably 0.5 to 2.5 % by weight of lactic acid
0.5 to 5 % by weight, preferably 0.5 to 2.5 % by weight of citric acid
monohydrate
0.1 to 3 % by weight, preferably 0.5 to 2 % by weight of non-ionic surface-active agents the rest being distilled water.
Using this composition, particularly good results have been accomplished with regard to the thermal shock resistance of the coated component. Defects in the lattice are completely eliminated, thus obtaining long-lasting protection from corrosion.
According to a preferred embodiment, the surface treatment agent additionally comprises molybdenum disulfide and/or bismuth. Of particular advantage is an added quantity of 0.01 to 5 % by weight, preferably 0.02 to 0.04 % by weight of molybdenum disulfide and/or 0.01 to 5 % by weight, preferably 0.02 to 0.04 % by weight of bismuth. In passivating, the molybdenum sulfide or the bismuth will be chemically bound in the matrix of the surface. Thereby, the heat resistance and the wear resistance of the casting mold or of the workpiece can be further increased, and the lubricating effect can be improved.
The above described object is also achieved by a spray-type surface treatment agent wherein the surface treatment agent of the invention additionally comprises up to 60 % by weight of a thickening agent. This provides for sprayability, thus obviating the need for a bothersome cleaning of several baths. Contamination of the surface treatment agent as might occur when performing a treatment in baths, are excluded.
The object of providing a method which in comparison to the state of the art is simplified and less expensive, is achieved by a method wherein the workpiece or the casting mold will be immersed into a bath of the inventive surface treatment agent, or the inventive spray-type surface treatment agent will be sprayed onto the surface of the workpiece or the casting mold. Thereby, pre-cleaning and post-cleaning steps can be omitted completely or at least partially so that the throughput time in the production of corrosion-preventing layers can be noticeably reduced. The surfaces treated in this manner can be cleaned to the
point of being absolutely free of residues and be passivated at the same time so that each further surface layer can be applied in a uniform and permanent manner. Onto the thus cleaned and passivated surface layer, one can apply e.g. separating agents, facings or also lacquers. Accordingly, the cleaning and passivation provided by the invention will increase the useful life and the functionality of the thus treated workpieces and molds.
It is advantageous to subsequently heat the workpiece or the mold to 200°C. Starting from this temperature, the inorganic components, metallic ions and mineral elements of the gelatin will be bound as a uniformly distributed nanosystem into the chemical compound which is undergoing a polymerization. The overall system will solidify by polycondensation.
According to an advantageous variant of the method for low-pressure casting molds, it is provided that, after immersion into the surface treatment agent or after spraying the spray-type surface treatment agent, a facing will be applied onto the cleaned and passivated surface of the casting mold. Said facing can be e.g. a sodium or potassium water glass facing which will be applied onto the surface, thereby smoothing the surface and additionally protecting it from thermal stresses.
Preferably, the facing will be applied at a mold temperature of 250°C. The heating required for applying the facing leads to polycondensation of the phosphate system and its organic components. The gelatin of the surface treatment agent will be bound into the chemical compound of the metal with the phosphate system, thus further increasing the adhesive strength. A separate heating of the surface treatment agent will thus not be necessary.
It is evident that the described method wherein a passivating and respectively surface treatment agent or spray-type surface treatment agent is used, makes it possible to omit various method steps and to reduce the energy consumption. Nonetheless, the surfaces of the casting molds or of the treated workpieces will be enhanced with regard to adhesive strength, promotion of adhesion and
thermal shock resistance, thus allowing for a long-term protection from corrosion.
Hereunder, some methods according to the invention wherein use is made of the spray-type surface treatment agent of the invention, will be described with reference to exemplary embodiments for surface treatment of casting molds and workpieces.
Embodiment 1:
In the first embodiment, the workpiece used was a non-precleaned, non-derusted and non-degreased test metal sheet of hot-working steel. For producing a surface treatment agent according to the invention, 1 % of GELITA NOVOTEC(R) gelatin FP200 was dissolved in advance in 14 % of distilled water. For this purpose, the gelatin was first swollen in distilled water, at room temperature, for about twenty minutes and then dissolved at a temperature of 60°C. At this temperature, 0.03 % of molybdenum sulfide was dispersed in the medium. Thereafter, citric acid (0.7 %), lactic acid (0.7 %), phosphoric acid (1.4 %) and an aqueous manganese phosphate solution of the type Brunofix GAM 5624 (36 %) were mixed and introduced into the suspension. The flowability of the spray-type surface treatment agent was set by use of a nearly equivalent portion of a thickening agent - comprising non-ionic tensides - of the type Ardrox 6085 so that a spray-type surface treatment agent in accordance with the invention was produced.
The test metal sheet, while arranged in a vertical position, was fully sprayed with the spray-type surface treatment agent. After a brief exposure time of 10 minutes, the metal sheet was washed by water and dried. Subsequent to cleaning, the metal sheet comprised a continuous black layer consisting of manganese phosphate and molybdenum phosphate. No additional heating of the metal sheet was required. The metal sheet was largely free of lattice defects so that a high corrosion resistance was reached.
Example 2:
Here, a pressure die casting mold was cleaned and passivated by a spray-type surface treatment agent according to the invention. For producing the surface treatment agent, 1 % of GELITA NOVOTEC(R) gelatin FP200 was in advance swollen, at room temperature, in 14 % of distilled water for about 20 minutes and then dissolved at a temperature of 60°C. At this temperature, 0.03 % of molybdenum disulfide was dispersed in the medium. Thereafter, citric acid (0.7 %), lactic acid (0.7 %), phosphoric acid (1.4 %) and an aqueous manganese phosphate solution of the type Brunofix GAM 5624 (36 %) were mixed and introduced into the suspension. The flowability of the spray-type surface treatment agent was set by use of a nearly equivalent portion of thickening agent - again comprising non-ionic tensides - of the type Ardrox 6085 so that a spray-type surface treatment agent in accordance with the invention was produced.
The casting mold was treated at room temperature by spraying the spray-type surface treatment agent onto it. After an exposure time of ten minutes, the cleaning residues were washed off. Again, there formed a uniform layer of manganese phosphate and molybdenum sulfide. Then, in the preheating phase and the balancing phase, the casting mold was tempered in the casting machine for four hours at 200°C. In the process, a continuous layer of manganese phosphate and molybdenum sulfide was generated.
For examining the thermal shock resistance, test metal sheets coated in the same manner and made from a material identical to that of the casting mold were heated for one hour at 800°C and subsequently quenched in water at room temperature. No lattice defects were observed on the phosphate layer. There was proven an extremely good adherence of the layer on the casting mold and, thus, there was reached an extraordinarily good thermal shock resistance.
Embodiment 3:
In this test, a low-pressure die casting mold was treated by a spray-type surface treatment agent according to the invention. For producing this spray-type surface treatment agent, again 1 % of GELITA NOVOTEC(R) gelatin FP200 was in advance dissolved in 14 % of distilled water. For this purpose, the gelatin was again first swollen at room temperature in distilled water for about 20 minutes and then was then dissolved at a temperature of 60°C. Thereafter, citric acid (0.7 %), lactic acid (0.7 %), phosphoric acid (1.4 %) and Brunofix Z 5526 (36 %), an aqueous zinc phosphate solution, were mixed and introduced into the suspension. Also in this example, the flowability of the spray-type surface treatment agent was set by use of the nearly equivalent portion of thickening agent - comprising non-ionic tensides - of the type Ardrox 6085.
The casting mold was treated at room temperature by spraying the spray-type surface treatment agent onto it. After an exposure time of ten minutes, the cleaning residues were washed off. Then, the casting mold was tempered for four hours at 250°C for application of a water-glass-bound facing.
For examining the adhesive effect, a water-glass-bound facing was applied at a casting temperature of 250°C. After 86 casting processes, the surface still presented a coating free of lattice defects. This demonstrates an excellent effect of the inventive spray-type surface treatment agent as an adhesive and a diffusion barrier with very good corrosion resistance. Usually, i.e. without the surface treatment agent of the invention, components subjected to higher temperatures, such as the cylinder spindles, have to be provided with fresh facing substance after every sixth casting process.
Embodiment 4:
In the fourth test series, a squeeze casting mold was sprayed by a spray-type surface treatment agent according to the invention. For producing this cleaning
agent, 1 % of GELITA NOVOTEC(R) gelatin FP200 was in advance dissolved in distilled water. For this purpose, the gelatin was again first swollen at room temperature in distilled water for about twenty minutes and then was then dissolved at a temperature of 60°C. At this temperature, 0.03 % of molybdenum disulfide was dispersed in the medium. Thereafter, citric acid (0.7 %), lactic acid (0.7 %), phosphoric acid (1.4 %) and Brunofix GAM 5624 (36 %) were mixed and introduced into the suspension. Again, the flowability of the spray-type surface treatment agent of the invention was set by use of a nearly equivalent portion of thickening agent - comprising non-ionic tensides - of the type Ardrox 6085.
The casting mold was treated at room temperature by spraying the cleaning agent onto it. After an exposure time of ten minutes, the cleaning residues were washed off. Again, there formed a uniform layer of manganese phosphate and molybdenum sulfide. In the preheating phase and the balancing phase, the casting mold was tempered in the casting machine for four hours at 200°C.
For examining the thermal shock resistance, test metal sheets coated in the same manner and made from a material identical to that of the casting mold were heated for one hour at 800°C and subsequently quenched in water at room temperature. No lattice defects were observed on the phosphate layer. There was observed an extremely good adherence of the layer on the casting mold and, thus, an extraordinarily good thermal shock resistance was reached.
In conclusion, it is to be stated that the spray-type surface treatment agent did not cause caking in the casting process, while no need existed to use additional cooling or cooling/separating agents. The method for treatment of the surfaces is considerably facilitated, and the throughput times are correspondingly shortened. Treatment of the casting molds after each casting process is not necessary anymore.
It should be understood that the invention is not restricted to the above described embodiments. Thus, similar effects will be obtained when using
correspondingly formulated surface treatment agents in the cleaning and passivating of the casting molds and workpieces within an immersion bath. It is also possible to perform exclusively a passivation by use of an inventive passivating agent after a preceding cleaning process. Such a surface treatment will lead to an increase of the effect of the metal phosphate layer as an adhesive and a diffusion barrier. This is brought about particularly by the fixed binding of the phosphate system to the metallic surface due to the effect of the gelatin as a dispersing agent and a potential balancing system and due to the occupation of lattice defects.







CLAIMS
1. A passivating agent for metallic surfaces of workpieces or casting molds,
comprising an aqueous phosphate solution with metal ions,
characterized in that
said passivating agent comprises a gelatin.
2. The passivating agent for metallic surfaces of workpieces or casting molds
according to claim 1,
characterized in that
the redox potential of the gelatin is set in such a manner that the gold number of the gelatin is smaller than 50 µmol Au/g of gelatin.
3. The passivating agent for metallic surfaces of workpieces or casting molds
according to claim 1 or 2,
characterized in that
said aqueous phosphate solution with metal ions is an aqueous orthophosphate solution, wherein the orthophosphates comprise one or a plurality of the compounds zinc phosphate, aluminum phosphate, manganese phosphate, titanium phosphate, calcium phosphate, boron phosphate or iron phosphate.
4. The passivating agent for metallic surfaces of workpieces or casting molds
according to any one of the preceding claims,
characterized in that
said passivating agent has the following composition:
- 0.1 % by weight to 5 % by weight of gelatin,
- 5 % by weight to 50 % by weight of orthophosphates,
- the rest being water.
5. A surface treatment agent for cleaning and passivating metallic surfaces of
workpieces or casting molds, comprising a passivating agent according to
any one of claims 1 to 4, wherein said surface treatment agent further comprises non-ionic surface-active agents, lactic acid and a citric acid monohydrate.
6. The surface treatment agent for cleaning and passivating metallic surfaces
of workpieces or casting molds according to claim 5,
characterized in that
said surface treatment agent comprises the following composition:
- 0.1 to 5 % by weight, preferably 0.41 to 1 % by weight of gelatin
- 5 to 50 % by weight, preferably 5 to 10 % by weight of orthophosphates
- 0.5 to 5 % by weight, preferably 0.5 to 2.5 % by weight of lactic acid
- 0.5 to 5 % by weight, preferably 0.5 to 2.5 % by weight of citric acid monohydrate
- 0.1 to 3 % by weight, preferably 0.5 to 2 % by weight of non-ionic surface-active agents
- the rest being distilled water.
7. The surface treatment agent for cleaning and passivating metallic surfaces
of workpieces or casting molds according to claim 5 or 6,
characterized in that
said surface treatment agent further comprises molybdenum disulfide and/or bismuth.
8. The surface treatment agent for cleaning and passivating metallic surfaces
of workpieces or casting molds according to claim 7,
characterized in that
said surface treatment agent further comprises 0.01 to 5 % by weight, preferably 0.02 to 0.04 % by weight of molybdenum disulfide and/or 0.01 to 5 % by weight, preferably 0.02 to 0.04 % by weight of bismuth.
9. A surface treatment agent for cleaning and passivating metallic surfaces of
workpieces or casting molds,
characterized in that
said surface treatment agent comprises the surface treatment agent according to any one of claims 5 to 8 and up to 60 % by weight of a thickening agent.
10. A method for treatment of metallic surfaces of workpieces or casting molds,
characterized in that
the workpiece or the casting mold is immersed into a bath of the surface treatment agent according to any one of claims 5 to 8 or the spray-type surface treatment agent according to claim 8 is sprayed onto the surface of the workpiece or the casting mold.
11. The method for treatment of metallic surfaces of workpieces or casting
molds according to claim 10,
characterized in that
the workpiece or the casting mold is subsequently heated to 200°C.
12. The method for treatment of metallic surfaces of low-pressure casting molds
according to claim 10,
characterized in that,
after immersion into the surface treatment agent or after spraying the spray-type surface treatment agent, a facing is applied onto the cleaned and passivated surface of the casting mold.
13. The method for treatment of metallic surfaces of casting molds according to
claim 12,
characterized in that,
the facing is applied at a temperature of the low-pressure casting mold of 250°C.

Documents:

http://ipindiaonline.gov.in/patentsearch/GrantedSearch/viewdoc.aspx?id=GrPBCHpEM1Ge5eC+DxRp5w==&loc=+mN2fYxnTC4l0fUd8W4CAA==


Patent Number 270384
Indian Patent Application Number 5261/DELNP/2010
PG Journal Number 51/2015
Publication Date 18-Dec-2015
Grant Date 17-Dec-2015
Date of Filing 21-Jul-2010
Name of Patentee KS ALUMINIUM-TECHNOLOGIE GMBH
Applicant Address HAFENSTRASSE 25, 74172 NECKARSULM, GERMANY
Inventors:
# Inventor's Name Inventor's Address
1 MANFRED LAUDENKLOS POMMERNSTRASSE 8, 61137 SCHONECK, GERMANY
2 STEPHAN BEER LINDENWIESE 2, 74751 LEHRENSTEINSFELD, GERMANY
3 MATTHIAS REIHMANN BRUCKNERSTR. 5, 69502 HEMSBACH, GERMANY
PCT International Classification Number C23C 22/74
PCT International Application Number PCT/EP2009/050846
PCT International Filing date 2009-01-26
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 10 2008 006147.6 2008-01-26 Germany