BINDER COMPOSITION FOR METAL POWDER INJECTION MOLDING

Abstract

The present invention relates to a binder composition for metal powder injection molding, and more specifically, to a binder composition for metal powder injection molding, which can be promptly debound, facilitates the setting of flow conditions in an injection process, and enables the minimization of poor debinding such as swelling, carbonization of low-molecular-weight binders, and other internal defects, during a debinding process.

The binder composition for metal powder injection molding of the present invention contains 10 to 50 wt % of a high-viscosity polyoxymethylene polymer and 50 to 90 wt % of a low-viscosity polyoxymethylene polymer.

By containing polyoxymethylenes alone, which has been produced with different viscosities, without feeding of other monomers in the polymerization process of polyoxymethylene, the binder composition for metal powder injection molding according to the present invention is more economical through low manufacturing costs compared with a conventional technique in which the rate of decomposition by a gas-phase acid is controlled by viscosity adjustment in a polymerization process, and has excellent injection characteristics and debinding/sintering characteristics compared with a technique in which polyoxymethylene and other polymer resins, such as polyolefins and polyamides, are used together.

Claims

1. A binder composition for metal powder injection molding, comprising 10 to 50 wt % of a high-viscosity polyoxymethylene polymer and 50 to 90 wt % of a low-viscosity polyoxymethylene polymer.

2. The binder composition for metal powder injection molding of claim 1, wherein the high-viscosity polyoxymethylene polymer has a melt flow index of 1 to 10 g/10 min when measured at a temperature of 190° C. and a load of 2.16 kg according to the ASTM D1238 standard, and the low-viscosity polyoxymethylene polymer has a melt flow index of 40 to 300 g/10 min when measured at a temperature of 190° C. and a load of 2.16 kg according to the ASTM D1238 standard.

3. The binder composition for a metal powder injection molding of claim 1, wherein the high-viscosity or low-viscosity polyoxymethylene polymer includes (a) an oxymethylene —(OCH.sub.2)n-group as a repeating unit, and (b) an oxymethylene homopolymer capped at both ends by an ester or ether group or an oxymethylene-based copolymer or terpolymer in which oxyalkylene units having 2 to 10 carbon atoms are randomly inserted into a polymer chain composed of oxymethylene monomer units, and (c) both ends of the polymer are capped by ester or ether groups.

4. A feedstock composition for metal powder injection molding, comprising the binder composition for the metal powder injection molding of claim 1.

5. The feedstock composition for a metal powder injection molding of claim 4, wherein the feedstock composition for the metal powder injection molding comprises: (a) the binder composition for the metal powder injection molding of any one of claims 1 to 3; and (b) a sinterable powdery inorganic material selected from a metal, a metal alloy, a metal carbonyl, a metal oxide, a metal carbide, a metal nitride, and a mixture thereof.

6. The feedstock composition for a metal powder injection molding of claim 5, wherein an average particle size of the powder-type inorganic material is 1 to 20 μm.

7. The feedstock composition for a metal powder injection molding of claim 5, wherein the binder composition for the metal powder injection molding is included in an amount of 20 to 80 volume % and the powder-type inorganic material is included in an amount of 20 to 80 volume %.

8. The feedstock composition for a metal powder injection molding of claim 5, wherein the feedstock composition for the metal powder injection molding further includes an additive selected from a lubricant and a dispersant.

9. A metal injection molding method, comprising: Injection-molding the feedstock composition for the metal powder injection molding of claim 4 to obtain a green part; removing a binder for metal powder injection molding from the green part to obtain a brown part; and sintering the brown part to manufacture a metal product.

10. The metal injection molding method of claim 9, wherein removing of the binder for metal powder injection molding is performed for 0.1 to 30 hours at 50 to 140° C. in an acid atmosphere.

Description

DESCRIPTION OF THE DRAWINGS

[0026] FIG. 1 is an explanatory diagram of a typical metal injection molding process.

MODE FOR INVENTION

[0027] The present invention is to confirm that when polyoxymethylene polymers having different viscosities are mixed within a specific range, although a polyolefin, which is necessarily used for a binder composition for a catalyst debinding method, is not used, a metal injection molding (MIM) process may be successfully conducted without product defects.

[0028] In the present invention, polyoxymethylene produced for each viscosity without adding other monomers in a polymerization process of the polyoxymethylenes is used to apply polyoxymethylenes with high viscosity and low viscosity in preparing a binder composition for a metal powder injection molding. Subsequently, a powder-type inorganic material is added to the prepared binder composition for metal powder injection molding, and then is kneaded to prepare a feedstock composition for metal powder injection molding, and the feedstock composition for metal powder injection molding is injection-molded to obtain a green part, the green part is debound to obtain a brown part, and then the brown part is sintered, finally obtaining a metal product. As a result of evaluating physical properties of the intermediates produced in each step and the final product, kneading characteristics of the feedstock, injection characteristics of the metal workpiece (brown part), debinding characteristics of the metal workpiece (brown part) after the debinding, and sintering characteristics and quality of the metal product after the sintering are all excellent.

[0029] Accordingly, in one aspect, the present invention relates to a binder composition for a metal powder injection molding including 10 to 50 wt % of a high-viscosity polyoxymethylene polymer and 50 to 90 wt % of a low-viscosity polyoxymethylene polymer.

[0030] In the present invention, when the content of the high-viscosity polyoxymethylene polymer is less than 10 wt %, a decomposition rate in acid in a gaseous state may not be controlled, so that poor debinding may occur, and when it exceeds 50 wt %, the viscosity increases and there is a problem that the injection molding process is difficult.

[0031] The high-viscosity polyoxymethylene polymer has a melt flow index of 1 to 10 g/10 min when measured at a temperature of 190° C. and a load of 2.16 kg according to the ASTM D1238 standard, and the low-viscosity polyoxymethylene polymer has a melt flow index of 40 g/10 min to 300 g/10 min when measured at a temperature of 190° C. and a load of 2.16 kg according to the ASTM D1238 standard.

[0032] In the present invention, when the high-viscosity polyoxymethylene polymer has a melt flow index of less than 1 g/10 min, an injection speed should be basically increased to inject small and complex shapes, but since a high molecular weight polymer is used, although an injection pressure is increased, it may be difficult to secure a desired injection speed and inject it into products. Accordingly, there may be injection defects, and since it is not uniformly kneaded with the powder, the products may collapse during the debinding and sintering process.

[0033] In addition, when the high-viscosity polyoxymethylene polymer has a melt flow index of greater than 10 g/10 min, since the polymer that serves as a support as much as desired during the debinding may be decomposed, the products may collapse in the debinding and sintering process.

[0034] When the low-viscosity polyoxymethylene polymer has a melt flow index of less than 40 g/10 min, overall viscosity of the composition prepared by kneading the high-viscosity and low-viscosity polyoxymethylenes may be lowered, resultantly causing difficulties in injecting small and complex-shaped products. In addition, when the melt flow index is greater than 300 g/10 min, since the polymer is a molecular weight polymer, injection process conditions may be easy to establish, but the products may collapse due to rapid decomposition during the debinding.

[0035] In the present invention, the high-viscosity or low-viscosity polyoxymethylene polymer includes (a) an oxymethylene —(OCH.sub.2)n- group as a repeating unit, and (b) an oxymethylene homopolymer capped at both ends by an ester or ether group or an oxymethylene-based copolymer or terpolymer in which oxyalkylene units having 2 to 10 carbon atoms are randomly inserted into a polymer chain composed of oxymethylene monomer units, and (c) both ends of the polymer are capped by ester or ether groups.

[0036] In another aspect, the present invention relates to a feedstock composition for the metal powder injection molding including the binder composition for the metal powder injection molding.

[0037] The feedstock composition for a metal powder injection molding may include: (a) the binder composition for metal powder injection molding; and (b) a sinterable powdery inorganic material selected from a metal, a metal alloy, a metal carbonyl, a metal oxide, a metal carbide, a metal nitride, and a mixture thereof.

[0038] Examples of the metal that may be present in powder form include stainless steel, aluminum, iron, in particular an iron carbonyl powder, chromium, cobalt, copper, nickel, silicon, titanium, and tungsten. Examples of powdered metal alloy include high- or low-alloy steels and metal alloys that include aluminum, iron, titanium, copper, nickel, tungsten, or cobalt as a base. These include powders of already-finished alloys, for example, superalloys such as IN713C, GMR 235, and IN 100, and alloys using main components such as Nd—Fe—B and Sm—Co and that are known from magnet technology and powder mixtures of individual alloy components. Metal powders, metal alloy powders, and metal carbonyl powders, metal oxides, metal carbides, and metal nitrides may also be used for the mixtures.

[0039] Suitable inorganic powders are also oxide ceramic powders such as Al.sub.2O.sub.3, ZrO.sub.2, and Y.sub.2O.sub.3, non-oxide ceramic powders such as SiC and Si.sub.3N.sub.4, and additional composite oxide powders such as NiZnFe.sub.2O.sub.4, and in addition, an inorganic color pigment such as CoAl.sub.2O.sub.4.

[0040] An average particle size of the powder-type inorganic material is desirably 1 to 20 μm.

[0041] The binder composition for the metal powder injection molding may be included in an amount of 20 to 80 volume % and the powder-type inorganic material may be included in an amount of 20 to 80 volume %.

[0042] When the binder composition for the metal powder injection molding is included in an amount of less than 20 volume %, there is a problem with mixing characteristics in the kneading and injection, and when the binder composition for the metal powder injection molding is included in an amount of greater than 80 volume %, there is no value in process characteristics as a metal powder injection molding process.

[0043] In the present invention, the feedstock composition for the metal powder injection molding further includes an additive selected from a lubricant and a dispersant.

[0044] The lubricant is distributed so that the powder-type inorganic material is uniformly and evenly spaced in the binder for metal powder injection molding to improve dimensional stability after sintering, and includes stearic acid, ethylene oxide, diethanolamine, glycerin, sorbitol, behenic acid, and the like, but is not limited thereto.

[0045] The dispersant may be a commonly-used dispersant, stearic acid, zinc-stearate, calcium-stearate, and the like may be exemplified, but is not limited thereto.

[0046] Desirably, the lubricant and the dispersant are included in each amount of 3 volume % or less based on 100 volume % of the feedstock composition for the metal powder injection molding.

[0047] In another aspect, the present invention relates to a metal injection molding method that includes: injection-molding the feedstock composition for the metal powder injection molding to obtain a green part; removing a binder for metal powder injection molding from the green part to obtain a brown part; and sintering the brown part to manufacture a metal product.

[0048] FIG. 1 is an explanatory diagram of a typical metal injection molding process. The metal injection molding method of the present invention is similar to the conventional metal injection molding process of FIG. 1, but is characterized by using the feedstock composition for a metal powder injection molding.

[0049] The injection molding may be performed by conventionally using a screw and a ram injection molding machine, and in general, a mold having a temperature of 160° C. to 250° C. under a pressure of 300 bar to 2000 bar at 30 to 250° C.

[0050] A green part obtained through the injection molding should be treated through a debinding reaction to remove a binder for metal powder injection molding, and in the present invention, the debinding reaction is performed under an acid atmosphere at 50° C. to 150° C. for 0.1 hours to 30 hours. An acid for creating the acid atmosphere may be already be in a gaseous form at room temperature or use an inorganic acid that is evaporable at least at a treatment temperature. Examples of the acid may be hydrohalic acid, nitric acid, and the like, but is not limited thereto.

[0051] After the debinding reaction, the produced brown part is finally made into a metal product through a sintering process, and the sintering process may be performed at 600° C. to 2000° C.

Examples

[0052] Hereinafter, the present invention will be described in more detail through examples. These examples are only for illustrating the present invention, and it will be apparent to those of ordinary skill in the art that the scope of the present invention is not to be construed as being limited by these examples.

Examples 1-24 and Comparative Examples 1-12: Preparation of Feedstock Composition for Metal Powder Injection Molding

[0053] Each feedstock was prepared by kneading each composition of Tables 1 to 4 in a mixer.

TABLE-US-00001 TABLE 1 Example Example Example Example Example Example Comparative Comparative Comparative vol % 1 2 3 4 5 6 Example 1 Example 2 Example 3 Powder-type 55 55 55 55 20 80 55 55 55 inorganic material Polyoxymethylene 20 15 10 4 40 10 30 0 7.5 polymer (MFI: 1) Polyoxymethylene 20 25 30 36 40 10 0 30 7.5 polymer (MFI: 40) Additive 5 5 5 5 0 0 5 5 30 Polyolefin 0 0 0 0 0 0 10 10 0

TABLE-US-00002 TABLE 2 Example Example Example Example Example Example Comparative Comparative Comparative vol % 7 8 9 10 11 12 Example 4 Example 5 Example 6 Powder-type 55 55 55 55 20 80 55 55 55 inorganic material Polyoxymethylene 20 15 10 4 40 10 30 0 7.5 polymer (MFI: 1) Polyoxymethylene 20 25 30 36 40 10 0 30 7.5 polymer (MFI: 300) Additive 5 5 5 5 0 0 5 5 30 Polyolefin 0 0 0 0 0 0 10 10 0

TABLE-US-00003 TABLE 3 Example Example Example Example Example Example Comparative Comparative Comparative vol % 13 14 15 16 17 18 Example 7 Example 8 Example 9 Powder-type 55 55 55 55 20 80 55 55 55 inorganic material Polyoxymethylene 20 15 10 4 40 10 30 0 7.5 polymer (MFI: 10) Polyoxymethylene 20 25 30 36 40 10 0 30 7.5 polymer (MFI: 40) Additive 5 5 5 5 0 0 5 5 30 Polyolefin 0 0 0 0 0 0 10 10 0

TABLE-US-00004 TABLE 4 Example Example Example Example Example Example Comparative Comparative Comparative vol % 19 20 21 22 23 24 Example 10 Example 11 Example 12 Powder-type 55 55 55 55 20 80 55 55 55 inorganic material Polyoxymethylene 20 15 10 4 40 10 30 0 7.5 polymer (MFI: 10) Polyoxymethylene 20 25 30 36 40 10 0 30 7.5 polymer (MFI: 300) Additive 5 5 5 5 0 0 5 5 30 Polyolefin 0 0 0 0 0 0 10 10 0 [0054] Powder-type inorganic material: STS-316L D50 8 μm, Epson Atmix Corp. [0055] Polyoxymethylene polymer (high viscosity): A material developed by Kolon Plastics Inc. (melt flow index=1) [0056] Polyoxymethylene polymer (high viscosity): Kolon Plastic K300 (melt flow index=10) [0057] Polyoxymethylene polymer (low viscosity): Kolon Plastic K900 (melt flow index=40) [0058] Polyoxymethylene polymer (low viscosity): A material developed by Kolon Plastics Inc. (melt flow index=300) [0059] Additive: carnayba wax and stearic acid (mixing ratio=1:1 in a volume ratio) [0060] Polyolefin: UL814, Lotte Chemical Corp.

Experimental Example 1: Manufacturing of Metal Products

[0061] (1) Manufacture of Extruded Body

[0062] The feedstocks according to the examples and the comparative examples were manufactured into extruded bodies (green parts) by fixing extrusion pressure at 1500 bar and molding at 120° C.

[0063] (2) Debinding of Extruded Body

[0064] After adding nitric acid thereto, the extruded bodies (green parts) were debound at 120° C. under an acid atmosphere for 6 hours, preparing metal debound bodies (brown parts).

[0065] (3) Sintering of Metal Workpieces

[0066] The metal debound bodies (brown parts) were sintered at 1250° C. and 2° C./min under an H.sub.2 and N.sub.2 mixed gas atmosphere, preparing metal products having a diameter of about 10×20 mm and a weight of 20 g to 30 g.

Experimental Example 2: Evaluation for Each Process

[0067] The feedstocks according to Examples 1 to 24 and Comparative Examples 1 to 12 and prepared in each step of Experimental Example 1 were evaluated with respect to kneading characteristics, injection characteristics of metal work bodies (brown parts), debinding characteristics of the metal work bodies (brown part) after debinding, and sintering characteristics and quality of metal products after sintering, and the results are shown in Tables 5 to 8.

TABLE-US-00005 TABLE 5 Inspection results Example Example Example Example Example Example Comparative Comparative Comparative by process 1 2 3 4 5 6 Example 1 Example 2 Example 3 Kneading ◯ ◯ ⊚ ⊚ ⊚ Δ X ⊚ X characteristics Injection Δ ◯ ⊚ ⊚ ⊚ Δ Δ Δ X characteristics Debinding ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ Δ X X characteristics Sintering ◯ ⊚ ⊚ ◯ ◯ ⊚ ◯ Δ Δ characteristics Quality inspection ◯ ⊚ ⊚ ◯ ◯ ◯ ◯ ◯ X

TABLE-US-00006 TABLE 6 Inspection results Example Example Example Example Example Example Comparative Comparative Comparative by process 7 8 9 10 11 12 Example 4 Example 5 Example 6 Kneading ◯ ◯ ⊚ ⊚ ⊚ Δ X ⊚ X characteristics Injection ◯ ◯ ⊚ ⊚ ⊚ ◯ Δ Δ X characteristics Debinding ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ ◯ X X characteristics Sintering ◯ ⊚ ⊚ ◯ ◯ ⊚ ◯ Δ Δ characteristics Quality inspection ◯ ⊚ ⊚ ◯ ◯ ◯ ◯ ◯ X

TABLE-US-00007 TABLE 7 Inspection results Example Example Example Example Example Example Comparative Comparative Comparative by process 13 14 15 16 17 18 Example 7 Example 8 Example 9 Kneading ◯ ◯ ⊚ ⊚ ⊚ Δ X ⊚ X characteristics Injection ◯ ◯ ⊚ ⊚ ⊚ ◯ X ◯ X characteristics Debinding ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ ◯ X X characteristics Sintering ⊚ ⊚ ⊚ ◯ ◯ ⊚ ◯ X Δ characteristics Quality inspection ◯ ⊚ ⊚ ◯ ◯ ◯ ◯ ◯ X

TABLE-US-00008 TABLE 8 Inspection results Example Example Example Example Example Example Comparative Comparative Comparative by process 19 20 21 22 23 24 Example10 Example11 Example12 Kneading ◯ ◯ ⊚ ⊚ ⊚ ◯ X ⊚ X characteristics Injection ◯ ◯ ⊚ ⊚ ⊚ ◯ Δ Δ X characteristics Debinding ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ ◯ X X characteristics Sintering ◯ ⊚ ⊚ ◯ ◯ ⊚ ◯ Δ Δ characteristics Quality inspection ◯ ⊚ ⊚ ◯ ◯ ◯ ◯ ◯ X

[0068] Characteristic Evaluation Method

[0069] 1) Kneading characteristics: flow characteristics (Rheological behavior, Viscosity)

[0070] 2) Injection characteristics: exterior inspection of the extruded body, X-ray internal non-destructive inspection

[0071] 3) Debinding characteristics: external inspection of debound body, X-ray internal non-destructive inspection

[0072] 4) Sintering characteristics: Density Measurement

[0073] 5) Quality inspection: hardness of sintered body, X-ray internal non-destructive inspection [0074] Marking method: Very good—⊚, Good—◯, Normal—Δ, Poor—X

[0075] Referring to Tables 5 to 8, kneading characteristics, injection characteristics, debinding characteristics, sintering characteristics, and quality of Examples 1 to 24 were normal to very good, and Comparative Examples 1, 4, 7, and 10 using a high-viscosity polyoxymethylene polymer alone exhibited poor kneading characteristics, Comparative Examples 2, 5, 8, and 11 using a low-viscosity polyoxymethylene polymer alone exhibited poor debinding characteristics, and Comparative Examples 3, 6, 9, and 12 including low contents of a powder-type inorganic material and a polyoxymethylene polymer exhibited poor kneading, injection, and debinding characteristics and thereby poor quality.

[0076] As the specific parts of the present invention have been described in detail above, for those of ordinary skill in the art, it is clear that these specific descriptions are only preferred embodiments, and the scope of the present invention is not limited thereby. Accordingly, the actual scope of the present invention will be defined by the appended claims and their equivalents.

INDUSTRIAL APPLICABILITY

[0077] By containing polyoxymethylenes alone, which has been produced with different viscosities, without feeding of other monomers in the polymerization process of polyoxymethylene, the binder composition for metal powder injection molding according to the present invention is more economical through low manufacturing costs compared with a conventional technique in which the rate of decomposition by a gas-phase acid is controlled by viscosity adjustment in a polymerization process.