KR20040013342A - Method for making fragnant porous metal sintering body - Google Patents

Method for making fragnant porous metal sintering body Download PDF

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Publication number
KR20040013342A
KR20040013342A KR1020020046212A KR20020046212A KR20040013342A KR 20040013342 A KR20040013342 A KR 20040013342A KR 1020020046212 A KR1020020046212 A KR 1020020046212A KR 20020046212 A KR20020046212 A KR 20020046212A KR 20040013342 A KR20040013342 A KR 20040013342A
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powder
mold
sintered metal
metal
metal compact
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KR1020020046212A
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Korean (ko)
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최성조
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최성조
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Publication of KR20040013342A publication Critical patent/KR20040013342A/en

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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
    • B22F3/10Sintering only
    • B22F3/11Making porous workpieces or articles
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L9/00Disinfection, sterilisation or deodorisation of air
    • A61L9/015Disinfection, sterilisation or deodorisation of air using gaseous or vaporous substances, e.g. ozone
    • A61L9/04Disinfection, sterilisation or deodorisation of air using gaseous or vaporous substances, e.g. ozone using substances evaporated in the air without heating
    • 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
    • B22F2201/00Treatment under specific atmosphere
    • B22F2201/01Reducing atmosphere
    • B22F2201/013Hydrogen
    • 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
    • B22F2201/00Treatment under specific atmosphere
    • B22F2201/20Use of vacuum

Abstract

PURPOSE: A method for manufacturing aromatic porous sintered metal compact is provided which obtains a three-dimensional shaped beautiful surface expressed by mold and maintains fragrance for a long time by injecting incense into the finish processed sintered metal compact after performing finish processing such as surface grinding and coating. CONSTITUTION: The method for manufacturing aromatic porous sintered metal compact comprises the processes of injecting the mixture into a mold after preparing a mixture in the liquid fluid state by mixing fine metallic powder with binder; extracting the preform from the mold after preparing a preform by drying the mixture injected into the mold; obtaining a porous sintered metal compact by sintering the preform at a vacuum or reductive atmosphere; performing post-treatment on the surface of the porous sintered metal compact by mechanical grinding or chemical grinding; and finish processing the post-treated sintered metal compact by coating so that incense is injected into the surface of the porous sintered metal compact, wherein the metallic powder includes stainless powder, copper and brass powder, bronze powder, zinc powder, zinc alloy powder, tin powder and tin alloy powder, gold powder, gold alloy powder, silver powder and silver alloy powder having a particles size of 1 to 150 microns, wherein the binder is a mixture of paraffin wax or polyethylene and base constituents of polyvinyl alcohol and methyl cellulose, and 30 to 50 vol.% of the binder is added to the metallic powder, wherein the mold is silicone rubber mold or metallic mold, and wherein the sintering process is performed in the temperature range corresponding to 70 to 95% of metal melting point at an atmosphere of vacuum, hydrogen gas or a mixed gas of hydrogen and nitrogen.

Description

방향성 다공질 금속소결체의 제조방법{Method for making fragnant porous metal sintering body}Method for making aromatic porous metal sintered body {Method for making fragnant porous metal sintering body}

본 발명은 금속분말을 결합제와 혼합하여 예비성형체를 만든후 고온에서 소결하므로서 다공질의 금속소결체를 제조하는 방법에 관한것으로, 더욱 상세하게는 직경이 1 미크론 이상 이고 150 미크론 이하인 금속분말을 파라핀왁스,메칠 셀룰로우스 등으로 이루어진 결합제와 혼합하여 액상의 유동상태를 얻은다음 분리가 가능한 주형에 주입하여 예비성형체를 얻고 주형을 분리한후 환원성분위기 혹은 진공분위기에서 소결처리하여 다공질의 금속소결체를 얻는 제조방법에 관한 것이다.The present invention relates to a method for preparing a porous metal sintered body by mixing a metal powder with a binder to form a preform and then sintering at a high temperature. More specifically, a metal powder having a diameter of 1 micron or more and 150 microns or less is used as paraffin wax, Preparation of a porous metal sintered body by mixing with a binder made of methyl cellulose to obtain a liquid state, and then injecting it into a mold that can be separated to obtain a preform, separating the mold, and then sintering in a reducing or vacuum atmosphere. It is about a method.

이러한 다공질의 소결체는 미세한 기공을 가지고 있어 그 기공안에 오일을 함침시켜 회전체의 마찰을 감소시키는 오일레스 베어링으로 사용하거나 향료를 기공중에 주입하므로서 방향성을 가지는 장신구등의 제조에 이용되고 있다. 장신구등의 제조에 사용하기 위해서는 그 표면이 미려하면서도 기공율이 15-30% 정도를 유지하는 것이 좋다. 기공율이 15% 이하가 되면 향료의 주입이 어렵고 30%이상이 되면 표면의 미려도가 떨어지고 방향성을 오래 유지하기 어렵다.Such porous sintered bodies have fine pores and are used as oilless bearings to impregnate oil in the pores to reduce friction of the rotating body or to inject perfume into the pores and to produce directional jewelry. In order to be used for the production of jewelry, the surface is beautiful, but porosity should be maintained about 15-30%. If the porosity is less than 15%, it is difficult to inject fragrance, and if it is more than 30%, the surface is less attractive and it is difficult to maintain the long direction.

종래의 방향성을 가지는 다공질 금속소결체를 얻는 방법으로는 특허100255185, 출원1020010061313에서 보듯이 직경 100 미크론 이상되는 금속분말이나 직경 50 미크론 이하의 금속섬유상분말을 사용하여 금형에 주입한후 고압의 프레스에서 600Mpa 이상으로 성형하여 예비성형체를 얻는다. 이때 600Mpa의 고압으로 성형하는 이유는 예비성형체의 그린강도(green strength)를 확보하기위한 것으로 이러한 강도가 없으면 다음공정의 취급시 성형체의 파손이 일어나 제조를 할수없는 것이다. 따라서 사용하는 분말이 100 미크론 이하가 될경우 제조된 소결체의 기공율이 15% 이하가 되어 용이하게 향료를 주입할수 없으므로 100 미크론 이상의분말을 600Mpa의 고압으로 성형하게된다 (특허100255185). 출원1020010061313 에서는 금속소결체의 기공율을 증가하기위해 금속섬유상 분말을 사용하거나 구형분말과 혼합하여 사용한다. 그러나 이와같은 종래기술은 고압에서 상하방향으로 동작하는 프레스에서 금형에 분말을 주입하여 성형하기때문에 그 성형체의 형상이 2차원적인 판상위에 약간의 요철을 가지는 형태로 밖에 나타날수 없어 보다 입체적이고 실체형상을 표현하는데 한계가 있다. 또한 기공율을 확보하기 위해 100미크론 이상의 분말을 사용하므로 표면이 미려한 보다 심미적인 제품을 제조하기 어려운 것이다.As a method of obtaining a porous metal sintered body having a conventional directionality, as shown in Patent 100255185, Application 1020010061313, a metal powder of 100 microns or more in diameter or a metal fibrous powder of 50 microns or less in diameter is injected into a mold and 600 Mpa in a high pressure press. It is shape | molded above and a preform is obtained. At this time, the reason for molding at a high pressure of 600Mpa is to secure the green strength of the preform, and if there is no such strength, the molded body may be broken during the handling of the next process and cannot be manufactured. Therefore, when the powder to be used is less than 100 microns, the porosity of the manufactured sintered compact is 15% or less, so fragrance can not be easily injected, thereby forming a powder of 100 microns or more at a high pressure of 600 Mpa (Patent 100255185). In application 1020010061313, in order to increase the porosity of the metal sintered body, metal fiber powder is used or mixed with spherical powder. However, such a conventional technique is formed by injecting powder into a mold in a press operating in a vertical direction at a high pressure, so that the shape of the molded body can only appear in a form having a slight unevenness on a two-dimensional plate. There is a limit to expressing. In addition, it is difficult to produce a more aesthetic product with a beautiful surface because it uses a powder of 100 microns or more to secure porosity.

따라서 본 발명에서는 금속분말에 결합제를 혼합하여 유동성을 부여한후 주형에 성형하므로서 입체적이고 실체적인 형상을 가지는 방향성을 가지는 것을 특징으로 하는 다공질 금속 소결체를 고안하고자 하였다.Therefore, the present invention was intended to devise a porous metal sintered body characterized by having a three-dimensional and tangible shape by forming a mold after mixing the binder with the metal powder to impart fluidity.

본 발명은 금속분말에 결합제를 첨가하여 유동성을 부여한뒤 분리가 가능한주형내에서 성형하여 예비성형체를 제조하고 고온에서 소결처리하여 다공질의 금속소결체를 제조하는것을 목적으로 한다. 이러한 제조방법은 금속분말에 유동성을부여하므로서 입체적인 형상을 가능하게 하고 미세한 분말을 사용하여 미려한 표면을 얻을수 있다. 또한 기공율을 조정하여 방향성이 오래 유지되는 액세서리,귀금속 장신구 등의 제조를 가능하게 한다.An object of the present invention is to prepare a preform by adding a binder to a metal powder to impart fluidity and molding in a mold that can be separated, and to prepare a porous metal sintered body by sintering at a high temperature. Such a manufacturing method enables three-dimensional shape by imparting fluidity to the metal powder and obtains a beautiful surface using fine powder. In addition, by adjusting the porosity, it is possible to manufacture accessories, precious metal jewelry, etc., which maintains long orientation.

본 발명의 다공질 금속 소결체는 금속분말과 결합제를 혼합하여 유동성을 부여 하는 단계, 분리가 가능하도록 고안된 주형내에 주입하는 단계, 주형에서 분리후 환원분위기 혹은 진공중에서 소결처리하는 단계, 소결된 다공질체를 연마하거나 표면에 코팅한후 향료를 주입하여 방향성을 부여하는 단계로 이루어져있다.The porous metal sintered body of the present invention comprises the steps of imparting fluidity by mixing the metal powder and the binder, injecting into a mold designed to be separated, sintering in a reducing atmosphere or vacuum after separation in the mold, sintered porous body After polishing or coating on the surface, the fragrance is injected to give directionality.

본 발명을 좀더 상세하게 설명하면 다음과 같다. 금속분말의 크기는 직경 1-150 미크론이 적당하다. 1 미크론 이하는 형성되는 기공의 크기가 너무 작아 향료의 주입이 어려워지며 150 미크론 이상이 되면 소결체의 표면이 미려하지 않아 장식품으로 적당하지가 않다. 결합제는 파라핀 왁스나 열가소성 수지를 사용하기도 하지만 분말에 유동성을 부여하고 성형체의 강도를 유지하기 위해 수용성 고분자인 폴리비닐알콜 이나 메칠 셀룰로우스를 사용한다. 결합제의 사용량은 금속분말 대해 부피비율로 30-50% 범위에서 사용하는 것이 좋다. 30% 이하가 되면 금속분말의 유동도가 떨어지고 50% 이상이 되면 성형체의 강도가 약해져서 파손의 위험이 있다.The present invention will be described in more detail as follows. The size of the metal powder is preferably 1-150 microns in diameter. Less than 1 micron, the size of the pores formed is so small that it is difficult to inject fragrance, and if the surface is more than 150 microns, the surface of the sintered body is not beautiful and is not suitable as an ornament. The binder may be paraffin wax or thermoplastic resin, but water-soluble polymers such as polyvinyl alcohol or methyl cellulose are used to impart fluidity to the powder and maintain the strength of the molded body. The amount of the binder to be used is preferably in the range of 30-50% by volume with respect to the metal powder. If it is 30% or less, the flow rate of the metal powder is lowered, and if it is 50% or more, the strength of the molded body becomes weak and there is a risk of breakage.

주형은 분리가 가능하여 주입된 금속의 유동체가 내부에서 건조되어 예비성형체가 된후 취출이 용이해야한다. 주형은 실리콘 고무로 사용하는 것이 경제적이고 좋다. 금속금형을 가공하는 것도 가능하며 이것은 수명은 길지만 다양한 주형을 필요로 하는 장신구 제품에 사용하기에는 비용이 많이 든다. 성형체의 형상은 주형의 모양대로 표현이 가능하므로 입체적이고 심미적인 제품의 표현이 가능하다.The mold must be separable so that the fluid of the injected metal is dried inside to become a preform, and then easy to take out. The mold is economical and good to use as silicone rubber. It is also possible to machine metal molds, which have a long life but are expensive to use in jewelry products that require a variety of molds. The shape of the molded body can be expressed according to the shape of the mold, so that a three-dimensional and aesthetic product can be expressed.

성형체의 소결은 진공분위기나 환원성분위기 즉 수소분위기나 암모니아를 분해시킨 수소와 질소의 혼합가스 분위기를 쓸수 있다. 금속의 종류가 금이나 은과 같은 귀금속일경우에는 대기 분위기를 그대로 사용해도 무방하다. 소결온도는 금속의 종류에 따라 결정되며 금속의 용융온도의 70%-95%범위에서 실시하는 것이 좋다.The sintering of the molded body may use a vacuum atmosphere or a reducing component atmosphere, that is, a mixed gas atmosphere of hydrogen and nitrogen in which hydrogen atmosphere or ammonia is decomposed. If the metal is a precious metal such as gold or silver, the atmosphere may be used as it is. The sintering temperature is determined by the type of metal and is preferably in the range of 70% -95% of the melting temperature of the metal.

이와같이 제조된 금속소결체는 기공율 20%-40%의 다공질로 되어있으며 적당한 표면연마와 코팅등으로 장신구의 목적에 따라 가공한후 향료를 표면에 떨어 뜨리면 형성된 미세한 기공을 통해 향료가 모세관 현상에 의해 내부로 침투되고 방향성을 장시간 유지하는 금속장신구로 이용되는 것이다.The metal sintered body manufactured in this way is porous with 20% -40% porosity, and the fragrance is formed by capillary phenomenon through the fine pores formed by dropping the fragrance on the surface after processing according to the purpose of the jewelry with proper surface polishing and coating. It is used as metal jewelry to penetrate into and keep the directionality for a long time.

그리고,상기 와같이 기술된 본 발명은 일실시예로서 설명하였으나 이는 상기에 기술된 바람직한 일실시예에 한정하지 아니하며,청구범위에서 청구하는 본 발명의 요지를 벗어남이 없이 당해 본 발명이 속하는 기술분야에서 통상의 지식을 가진자라면 다양하게 변형실시가 가능한것은 물론이고, 그와같은 변경실시는 본 발명의 핵심요소로 기재된 청구범위 내에 존재한다고 할 것이다.And, the present invention described as described above has been described as an embodiment, which is not limited to the preferred embodiment described above, the technical field to which the present invention belongs without departing from the spirit of the invention claimed in the claims Of course, those skilled in the art will be able to make various modifications, as well as such modifications will be within the scope of the claims as the core elements of the present invention.

<실시예1>Example 1

평균 직경 35 미크론 스테인레스 분말 350 g 과 5% 폴리비닐알콜 50cc 를 잘 혼합하여 스러리 형태로 만들었다. 이 스러리를 실리콘고무로 만든 주형에 부어 섭씨 100도에서 30분간 건조하여 예비성형체를 만들었다. 이 성형체는 수분은 건조되어 딱딱한 상태로 다음 공정으로 취급하는데 전혀 지장이 없었다. 이 성형체를 진공도 1 토르 이하의 진공로에서 섭씨 1200도에서 1시간 가열하여 소결하였다. 소결된 다공질체는 밀도가 진밀도의 65%였으며 미려한 표면이 얻어졌다. 진공증착으로 금 0.5 미크론을 코팅한뒤 향료를 표면에 떨어트려 주입하여 방향성을 가지는 장신구를 만들었다.350 g of an average diameter of 35 micron stainless powder and 50 cc of 5% polyvinyl alcohol were mixed well to form a slurry. The slurry was poured into a mold made of silicone rubber and dried at 100 degrees Celsius for 30 minutes to form a preform. This molded article had no problem in handling in the next process while the moisture was dried and hard. The molded body was heated and sintered at 1200 degrees Celsius for 1 hour in a vacuum furnace having a vacuum degree of 1 Torr or less. The sintered porous body had a density of 65% of true density and a beautiful surface was obtained. 0.5 micron of gold was coated by vacuum deposition, and then perfume was dropped on the surface to make directional jewelry.

<실시예2>Example 2

평균 직경 5 미크론의 은(Ag)분말 50g을 5% 농도의 메칠 셀룰로우스 수용액에 혼합하여 잘 교반하여 스러리형태를 만들었다. 실리콘 고무로 만든 주형에 부어 섭씨100도에서 20분간 건조하면 수분이 제거되면서 겔상태로 고형화 된다. 이 성형체를 산화분위기의 전기로에서 섭씨 900도로 1시간 가열하여 소결하였다. 진공이나 환원분위기가 아니더라도 은 분말은 충분히 소결이 이루어져 기공도 30%의 다공질 소결체가 되었다. 표면을 연마하고 세공한후 향료를 주입하여 방향성을 가지는 은 세공 장신구를 제조할수 있었다.50 g of silver (Ag) powder having an average diameter of 5 microns was mixed with a 5% aqueous solution of methyl cellulose and stirred well to form a slurry. It is poured into a mold made of silicone rubber and dried at 100 degrees Celsius for 20 minutes to remove moisture and solidify to a gel state. The molded body was heated and sintered at 900 degrees Celsius for 1 hour in an electric furnace in an oxidizing atmosphere. Even in the absence of vacuum or reducing atmosphere, the silver powder was sufficiently sintered to form a porous sintered body having a porosity of 30%. After polishing the surface and injecting the fragrance, it was possible to prepare the silver fine jewelry having a directionality.

본 발명은 외부의 가압이 없이 분말에 결합제를 혼합하여 일정 형상을 손쉽게 다공질 소결체로 제조할 수 있게 하므로서 향료를 주입 할 수 있는 방향성의 장신구를 경제적으로 만들수 있다. 종래의 방법은 고가의 고압 프레스로 성형하여 제조 비용이 높고 2차원적인 형상제조에 그친데 비해 본 발명은 프레스 성형장치가 필요없이 주형에 주입하여 제조하므로 비용이 현저히 저렴하고 3차원적인 형상의 제조가 가능하다. 본 발명은 방향성 금속소결체 뿐만 아니라 다공질 성질이 가지는 높은 비표면적을 이용한 촉매담체 등에 활용하는 효과가 기대된다.The present invention enables the economical manufacture of the directional ornaments that can be injected into the fragrance by mixing the binder into the powder without external pressurization, so that a certain shape can be easily produced as a porous sintered body. The conventional method is a high-pressure high-pressure press molded to produce a high cost and two-dimensional shape, but the present invention is manufactured by injecting the mold without the need for a press molding apparatus, significantly lower cost and manufacture of three-dimensional shape Is possible. The present invention is expected to be effective in use not only in the aromatic metal sintered body but also in the catalyst carrier using a high specific surface area having porous properties.

Claims (5)

미세한 금속분말을 결합제와 혼합하여 액상유동상태를 만들어 주형에 주입한후 건조시켜 예비성형체를 만들어 주형에서 취출한다. 이 예비 성형체를 진공 혹은 환원성분위기에서 소결하여 다공질의 금속소결체를 얻은 다음 표면을 기계연마나 화학연마등의 방법으로 후처리를 하여 코팅등의 밥법으로 마무리한 장식용의 향료주입이 가능한 다공질 금속 소결체의 제조방법The fine metal powder is mixed with the binder to form a liquid state, injected into the mold and dried to form a preform, and taken out from the mold. This preform is sintered in vacuum or reducing atmosphere to obtain porous metal sintered body, and then the surface is post-treated by mechanical polishing or chemical polishing, etc. Way 1항의 금속분말은 1 미크론 이상 150 미크론 이하의 스테인레스분말,구리및 황동,청동분말,아연및 그합금분말,주석및 그 합금분말, 금 및 그 합금분말,은 및 그합금분말로 한다.The metal powder of paragraph 1 is made of stainless powder, copper and brass, bronze powder, zinc and alloy powder, tin and its alloy powder, gold and its alloy powder, silver and its alloy powder. 1항의 결합제는 폴리비닐알콜,메칠 셀룰로우스를 기본으로 한 파라핀왁스나 폴리에틸렌의 혼합체로 하며 금속분말에 대한 부피비는 30%-50%로 한다.The binder in paragraph 1 is a mixture of polyvinyl alcohol and methyl cellulose based paraffin wax or polyethylene, and the volume ratio to the metal powder is 30% -50%. 1항의 주형은 분리가 가능하도록 만든 실리콘 고무 주형이나 금속주형으로 한다.The molds of paragraph 1 are made of silicone rubber molds or metal molds made to be removable. 1항의 소결은 금속의 용융온도의 70%-95% 사이에서 실시하며 진공분위기 혹은 수소가스나 수소및 질소의 혼합가스 분위기에서 실시하다.Sintering of 1 is carried out between 70% and 95% of the melting temperature of the metal and is carried out in a vacuum atmosphere or a mixed gas atmosphere of hydrogen gas or hydrogen and nitrogen.
KR1020020046212A 2002-08-06 2002-08-06 Method for making fragnant porous metal sintering body KR20040013342A (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20040041813A (en) * 2002-11-12 2004-05-20 최성조 Process for preparing a fragnant metal body using a sintered porous metal plate
KR100505850B1 (en) * 2002-08-21 2005-08-04 오승묵 metallic perfume bottle and manufacturing method thereof
KR100851730B1 (en) * 2007-11-22 2008-08-11 주학식 Fragrance emitting and method for manufacturing the same
KR100918593B1 (en) * 2008-08-07 2009-09-24 주학식 Fragrance emitting and method for manufacturing the same
CN101559491B (en) * 2009-05-25 2011-04-20 西安宝德粉末冶金有限责任公司 Integral molding die of large scale sintering porous cone pipe and isotropic molding method therewith
KR101040768B1 (en) * 2008-08-12 2011-06-13 주학식 Fragrance emitting and method for manufacturing the same

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6244506A (en) * 1985-08-21 1987-02-26 Yoshida Kogyo Kk <Ykk> Manufacture of porous sintered body of stainless steel powder
JPH09217101A (en) * 1995-12-05 1997-08-19 Toto Ltd Production of powder metallurgical product
JP2002038203A (en) * 2000-07-26 2002-02-06 Dainippon Ink & Chem Inc Method for producing metallic porous body

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6244506A (en) * 1985-08-21 1987-02-26 Yoshida Kogyo Kk <Ykk> Manufacture of porous sintered body of stainless steel powder
JPH09217101A (en) * 1995-12-05 1997-08-19 Toto Ltd Production of powder metallurgical product
JP2002038203A (en) * 2000-07-26 2002-02-06 Dainippon Ink & Chem Inc Method for producing metallic porous body

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100505850B1 (en) * 2002-08-21 2005-08-04 오승묵 metallic perfume bottle and manufacturing method thereof
KR20040041813A (en) * 2002-11-12 2004-05-20 최성조 Process for preparing a fragnant metal body using a sintered porous metal plate
KR100851730B1 (en) * 2007-11-22 2008-08-11 주학식 Fragrance emitting and method for manufacturing the same
KR100918593B1 (en) * 2008-08-07 2009-09-24 주학식 Fragrance emitting and method for manufacturing the same
KR101040768B1 (en) * 2008-08-12 2011-06-13 주학식 Fragrance emitting and method for manufacturing the same
CN101559491B (en) * 2009-05-25 2011-04-20 西安宝德粉末冶金有限责任公司 Integral molding die of large scale sintering porous cone pipe and isotropic molding method therewith

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