TW201142082A - Process for producing functional layers on the surface of workpieces, a functional layer thus produced and a workpiece - Google Patents

Abstract

The invention relates to a process for producing functional layers, especially antiwear and/or anticorrosion layers, on the surface of workpieces. The object of the invention is to specify options for the production of functional layers on workpiece surfaces, in which a wide variety of different functional layers can be produced simply, flexibly and inexpensively, and no influence of the actual workpiece material is caused. In the process according to the invention, a film-shaped precursor formed with a polymer, in which metallic particles are embedded, is positioned with respect to a surface region of a workpiece which is to be provided with a functional layer, and brought into contact with the surface. Subsequently, the surface is irradiated with a layer beam or electron beam, with simultaneous relative movement of workpiece and layer or electron beam. The irradiation thermally decomposes organic constituents of the precursor and at least partly melts the metal to form the functional layer. At the same time, the thermal decomposition starts before the melting.

Description

201142082 乂 ^ VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a method of manufacturing a functional layer, particularly an anti-wear and/or anti-corrosion layer, on a surface of a workpiece. It is more about the functional layer produced by the method and the workpiece having the functional layer. Substantially the pressed surface or surface area of the metal workpiece has such functional layers to increase the life under the corresponding environment or conditions of use. It is also possible to compensate for the wear caused by the use of the workpiece or the loss of material in some other way. [Prior Art] In general, such functional layers are produced by the application of a heat-treated material. It is formed of a material different from the material of the actual workpiece, and the properties of the workpiece material and the functional layer material are different to achieve different functions. The functional layer is especially useful for reducing wear, improving friction characteristics or providing better protection against corrosion. For example, in an application method carried out by powder metallurgy, powder is applied to a specific workpiece surface, followed by heating until melting. In this way, the energy that causes heating can be applied in different forms. Typically, laser irradiation is used for this purpose. In this case, however, it is difficult to achieve a uniform film layer, especially a fixed film thickness of a homogeneous material within the film volume. It is also impossible to avoid the considerable cost factors caused by powder loss. It is pointed out, for example, in DE 39 36 479 A1 that these disadvantages can be eliminated only in the limited case of applying a powder of a suitable adhesive having a paste-like thick form. 4 201142082 Metal plate elements which can be welded from suitable metal alloys are also known. However, this does not achieve all of the desired functional layer characteristics. Recently, it has begun to use a film layer of a hard material having a suitable metal and a hard material, especially in the form of an organic matrix. These layers should be placed on a specific surface of the workpiece and then sintered in a sizzling furnace; heating first drives the organic components out before sintering, or melts the components present in the film and melting at low temperatures. However, higher temperatures above 900 °C are required for this purpose, but this creates undesirable changes to the structure of the workpiece material because its characteristics are selected for the particular application or pressure on the workpiece. When attempting to fabricate a functional layer using such a film layer and a conventional heat treatment, it was found that in the case of using plasma, in the case of treatment with pda, a combustion reaction occurs and a functional layer cannot be formed. SUMMARY OF THE INVENTION It is therefore an object of the present invention to point out the choice of manufacturing a functional layer on the surface of a workpiece, with the option of making various functional layers simply, elastically and inexpensively without affecting the actual workpiece. material. According to the invention, this object is achieved by a method having the features of claim 1 of the patent application. Patent Application No. 12 is directed to a functional layer manufactured by the method, and Patent Application No. 13 is directed to a workpiece having the functional layer. The superior structure and development of the present invention can be achieved by utilizing the technical features indicated in the scope of the appended claims. According to the invention, the method is: a polymer with metal particles embedded therein

S 5 201142082 The surface contact. The shape of the two-displacement material is placed on the surface area where the functional layer is to be formed and is relatively moved between the electron beam and the electron beam by irradiating the surface with a laser or an electron beam. The radiant heat decomposes the former while at least a large r t to J partially melts the metal and forms a functional layer. The organic component should be decomposed and the main part of the metal particle is mostly produced, under the tooth, and in the process, different temperatures can be utilized. For example, at the temperature (usually between °c and the lion's melting temperature of the 4th genus alloy before the glare, so the thermal decomposition is 6 A, before the start of the glutenization, the thermal decomposition should be at least very substantial. ^ , ° This can be achieved by affecting the temperature increase in the illuminated area: control = two times by, for example, the appropriate forward speed, more specifically, the energy Μ and the irradiation time. The main part = ^ compares the first field to at least the metal to at least materialize the functional precursor. The functional layer can be flattened according to the desired material layer before the invention can be used to drive the normal ambient temperature. The particles in the polymeric matrix are beamed or electrically placed, and the secret system is made by using the temperature of the Ryerson and the temperature above the minimum temperature. The particles of the corpse W are fixed in the polymer, so no grain = 6 201142082 Drop out. Maintaining the desired distribution of particles within the polymeric matrix to enable the formation of a reconstituted functional layer utilizing the desired surface homogeneity in each case and/or the functional layer volume produced in accordance with the present invention. Due to The treatment does not sufficiently ensure that the particles can be applied as a functional layer in a desired distribution, especially in a uniformly distributed manner, and therefore the present invention allows the disadvantages of applying the powder to the welding, even in the case of using a paste, which can be avoided by laser irradiation. Such a film layer can be manufactured by a film casting process. The film can be adjusted to a limited extent during the process of placing the film in contact with a surface on the surface of the workpiece where the functional layer is to be formed. For example, a functional layer can be used for A convex curvature or a concave curvature surface with a minimum radius. It can be provided for different shapes and geometric features. The film used can have a suitable thickness and a fixed thickness in area. The thickness range should be between 〇. 〇1 mm up to 10 mm. However, before the precursor is brought into contact with the surface of a particular workpiece, the precursor can also be transformed into a shape that conforms to the surface profile of the workpiece to be coated, followed by curing or polymerization to precursor It is fixed to a shape conforming to the contour of the surface of the workpiece. In this case, a suitable polymer or polymer precursor can be used. The reaction can be carried out by irradiation with a suitable electromagnetic radiation such as UV light. However, the shaping can also be carried out by casting a suitable viscous resin into the mold and curing therein. In this case, the metal particles and the selectivity The extra hard material particles are dispersed in the resin. However, the precursor prepared in this way additionally contains a polymer. The organic component is only thermally decomposed during the irradiation process. Therefore, the pretreatment of the metal particles should not be performed. sintering.

S 7 201142082 In addition to the metal particles, at least one hard material having a specific form is also optionally present in the precursor Yin, especially in the manufacture of an anti-wear layer. The hard material particles may also have a metal shell or be bonded to the metal particles. In this case, the hard material generally has at least a higher hardness than the workpiece material. This can improve the anti-wear properties. Hard materials should have a hardness of at least 1000 HV. Advantageously, it should also have better stability or stability against corrosion. In the present invention, a precursor preferably having metal iron, steel, sho, chin, crane, diamond or nickel can be used. It is of course also possible to have alloys of such metals. The hard material used may be a known carbide, stony compound or nitride. However, an oxide having a hard material property is also suitable for this purpose. A combination of such compounds such as carbonitride may also be used as the hard material in the present invention. In addition, granular diamonds can also be used as the hard material. In the evening, the genus, hard material and/or polymer composition can be tailored to each other. The 4 inch I, however, should not exceed the ratio of organic matter = Berry: °, °, 'ratio should be sufficient to achieve the function of the hard material particles in the metal to the functional layer. The organic component used in the precursor may be an organic binder and a plasticizer. Therefore, the two components of C should be thermally decomposed at a temperature lower than 400 ° C. There is a polysulfonate such as coffee, vinegar, polyacrylic acid vinegar, or a copolymer thereof such as polyepoxide, polyethyl bromide, polyfluorene or polyethylene. In particular, fine hydrocarbons, especially those of the group of polyacrylic acid vinegar, can be used to embed solid 8 201142082 particles in a matrix and bond them to the precursor. The polymer that can be used should have good solubility to the solvent and can be used together with other additives such as dispersants. The polymer of the viscous granular solid should be used as a suspension with appropriate viscosity and sufficient stability and should be thermally decomposable without residue. This can be achieved by polydeacetal, polyacrylate or polydecyl acrylate which will depolymerize so that the liberated monomer can then be burned or evaporated. The use of a polymer as a binder improves the life and handling of the precursor in an immature state. Cracking during the drying process can be avoided. Suitable plasticizers are, for example, phthalic acid esters (for example, phenyl phthalate), gums, waxes, gelatin, dextrin, gum arabic, oils, especially paraffin oils, or other polymers such as polyolefin esters. Especially polyethylene. The use of one or more plasticizers reduces the glass transition temperature of the polymer binder and improves the flexibility of the precursor. The plasticizer penetrates into the mesh structure of the polymeric binder thereby reducing the viscosity. The fracture strength, the deformation ability and the ductility can be favorably affected by appropriately selecting the polymer and the plasticizer and the specific ratio present. At the above temperature for the polymer, the plasticizer should also be pyrolyzed without residue. At least one polymer present in the precursor should be capable of effectively absorbing the particular laser radiation used or comprising a correspondingly preferred preferred absorbing additive. Prior to irradiation, the precursor may advantageously be attached to the surface of the workpiece by means of an adhesive promoter such as a pressure sensitive adhesive or a hot melt adhesive. In this manner, the corresponding surface of the precursor may be coated with an adhesive promoter. In order to correspondingly fix the precursor to the surface of the material, the polymer or organic component present in the precursor may also be partially dissolved by a suitable solvent that wets the surface. It

After S 9 1 1201142082, the precursor prepared in this way can be placed on the surface of the workpiece. After the removal of the / Valley sword, the material can be bonded to the material (cohesive bond; material lock ( Material-locking)). In the present invention, more than one precursor can also be used to make a functional layer. In this case, at least two precursors may form a plurality of layers. In this case, the precursors are bonded to each other by means of an adhesive accelerator. However, multiple layers of precursors can also be used in the present invention. This can handle precursors with different concentrations/compositions. In this way, different particles can be embedded in a polymer, maintained in different proportions in the precursors used thereby, or contain different particle sizes. In this form, a compensation layer can be formed on the surface of the workpiece, followed by a true functional layer formed thereon. By virtue of the following facts, it is preferable to compensate for the different thermal expansion coefficients of the mold material and the functional layer material, which can improve the adhesion of the functional layer. However, the compensation layer may also have a barrier function. The chemical reaction or diffusion between the components of the real functional layer and the workpiece material may be avoided. The thickness of the compensation layer may vary depending on the structure of the film. ^ Precursor or multiple materials bonded to each other as a film layer before the bond bond = several layers Yes. In the case of a cut, it is also possible to use a functional layer that can be fabricated in the case of a plurality of precursors. In this case, the surface directly on the surface of the workpiece may be present, for example, in at least a region with a surface precursor of another precursor. The area of the other precursor may be smaller than directly on the surface of the workpiece. The product was not completely covered. For example, a functional surface or other pattern can be formed on the functional layer. This may facilitate, for example, a wide pattern of the roller-shaped surface of the mold. 201142082 However, in this mold, it is also possible to obtain different specific regions on a functional layer. In the method according to the invention, the precursors used can also be separately shaped. This can also advantageously be achieved by the same energy beam that is also used for thermoforming of the functional layer. To crop the contour, the contoured plaque can then be moved with a higher advancement speed and/or with a higher energy density to move the focused plaque along the contour to be cropped. After cutting, the portion of the precursor that is not used to form the functional layer can be removed. These removed precursors can then be used to make another functional layer or sent for recycling, which can reduce costs. At least for the purpose of thermally decomposing the organic component, the precursor can be illuminated in such a way that the focused plaque is not in the plane of the focus point (i.e., the energy beam is unfocused). The source of illumination used may preferably be a Nd-YAG laser, a diode laser or a fiber laser. The method according to the invention can be used to make a wide variety of different functional layers on workpieces made from different materials. The invention can be used to make new work or to repair both. The functional layer can be produced with a high remanufacturability in a manner that greatly reduces the loss of expensive raw materials, especially hard materials. Partial and extremely controlled heating and temperature increase can be achieved during the heat treatment with the energy beam to be used. Especially on workpiece materials, a small increase in temperature of such materials avoids undesired thermal effects on the material compared to conventional methods, and more particularly, no structural transformation and no change in lattice structure. In addition, the requirements for the powdered metal or hard material used can be reduced. This will first be related to the matching between each other, especially the chemical reactivity, and then it will be closed.

S 11 201142082 = The surface of the piece and then at least partially stunned, the requirements of the foot. The fluidity of the present invention will be described in detail by way of example. If only the powder is supplied to the heat application, the fluidity is a must. [Embodiment] The thin St casting process of Example 1 is used to manufacture (4) a fixed thickness 5.5 face 59 酉曰' and as plasticizing Agent of propylene carbonate. Also has: a sintered carbonized crane of a hard material element (which may be a particle size of Fan Yichuan: a commercially available product of 63 μηι to 180 μηι), and a mass% of nickel as a metal binder Alloy (3 ft% of Shi Xi, 3 mass % of boron, and nickel remaining). M is a kind of sintered tantalum carbide, in which each wc hard material particle is coated with single tungsten carbide (single _wc) Thin layer. This layer generally avoids the decomposition of hard material particles during the introduction of heat. A strip having a width of 22 mm and a length of 65 mm is cut from the film A1. A film having a still strong but flexible deformation is placed. The surface of the workpiece was then irradiated with a Nd-YAG laser source with a maximum power of 3 kW. The laser source was operated continuously (cw mode) at a power of 7 〇〇 W. 2000 mm/min on the surface of the film Ai The forward speed moves the focused plaque. Once the organic component is thermally decomposed and removed from the precursor, it will dissolve the nickel-based alloy. During the irradiation, argon gas is supplied as a protective carcass. The layer system is only embedded in the hard material particles are 12 201142082 The nickel-based alloy matrix is formed. The mass ratio is approximately equal to the initial ratio minus the 2% by mass organic component removed by thermal decomposition. In this way, the workpiece consisting of low-alloy stainless steel such as St 35 will have merits. Layers. The functional layers produced on the surface of the workpiece in this manner are shown in micrographs 1 to 3. 'Example 2 As described in Example 1, 'the conventional film casting process is used to make a fixed thickness of 2.0 mm. Film A2 is used as a precursor. In film A2, there are 59% by mass of hard material particles, 39% by mass of metal particles, and 2% by mass of organic components. The inner hard material particle mixture contains: 80% by mass of sintered carbonized crane (Macroline) It may have a particle diameter ranging from 63 μm to 18 μm. In addition, it has a single-WC of 20 mass/〇 (DM 300 type, which is a commercially available product from HC Starck GmbH and has 3,1 μm FSSS value (Fisher Sub-Sieve Sizer). A strip of 100 mm in length and 346 mm in length was cut from the film A2. Dreams of water-soluble adhesion promoter (acry-smelling product Acrysol ASE 60 from Rohm-Haas) Will still have a strong green However, the flexible deformable film A2 is applied to the outer surface of a low alloy non-town steel pipe (for example, St 35). The stainless steel pipe whose surface has been previously sandblasted has an outer diameter of 11 〇 and a length of 100 mm. The end of the film A2 which is flushed straight out of the stainless steel tube. The outer diameter of the steel tube which has been bonded to the green film A2 by the material lock is clamped in the workpiece chuck (drill chuck), and Spin at 5/min

13 S 201142082 ί 接 ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ During the irradiation, the tube is coated with f U-type operating laser. On the rotating stainless steel 2 table (4) field, the moving force of the toilet dirty/min is moved to perform the movement of the focus plaque on the (ring) _ after the mother # is shifted by a spiral force or spiral movement. The film A2 is formed into a ring shape or a rear surface, and the film is stunned. Nitrogen is used as a protection = the anti-wear layer made by the method of the mountain is formed only by a nickel-based alloy matrix in which the hard material particles are in the second knives. The quality in the anti-wear layer is greater than the ratio of the starting material used minus the proportion of organic components removed during thermal decomposition. Example 3 As described in Example 1, the conventional film casting method was used to manufacture two films A3 and B3 each having a fixed thickness of 1.0 mm as a precursor. As in the case of Example 1, the first film A3 contained 98% by mass of cemented tungsten carbide (MTC Macroline) and 2% by mass of an organic component. The second film B3 contains 97% by mass of a nickel-based alloy (containing 3 质/〇 of yttrium, 35% by mass of boron as an alloy element, and a residual ratio of nickel) and 3 masses. /〇 The organic component (equivalent to the ingredients in the examples). Two strips having a width of 100 mm and an A3 length of 314 mm and a B3 length of 308 mm were cut from the films A3 and B3. The flexible deformed film A3 green strip was fixed on the corresponding surface of the inner surface of the steel pipe by means of a water-soluble adhesion promoter Acrysol ASE 60 in a manner of 201142082 which is annularly adjacent to the inner wall of the low-alloy stainless steel tube. The film A3 uses the same adhesive adjacent to the entire area; promotes ft sandblasting of the steel pipe. The strips are fixed at the end of each of the adjacent regions of the B3, and are all flush with the steel pipe at the end points. 〃 ^A3 strip On the surface, the two strips of stainless steel prepared in this way can be stored at a speed of 5 -, which is the same as the reference, irradiated with a laser beam from the surface as shown in Example 2. As in Example 2, the inward surface of the layer structure formed by the surface structure of the layer structure moves. The age of the film B3 is lost, and the film Λ3 matrix formed by the focused plaque of the laser beam is substantially broken. After the tungsten carbide is sintered, these operations are carried out. The organic component of the gas is thermally decomposed and removed, and the anti-wear produced in this manner is used as a shielding gas. The nickel-based alloy base which is aged is distributed by Hard material particles 60% by mass of carbonized cranes and 4 ounces of jins are formed. The obtained functional layer has the nickel-based alloy of Example 4 - Summer %. As described in Example 1, the scaly has a fixed thickness U) The manufacturing method is used for manufacturing each, and in the case of manufacturing a fixed thickness 〇5m 'A404 as a precursor °, the first film A" is included? Third film C4. Example 1

Machine) and 2% by mass of organic octagonal cemented tungsten carbide (MTC/personal beta human component. In the second film B4, 97% by mass of the nickel-based alloy is 3 mass% _, 3% by mass The second is the i-gold component, the remaining ratio is nickel) and 3 brilliant. (four) components in !). The third organic component (corresponding to the example, ^4 contains 97% by mass of a nickel-based alloy (the 201142082 0.5% by mass of boron, the 2.5% of the 2.5% organic having 0.2% by mass of carbon, and the *% by mass of chromium) , the mass of the second, the remaining proportion is nickel) and as an example component. From the two film Α 4, Β 4 and C4 cut 70 sides of the strip. Use water to dissolve = 60 faces and the length of the flexible deformation of the green The Acrys〇1 ASE 60 will be placed on the surface of the workpiece. The workpiece # was previously cleaned with a total of EN-GJN-HV600 (2.1 mass 〇 / ^, 1 produced by the material, the reverse, 23% by mass The composition of the 收 暂 暂 暂 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 And the surface of the county light age strip C4. The long 怿Β 4^ is added to the outward appearance of the film strip Λ4, then using the example 2 and 3 three film strips Β 4, A4 and C 4 (four), nine mining * ,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, Move on the surface of the shot. Right a le, ^^ # In this process 'after the decomposition of the organic component ' 存在 存在 存在 存在 存在 存在 存在 存在 存在 存在 存在 存在 存在 存在 存在 存在 存在 存在 存在 存在 ^ 存在 存在 ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ In this process:: This recording = will contain the hard-shell particles and consist of the film A4 5 = in the film layer. Since the film C4 has a higher definition temperature than the film β4, the nickel alloy of the film C4 It will only partially melt, so in the material of the workpiece material according to the amount of the anti-material phase (4) - compensation layer, its main function is to avoid carbon diffusion. In the heat treatment of the laser beam + _ using argon as Protective gas 201142082. The functional layer produced in this way is formed by a compensation layer of a nickel-based alloy directly on the surface of the workpiece material, on which is a nickel-based alloy matrix in which wc hard material particles are embedded. It is formed by using 60% by mass of cemented tungsten carbide and 40% by mass of a nickel-based alloy. In all cases, a functional layer having a hardness of at least 55 HRC can be obtained. [Simplified Schematic] FIGS. 1 to 3 are according to Example 1. Different magnification micrographs of the functional layers produced. Required component symbol description]

S 17

Claims (1)

201142082 VII. Patent application scope: 1. A method for manufacturing a functional layer on a surface of a workpiece, wherein a film forming precursor formed of a polymer having metal particles is placed on and in contact with a surface region where a functional layer is to be formed, The surface is then illuminated with a laser or electron beam while at the same time having a relative movement between the workpiece and the laser or electron beam, wherein during the irradiation, the organic component of the precursor thermally decomposes and the metal at least partially dissolves To form the functional layer, whereby thermal decomposition begins before the melting. 2. The method of claim 1, wherein the precursor is in the form of a flexible deformable film. 3. The method of claim 1, characterized in that the precursor is shaped to conform to the surface profile of the workpiece to be coated, and then the precursor is cured or polymerized to conform to the shape of the surface contour of the workpiece. To fix the precursor. 4. A method according to any one of the preceding claims, characterized in that a precursor which additionally presents at least one hard material, hard material particles bonded to the metal particles and/or metal material particles having a metal shell is used. 5. The method of any of the preceding claims, wherein a precursor is fixed to the workpiece by a material-locking means by means of an adhesion promoter prior to irradiation with the laser or electron beam. 6. The method of any of the preceding claims, wherein at least two precursors forming a plurality of layers or a plurality of layers are placed on the surface, and a precursor is exposed to the laser toward the outer surface or Electron 18 201142082 The beam is in contact with the surface prior to illumination. 7. The method of claim 6 wherein the plurality of precursors having different concentrations, thicknesses, sizes and/or shapes are used. 8. A method according to any one of the preceding claims, characterized in that the laser or electron beam is used to focus the relatively high abilities in the plaque before the decomposition of the organic component occurs and the metal melts to form the functional layer. Density and/or advancement speed to cut the outer contour of the precursor. 9. The method of any of the preceding claims, wherein only a portion of the surface of the precursor is illuminated by the laser or electron beam to form a predefined edge contour or functional layer or layer to achieve the Forming of the functional layer. 10. The method of any of the preceding claims, wherein the laser or electron beam system is directed to the surface of the precursor at least during thermal decomposition of the organic component such that the focused plaque is located The focus is out of plane. The method of any of the preceding claims, characterized in that at least two precursors forming a plurality of layers and having different concentrations/components are used to form a compensation layer having the precursor directly placed on the surface of the workpiece The functional layer formed by the method of any one of the above claims 1 to 11 is formed. 13. A workpiece having a functional layer as in claim 12 of the patent application. 19