CN113828778A - Water-soluble binder, preparation method of binder and method for preparing parts - Google Patents

Water-soluble binder, preparation method of binder and method for preparing parts Download PDF

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Publication number
CN113828778A
CN113828778A CN202111125584.1A CN202111125584A CN113828778A CN 113828778 A CN113828778 A CN 113828778A CN 202111125584 A CN202111125584 A CN 202111125584A CN 113828778 A CN113828778 A CN 113828778A
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water
degreasing
binder
soluble binder
parts
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CN113828778B (en
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张辰
秦晓冬
包崇玺
朱志荣
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Mbtm New Materials Group Co ltd
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Mbtm New Materials Group Co ltd
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/22Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces for producing castings from a slip
    • B22F3/225Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces for producing castings from a slip by injection molding
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10Sintering only
    • B22F3/1003Use of special medium during sintering, e.g. sintering aid
    • B22F3/1007Atmosphere
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10Sintering only
    • B22F3/1017Multiple heating or additional steps
    • B22F3/1021Removal of binder or filler

Abstract

The invention relates to a water-soluble binder, a preparation method of the binder and a method for preparing a part, and the water-soluble binder is characterized by comprising the following components in percentage by mass: PEG 1000-1500: 30-37%, PEG 2000-3000: 35-40%, POM: 10% -15%, SA: 5-6%, antioxidant: 1% -2% and framework material: 5 to 9 percent. The degreasing agent can ensure that a blank has certain strength while providing a faster degreasing rate, has good shape retention, has no influence on parts and has no pollution.

Description

Water-soluble binder, preparation method of binder and method for preparing parts
Technical Field
The invention belongs to the field of metal powder injection molding, and particularly relates to a water-soluble binder, a preparation method of the water-soluble binder and a method for preparing a part by using the water-soluble binder.
Background
The injection molding technology is an environment-friendly mass production technology which is energy-saving, material-saving, excellent in performance, high in product precision and good in stability, and is widely applied to materials such as stainless steel, tungsten-based powder and the like.
The currently used adhesives for injection molding are mainly divided into two types, namely a plastic base and a wax base, wherein the main matrix of the plastic base adhesive is a POM material, special equipment is required for degreasing, oxalic acid or nitric acid is used as a catalyst for catalytic degreasing, and waste gas generated by degreasing needs to be subjected to high-temperature combustion treatment. The main matrix of the wax-based binder is paraffin, and the degreasing is carried out by adopting an organic solvent, so that the degreasing time is long and the cost is higher. How to reduce the degreasing cost, shorten the degreasing time and reduce the pollutant discharge is a difficult problem faced by injection molding.
At present, as the invention patent of China, a precursor water-soluble binder for powder injection molding and a preparation method thereof, the patent number ZL201010230561.2 (the publication number is CN 101885614B) discloses a water-soluble binder, which is characterized in that the water-soluble binder is prepared by mixing 60-70% of PEG (1000-plus-6000), 10-25% of PVB, 10-25% of PCS and 5-10% of SA in percentage by weight, wherein the PCS is used for powder injection molding as a binder component, SiC particles are generated after cracking to play a certain reinforcing role on a base material, but SiC has a certain carbide precipitation during powder sintering and plays a negative role on parts with special requirements.
Also for example, the chinese patent application of the present invention, a MAX phase cermet injection molding process, whose patent application No. CN202010704456.1 (application publication No. CN111826540A), discloses a MAX phase cermet injection molding process, which is characterized in that, calculated by weight percentage, it is made by mixing 25-35% CAB, 60-80% PEG, 1-3% SA, 0.4-0.6% PTZ, but the physical properties and water solubility of PEGs with different molecular weights are not the same, and PEGs with partial molecular weights cannot be molded during the bonding process; PEG with partial range molecular weight has a slow rate of degreasing in water and is not suitable for extended range production.
For metal powder injection molding, a green body of the metal powder injection molding machine needs to be ensured to have certain strength in the molding process, other components are introduced as little as possible, and the degreasing rate is high in the degreasing process. The above-mentioned patents introduce ingredients such as SiC which are not suitable for metal injection molding, which adversely affect the properties of the sintered parts, and thus the above-mentioned binders are not well suited for use in the metal powder injection molding process.
Disclosure of Invention
The first technical problem to be solved by the present invention is to provide a water-soluble adhesive with high degreasing speed and low or no pollution in view of the current state of the prior art.
The second technical problem to be solved by the invention is to provide a preparation method of the water-soluble adhesive which is easy to degrease, low in pollution or free of pollution and has good shape retention.
The third technical problem to be solved by the invention is to provide a method for preparing parts by using the water-soluble binder, wherein the porosity is reduced.
The technical scheme adopted by the invention for solving the first technical problem is as follows: the water-soluble binder is characterized by comprising the following components in percentage by mass: PEG 1000-1500: 30-37%, PEG 2000-3000: 35-40%, POM: 10% -15%, SA: 5-6%, antioxidant: 1% -2% and framework material: 5 to 9 percent.
The PEG1000-1500 is PEG with molecular weight of 1000-1500, and the PEG2000-3000 is PEG with molecular weight of 2000-3000, i.e. the PEG with molecular weight of 1000-1500 and 2000-3000, for the polyethylene glycol (PEG) with lower molecular weight, the polyethylene glycol (PEG) is a liquid and can not be used as a binder; the polyethylene glycol with overlarge molecular weight has slightly poorer degreasing speed than the polyethylene glycol with low molecular weight, so that the PEG1000-1500 and the PEG2000-3000 are matched for use, a body can be ensured to have certain strength while higher degreasing speed is provided, and the shape-keeping property is good.
Preferably, the antioxidant is an oil-soluble antioxidant, and the oil-soluble antioxidant is at least one of TBHQ, BHA, and BHT.
Preferably, the backbone material is at least one of HDPE, LDPE and PP.
The technical scheme adopted by the invention for solving the second technical problem is as follows: the preparation method of the water-soluble binder is characterized by sequentially comprising the following steps of:
step 1) melting 10% -15% of POM;
and 2) sequentially adding 30-35% of PEG1000-1500, 35-40% of PEG2000-3000, 5-6% of SA, 1-2% of antioxidant and 5-9% of framework material into the step 1), and obtaining the water-soluble binder after all the raw materials are melted and uniformly mixed. In the preparation method of the water-soluble binder, after the POM is melted, the PEG, the SA, the antioxidant and the framework material are sequentially added, so that the loss of the PEG, the SA and the framework material caused by high-temperature oxidation and decomposition can be effectively reduced.
The technical scheme adopted by the invention for solving the third technical problem is as follows: the method for preparing the part by using the water-soluble binder is characterized by sequentially comprising the following steps of:
s1 Mixed feed
The adhesive comprises the following components in percentage by mass: the metal powder is uniformly mixed in a molten state according to the proportion of (7-12) to (100), the binder used in the proportion is less, and the basic requirement of injection flow can be met;
s2 Forming
The feed obtained in step S1 is injection molded to obtain parts.
Preferably, after step S2, degreasing is performed, that is, the molded part is placed in distilled water for degreasing, and after degreasing, drying is performed at a temperature of 45 to 55 ℃.
Specifically, a stirrer is used for stirring in distilled water during degreasing, the rotating speed of the stirrer is 50-100rpm, and the degreasing time is 5-7 h. When the rotating speed is too low (such as lower than 50rpm), the extracted binder cannot be ensured to be diffused in time; when the rotating speed is too high (such as higher than 100rpm), certain damage can be caused to the parts. In addition, a flowing degreasing pool can be used for replacing stirring in large-scale production, certain continuity is achieved, production is facilitated, and production efficiency is improved.
Preferably, the degreasing time is 3.5-6 h.
Preferably, the part after the degreasing treatment is sintered under a vacuum condition, and the vacuum sintering has an obvious shrinkage effect on the part in the later sintering period, so that the porosity of the part is reduced, and the density of the part is improved.
Preferably, the sintering temperature in the sintering treatment is 1250-1500 ℃, the sintering time is 1-3h, and the higher temperature and sufficient time of the process are beneficial to the full shrinkage of parts so as to achieve higher density.
Compared with the prior art, the invention has the advantages that: the water-soluble binder is prepared by mutually mixing PEG1000-1500, PEG2000-3000, SA, POM and the like, wherein PEG has good cohesiveness and water solubility, and the PEG1000-1500 and PEG2000-3000 are matched for use, so that a body can be ensured to have certain strength while a faster degreasing rate is provided, and good shape retention is achieved; SA provides good lubricity, ensuring good extrudability during molding. All components in the binder are organic matters which can be removed in the degreasing and sintering processes, and have no influence on parts. The degreasing can be carried out by using distilled water, the cost is low, no pollution is caused, and the environmental protection requirement is met. The method has simple process, is suitable for injection molding process of different materials, has universality, and is beneficial to popularization and large-scale production.
Drawings
FIG. 1 is a sintered porosity of an injection molded part of example 1;
FIG. 2 is a sintered porosity of the injection molded part of example 2;
FIG. 3 is a sintered porosity of the injection molded part of example 3.
Detailed Description
The invention is described in further detail below with reference to the accompanying examples.
Example 1:
as shown in fig. 1, it is the 1 st preferred embodiment of the present invention. The metal powder of this example was 316 stainless steel powder, the antioxidant was BHT (2, 6-di-tert-butyl-4-methylphenol), and the skeletal material was HDPE (high density polyethylene).
The water-soluble binder of this example comprises, by mass%, 30% PEG1000, 40% PEG2000, 15% POM, 5% SA, 1% BHT, and 9% HDPE. In this embodiment, the method for preparing the water-soluble binder includes melting 15% of POM, and then adding 30% of PEG1000, 40% of PEG2000, 5% of SA, 1% of BHT, and 9% of HDPE to the melted POM, and mixing them uniformly after all the raw materials are melted, so as to obtain the water-soluble binder.
The method for preparing a part using the water-soluble binder of this example sequentially included the following steps: s1 Mixed feed: the adhesive comprises the following components in percentage by mass: mixing 316 stainless steel powder in a ratio of 7:100 uniformly in a molten state; s2 forming: and (4) performing injection molding on the feed obtained in the step S1 to obtain a part, wherein the bending strength of a green part is 6.3MPa through testing, and the strength of the green part is improved by about 14% compared with that of the wax-based feed part. And then placing the parts in distilled water, and stirring by using a stirrer for degreasing, wherein the rotating speed of the stirrer is 50rpm, the degreasing time at room temperature is 4 hours, and the degreasing time is obviously reduced compared with 6-12 hours of degreasing time of a wax base. And (3) drying the degreased parts in an oven at the drying temperature of 50 ℃, and finally, carrying out vacuum sintering on the dried degreased parts at the sintering temperature of 1300 ℃ for 1 h. The porosity after sintering is low and only 2.5%, as shown in fig. 1.
Example 2:
fig. 2 shows a 2 nd preferred embodiment of the present invention. The metal powder of this example is 316 stainless steel powder, the antioxidant is BHA (butylated hydroxyanisole), and the matrix material is LDPE (low density polyethylene is also called high pressure polyethylene).
This embodiment differs from embodiment 1 described above in that: 1) the water-soluble binder has different mass percentages of the components, and specifically, the binder of this embodiment includes, by mass percentage, 35% PEG1000, 35% PEG2000, 15% POM, 6% SA, 2% BHA, and 7% LDPE.
2) The proportion of the binder and the stainless steel powder in the mixed feed is different, specifically, the binder and the stainless steel powder are uniformly mixed according to the proportion of 12:100, the bending strength of a tested part is 6.0MPa, and the strength of a part blank is improved by about 11 percent compared with that of a wax-based feed part;
3) the rotation speed of the stirrer in the degreasing treatment and the sintering temperature are different, specifically, the rotation speed of the stirrer is 100rpm, the degreasing time is 3.5h, the time is obviously reduced compared with the time of 6-12h for degreasing of wax base, the sintering temperature is 1250 ℃, and the sintering time is 1 h.
The porosity of the sintered part in this example is as shown in fig. 2, and is low and only 5%.
Example 3:
as shown in fig. 3, is the 3 rd preferred embodiment of the present invention.
The antioxidant is TBHQ (tert-butyl hydroquinone), and the framework material is PP (polypropylene).
This embodiment differs from embodiment 1 described above only in that: 1) the water-soluble binder has different mass percentages of the components, specifically, the binder of the embodiment comprises, by mass percentage, 35% of PEG1000, 39% of PEG2000, 15% of POM, 5% of SA, 1% of TBHQ, and 5% of PP;
2) the proportion of the binder and the stainless steel powder in the mixed feed is different, specifically, the binder and the stainless steel powder are uniformly mixed according to the proportion of 10:100, the bending strength of a tested part is 5.8MPa, and the strength of a part blank is improved by about 5 percent compared with that of a wax-based feed part;
3) the rotation speed of the stirrer in the degreasing treatment is different, and specifically, the rotation speed of the stirrer is 60rpm, the degreasing time is 3.5h, and the time is obviously reduced compared with the time of 6-12h for degreasing wax base.
The porosity of the sintered part in this example is lower and only 3.5%, as shown in fig. 3.
Example 4:
this embodiment differs from embodiment 1 described above only in that:
1) the water-soluble binder has different mass percentages of the components, specifically, the binder of the present embodiment includes, by mass percentage, 37% of PEG1500, 38% of PEG3000, 10% of POM, 5% of SA, 1% of BHT, and 9% of PE;
2) the stainless steel powder in the mixed feeding adopts tungsten powder, and the proportion of the binder and the stainless steel powder is different, specifically, the binder and the stainless steel powder are uniformly mixed according to the proportion of 12: 100;
3) the sintering temperature is different, specifically, the sintering temperature is 1450 ℃, and the sintering time is 2 hours. The porosity of the sintered part is low.
Example 5:
this embodiment differs from embodiment 1 described above only in that:
1) the water-soluble binder has different mass percentages of the components, and specifically, the binder of the present embodiment includes, by mass percentage, 35% PEG1000, 39% PEG2000, 14% POM, 5% SA, 1.5% BHA, 5.5% LDPE;
2) the stainless steel powder in the mixed feed adopts 314 stainless steel powder, and the proportion of the binder and the stainless steel powder is different, specifically, the binder and the stainless steel powder are uniformly mixed according to the proportion of 9: 100;
3) the rotation speed of the stirrer in the degreasing treatment and the sintering temperature are different, specifically, the rotation speed of the stirrer is 70rpm, the sintering temperature is 1250 ℃, and the sintering time is 3.5 h. The porosity of the sintered part is low.
Example 6:
this embodiment differs from embodiment 1 described above only in that:
1) the water-soluble binder has different mass percentages of the components, and specifically, the binder of the present embodiment includes, by mass percentage, 35% PEG1000, 40% PEG2000, 10% POM, 5% SA, 1% BHA, and 9% LDPE.
2) The stainless steel powder in the mixed feeding adopts 434 stainless steel powder, and the proportion of the binder and the stainless steel powder is different, specifically, the binder and the stainless steel powder are uniformly mixed according to the proportion of 10: 100;
3) the rotation speed of the stirrer in the degreasing treatment and the sintering temperature are different, specifically, the rotation speed of the stirrer is 60rpm, and the sintering temperature is 1260 ℃. The porosity of the sintered part is low.
Example 7:
this embodiment differs from embodiment 1 described above only in that:
1) the mass percentages of the components in the water-soluble binder are different, and specifically, the binder of the embodiment comprises 30% of PEG1000, 40% of PEG2000, 15% of POM, 5% of SA, 1% of BHA and 9% of HDPE;
2) the stainless steel powder in the mixed feeding adopts 202 stainless steel powder, and the proportion of the binder and the stainless steel powder is different, specifically, the binder and the stainless steel powder are uniformly mixed according to the proportion of 10: 100;
3) the rotation speed of the stirrer in the degreasing treatment and the sintering temperature are different, specifically, the rotation speed of the stirrer is 100rpm, and the sintering temperature is 1280 ℃. The porosity of the sintered part is low.
Example 8:
this embodiment differs from embodiment 1 described above only in that:
1) the mass percentages of the components in the water-soluble binder are different, and specifically, the binder of the embodiment comprises 32% of PEG1000, 40% of PEG2000, 13% of POM, 5% of SA, 1% of BHA and 9% of LDPE;
2) the stainless steel powder in the mixed feeding adopts 316 stainless steel powder, and the proportion of the binder and the stainless steel powder is different, specifically, the binder and the stainless steel powder are uniformly mixed according to the proportion of 10: 100;
3) the rotation speed of the stirrer in the degreasing treatment and the sintering temperature are different, specifically, the rotation speed of the stirrer is 100rpm, and the sintering temperature is 1280 ℃. The porosity of the sintered part is low.
Example 9:
this embodiment differs from embodiment 1 described above only in that:
1) the mass percentages of the components in the water-soluble binder are different, and specifically, the binder of the embodiment comprises 32% of PEG1200, 40% of PEG2500, 13% of POM, 5.5% of SA, 1% of BHA and 9% of LDPE;
2) in the degreasing treatment, the degreasing time, the drying temperature and the sintering temperature are different, specifically, the degreasing time is 5 hours, the drying temperature is 45 ℃, and the sintering temperature is 1500 ℃. The porosity of the sintered part is low.
Example 10:
this embodiment differs from embodiment 1 described above only in that:
in the degreasing treatment, the degreasing time, the drying temperature and the sintering temperature are different, specifically, the degreasing time is 5 hours, the drying temperature is 55 ℃, and the sintering temperature is 1500 ℃. The porosity of the sintered part is low.

Claims (10)

1. The water-soluble binder is characterized by comprising the following components in percentage by mass: PEG 1000-1500: 30-37%, PEG 2000-3000: 35-40%, POM: 10% -15%, SA: 5-6%, antioxidant: 1% -2% and framework material: 5 to 9 percent.
2. The water-soluble binder according to claim 1, wherein: the antioxidant is an oil-soluble antioxidant, and the oil-soluble antioxidant is at least one of TBHQ, BHA and BHT.
3. The water-soluble binder according to claim 1, wherein: the framework material is at least one of HDPE, LDPE and PP.
4. A method for preparing a water-soluble binder according to any one of claims 1 to 3, characterized by comprising the following steps in sequence:
step 1) melting 10% -15% of POM;
and 2) sequentially adding 30-35% of PEG1000-1500, 35-40% of PEG2000-3000, 5-6% of SA, 1-2% of antioxidant and 5-9% of framework material into the step 1), and obtaining the water-soluble binder after all the raw materials are melted and uniformly mixed.
5. A method for producing a part using the water-soluble binder according to any one of claims 1 to 3, comprising the following steps in order:
s1 Mixed feed
The adhesive comprises the following components in percentage by mass: the metal powder is mixed uniformly in a molten state according to the proportion of (7-12) to (100);
s2 Forming
The feed obtained in step S1 is injection molded to obtain parts.
6. The method of parts as claimed in claim 5, wherein: and (4) degreasing after the step S2, namely degreasing the formed part in distilled water, and drying at the temperature of 45-55 ℃ after degreasing.
7. The method of parts as claimed in claim 6, wherein: and stirring in distilled water by using a stirrer during degreasing, wherein the rotating speed of the stirrer is 50-100rpm, and the degreasing time is 5-7 h.
8. The method of parts as claimed in claim 7, wherein: the degreasing time is 3.5-6 h.
9. The method of parts as claimed in claim 6, wherein: and sintering the degreased part under a vacuum condition.
10. The method of parts as claimed in claim 9, wherein: the sintering temperature in the sintering treatment is 1250-1500 ℃, and the sintering time is 1-3 h.
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