KR960012870B1 - Method of manufacturing tho2-w wire - Google Patents

Method of manufacturing tho2-w wire Download PDF

Info

Publication number
KR960012870B1
KR960012870B1 KR1019940010790A KR19940010790A KR960012870B1 KR 960012870 B1 KR960012870 B1 KR 960012870B1 KR 1019940010790 A KR1019940010790 A KR 1019940010790A KR 19940010790 A KR19940010790 A KR 19940010790A KR 960012870 B1 KR960012870 B1 KR 960012870B1
Authority
KR
South Korea
Prior art keywords
wire
sintering
impurities
thorium
aqueous solution
Prior art date
Application number
KR1019940010790A
Other languages
Korean (ko)
Other versions
KR950031329A (en
Inventor
김종대
최덕순
Original Assignee
대한중석 주식회사
나승렬
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 대한중석 주식회사, 나승렬 filed Critical 대한중석 주식회사
Priority to KR1019940010790A priority Critical patent/KR960012870B1/en
Publication of KR950031329A publication Critical patent/KR950031329A/en
Application granted granted Critical
Publication of KR960012870B1 publication Critical patent/KR960012870B1/en

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F5/00—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product
    • B22F5/12—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product of wires
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/12—Both compacting and sintering
    • B22F3/16—Both compacting and sintering in successive or repeated steps
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/12—Both compacting and sintering
    • B22F3/16—Both compacting and sintering in successive or repeated steps
    • B22F3/164—Partial deformation or calibration
    • B22F2003/166—Surface calibration, blasting, burnishing, sizing, coining
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2201/00—Treatment under specific atmosphere
    • B22F2201/01—Reducing atmosphere
    • B22F2201/013—Hydrogen

Landscapes

  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Microwave Tubes (AREA)
  • Powder Metallurgy (AREA)

Abstract

This method provides a good magnetic property of magnetron, emission property of hot electron by removing of impurities in the inside of powder particles during production of sintered metal. ThO2-W wire is produced by the processes of : 1) mixing raw powders with 150 to 300ppm K, 150 to 200ppm Al, 150 to 400ppm Si, 50 to 100ppm Ca, and the balance of tungsten oxide; 2) producing an aqueous solution of mixed powders, 3) adding 1.4 to 3.5wt.% thorium nitride to the solution, 4) drying for doping of thorium nitride on the surface of tungsten oxide at 100 to 200deg.C, 5) reducing at 750 to 950deg.C for 2 to 3 hrs under the atmosphere of reduction, 6) compacting, 7) 1st pre-sintering at 1,000 to 1,300deg.C for 20 to 120min, 8) 2nd sintering at 2,500 to 3,000deg.C for 20 to 60min, 9) swaging, and 10) drawing.

Description

산화토륨-텅스텐와이어(ThO2-W Wire)의 제조방법Method of manufacturing thorium oxide-tungsten wire (ThO2-W Wire)

본 발명은 산화토륨-텅스텐와이어(ThO2-W Wire)의 제조에 관한 것으로, 특히 소결체 제조시 분말입자 내부에 존재하는 불순물을 제거하여 열전자 방출특성 및 마그네트론의 전자기적 특성을 향상시키고, 불량율을 감소시키는데 적당한 제조방법에 관한 것이다.The present invention relates to the production of thorium-tungsten wire (ThO 2 -W Wire), in particular to remove the impurities present in the powder particles during the manufacture of the sintered body to improve the hot electron emission characteristics and the electromagnetic properties of the magnetron, the defect rate It relates to a method of manufacture suitable for reducing.

ThO2-W Wire는 주로 전자렌지 마크네트론의 열전자 방출용 필라멘트로 사용되는데, 이는 고온 열 Cycle에 대한 고온강도와 안정된 열전자방출 및 마그네트론의 전자기적 특성이 요구된다.ThO 2 -W Wire is mainly used as filament for the release of hot electrons of microwave oven macronet, which requires high temperature strength and stable hot electron emission for high temperature heat cycle and magnetron's electromagnetic characteristics.

마그네트론의 필라맨트는 진공관내에서 2000℃ 이상의 가열에 의해 열전자를 발산하여 마아크로파를 형성시키는 기기이므로 필라멘트 소재가 미량의 불순물을 함유하고 있으면 그 불순물이 휘발되어 열전자방출 특성 및 마그네트론의 전자기적 특성을 크게 저하시키는 문제 발생 요소가 된다.The filament of magnetron is a device that emits hot electrons by heating more than 2000 ℃ in a vacuum tube to form a microwave, so if the filament material contains a small amount of impurities, the impurities are volatilized to release the hot electrons and the electromagnetic characteristics of the magnetron. It is a problem occurrence factor that greatly lowers.

따라서 1% ThO2-W Wire 소재는 기본적으로 ThO2입자의 미세 균일 분산이 요구되지만 그와 더불어 소재에 포함되어 있는 불순물을 극소화 시키는 기술도 앞의 기 술 못지않게 중요하다.Therefore, 1% ThO 2 -W Wire material basically requires fine uniform dispersion of ThO 2 particles, but also the technology to minimize impurities contained in the material is just as important as the previous technology.

지금까지 알려진 1% ThO2-W Wire의 공업적 제조법은 일본 특허 공보 39-27181이 있다.The industrial production method of 1% ThO 2 -W Wire so far known is Japanese Patent Publication No. 39-27181.

이 방법은 원료 텅스텐 분말을 염산과 불산으로 세척한데 이어서 수(水) 세척으로 불순물을 제거하고 질산토륨을 도핑(doping)한 후 일반 분말 야금법으로 Wire를 제조하는 것으로 이 방법으로 불순물을 제거할 경우는 분말 입자 표면의 불순물은 산에 용해되어 제거되지만 분말입자 내부의 불순물의 제거는 불가능하다.In this method, raw tungsten powder is washed with hydrochloric acid and hydrofluoric acid, then impurities are removed by water washing, doping with thorium nitrate, and wire is manufactured by ordinary powder metallurgy. In this case, impurities on the surface of the powder particles are dissolved in an acid and removed, but it is impossible to remove impurities inside the powder particles.

본 발명은 상기한 종래의 문제점을 해결하기 위해 안출한 것으로, 불순물과 친화력이 강한 물질을 임의로 첨가하여 고온 소결중 불순물을 휘발 제거시킴으로서 고순도 소결체를 얻게되어 열전자 방출 특성 및 마그네트론의 전자기적 특성 향상과 불량율을 적게하는 산화토륨-텅스텐와이어의 제조방법을 제공하고자 하는데 그 목적이 있다.The present invention has been made to solve the above-mentioned problems, and by adding a material having a strong affinity for impurities to volatilize the impurities during high temperature sintering to obtain a high-purity sintered body to improve the hot electron emission characteristics and the electromagnetic properties of the magnetron and It is an object of the present invention to provide a method for producing a thorium oxide-tungsten wire having a low defect rate.

이하, 본 발명을 설명한다.Hereinafter, the present invention will be described.

본 발명은 산화텅스텐 백중량부에 칼륨(K) 150~300ppm, 알루미늄(Al) 150~200ppm, 실리콘(Si) 150~400ppm, 칼슘(Ca) 50~100ppm을 혼합하여 이를 물에 용해시켜 수용액을 만들고, 이 수용액에 질산토륨을 1.4~3.5중량부 가하여 질산토륨이 산화텅스텐에 도핑되도록 한 후 건조하는 공정과, 환원분위기에서 환원한 후 성형하고 1차 예비소결하는 공정과, 상기 예비소결체를 2차 소결하는 공정과, 이어서 상기 소결체를 공지의 가공방법인 스웨징(Swaging), 드로잉(Drawing) 하는 공정으로 하여 산화토륨-텅스텐와이어(ThO2-W-Wire)을 얻게된다.The present invention mixes 150 to 300ppm of potassium (K), 150 to 200ppm of aluminum (Al), 150 to 400ppm of silicon (Si), and 50 to 100ppm of calcium (Ca) and dissolves it in water. 1.4 to 3.5 parts by weight of thorium nitrate is added to the aqueous solution so that the thorium nitrate is doped with tungsten oxide, followed by drying, reducing and reducing the mold in a reducing atmosphere, and preliminarily pre-sintering the second sintered body. Subsequently, the sintered body is subsequently subjected to swaging and drawing, which are known processing methods, to obtain thorium oxide-tungsten wire (ThO 2 -W-Wire).

상기한 공정을 구체적으로 설명하면 산화텅스텐 분말에 첨가되는 4종 첨가원소(K,Al,Si,Ca)는 불순물(C,Fe,Cr,Ni 등)과 친화력이 큰 원소로써 소결과정(2차소결) 중 최고온도(2,500~3,000℃)에 이르는 동안 지속적으로 불순물과 결합되어 다음식의 과정을 통해 휘발된다.Specifically, the four additive elements (K, Al, Si, Ca) added to the tungsten oxide powder are elements having a high affinity for impurities (C, Fe, Cr, Ni, etc.) and the sintering process (secondary) During the sintering), it is continuously combined with impurities for the maximum temperature (2,500 ~ 3,000 ℃) and volatilized through the following formula.

X : 첨가물 X*,Y*: 활성화상태 Y : 불순물 S : 고체상태 G : 기체상태X: Additive X * , Y * : Active state Y: Impurity S: Solid state G: Gas state

상기한 4종 원소를 조성함에 있어 그 범위가 하한치 이하 일때는 불순원소와 동반 휘발효과가 적고, 그 범위 이상일때는 소결과정중 완전히 휘발되지 않아 순도를 저해한다.In forming the above four elements, when the range is below the lower limit, the impurity element and the accompanying volatilization effect are small, and when the range is above the range, the volatilization is not completely volatilized during the sintering process to inhibit purity.

상기한 4종 원소를 혼합하고 여기에 물을 가해 용해하여 수용액을 만들고, 이 수용액을 산화텅스텐 분말에 가한다.The four elements mentioned above are mixed and water is added to dissolve it to make an aqueous solution, and this aqueous solution is added to the tungsten oxide powder.

그리고 여기에 질산토륨을 가해 도핑(doping)한 후 건조한다.Thorium nitrate is added thereto and doped, followed by drying.

이때 건조온도는 100~200℃에서 행함이 바람직하다.At this time, the drying temperature is preferably carried out at 100 ~ 200 ℃.

건조에 이어서 수소분위기 중 750~950℃ 온도, 2~3시간 환원처리한 후 성형하고, 1000~1300℃ 온도에서 20~120분간 예비소결하고, 2500~3000℃에서 20~60분간 소결함으로써 본 발명에서 필요로하는 소결체를 얻는다.Following drying, hydrogenation is carried out at a temperature of 750 to 950 ° C. for 2 to 3 hours, followed by molding, pre-sintering at 1000 to 1300 ° C. for 20 to 120 minutes, and sintering at 2500 to 3000 ° C. for 20 to 60 minutes. The sintered compact required is obtained.

소결온도를 2500~3000℃로 설정한 것은 상기 온도에 이르면 휘발온도범위(Ca : 1,400~1,800℃, Si : 1,600~2,000℃, Al : 2,000~2,400℃, K : 1,900~3,000℃)를 갖는 첨가원소가 소결과정중 불순원소가 지속적으로 결합되면서 휘발되어 제거된다.When the sintering temperature is set to 2500 to 3000 ° C., the addition has a volatile temperature range (Ca: 1,400 to 1,800 ° C., Si: 1,600 to 2,000 ° C., Al: 2,000 to 2,400 ° C., K: 1,900 to 3,000 ° C.). Elements are volatilized and removed as the impurities are continuously bonded during the sintering process.

이와 같은 공정을 거친 소결제를 통상의 가공방법인 스웨징 및 드로잉을 행하여 완성된 산화토륨-텅스텐와이어를 얻게된다.The sintering agent which has undergone such a process is subjected to swaging and drawing, which is a conventional processing method, to obtain a finished thorium-tungsten wire.

따라서 본 발명은 종래의 세척방법 보다 고온 소결중 동반 휘발시키는 공정을 이용하므로 분말입자 경계면에 숨어있는 불순물까지도 제거할 수 있어 높은 순도를 갖게된다.Therefore, the present invention uses a process of volatilizing during the high temperature sintering than the conventional washing method, it is possible to remove even impurities hidden in the powder particle interface has a high purity.

다음은 실시예에 따라 설명한다.The following is described according to the embodiment.

1) 산화텅스텐 분말 1kg에 K, Al, Si, Ca 전체에 첨가물의 양이 500~1000ppm이 되도록 정량한 후 300cc의 물에 완전히 수용액을 만들고 교반기에서 상기한 분말과 첨가물 수용액과 질산토륨 수용액을 모두 장입하고 교반기에서 1~2hr 교반 후 100~200℃로 가열 건조하여 원료 산화 텅스텐 분말을 만든다.1) 1kg of tungsten oxide powder is quantified to the amount of additives in the whole of K, Al, Si, and Ca to 500 ~ 1000ppm, and then completely made an aqueous solution in 300cc of water, and the powder, additive aqueous solution and thorium nitrate aqueous solution After charging and stirring for 1 ~ 2hr in a stirrer, it was heated and dried to 100 ~ 200 ℃ to make raw tungsten oxide powder.

2) 상기한 분말을 750~950℃에서 2~3hr 수소환원하여 1.5~4.0㎛의 텅스텐 분말을 제조한 후 성형하고 1000~1300℃ 온도에서 예비소결한다.2) The above-mentioned powder is hydrogen-reduced at 750-950 ° C. for 2 to 3 hours to prepare 1.5-4.0 μm tungsten powder, then molded and presintered at 1000-1300 ° C.

3) 상기한 예비소결체를 융단전류 87~95%에서 25~50분간 통전소결하여 16.5~18.5g/㎤ 밀도를 갖는 소결체를 제조한다.3) The presintered body was energized and sintered for 25 to 50 minutes at a melt current of 87 to 95% to prepare a sintered body having a density of 16.5 to 18.5 g / cm 3.

4) 상기한 소결체를 스웨징과 드로잉 공정을 거쳐 고온 기계적 강도, 열전자 방출성, 전자기적 특성이 우수한 1% ThO2-W Wire를 제조한다.4) The above sintered body is subjected to swaging and drawing to manufacture 1% ThO 2 -W Wire having excellent high temperature mechanical strength, hot electron emission, and electromagnetic properties.

상기한 공정을 통한 불순물 제거 및 그에 따른 특성 결과는 (표1) 및 (표2)와 같이 나타났다.Impurity removal through the above process and the characteristic results thereof are shown in Tables 1 and 2.

[표1]Table 1

불순물 함량Impurity content

[표2][Table 2]

마그네트론 전자방출성, 전자기적 특성, 제조불량율Magnetron electron emission, electromagnetic characteristics, manufacturing defect rate

Claims (1)

산화텅스텐 백중량부에 칼륨(K) 150~300ppm, 알루미늄(Al) 150~200ppm, 실리콘(Si) 150~400ppm, 칼슘(Ca) 50~100ppm을 혼합한 후 물에 용해하여 만든 수용액과 질산토륨 1.4~3.5중량부를 물에 용해하여 만든 수용액을 혼합하여 100~200℃에서 건조하는 공정과, 환원분위기에서 750~950℃, 2~3시간 환원 후 성형하고 1,000~1,300℃, 20~120분간 1차 예비 소결한 소결체를 2,500~3,000℃, 20~60분간 2차 소결하여 소결체를 얻는 공정과, 상기 소결체를 스웨징(Swaging), 드로잉(Drawing)하는 공정으로 이루어짐을 특징으로 하는 산화토륨-텅스텐와이어(ThO2-W Wire)의 제조방법.An aqueous solution and thorium nitrate prepared by mixing potassium (K) 150-300ppm, aluminum (Al) 150-200ppm, silicon (Si) 150-400ppm and calcium (Ca) 50-100ppm in a white weight part of tungsten oxide 1.4-3.5 parts by weight of an aqueous solution made by dissolving in water, and drying at 100-200 ℃, and reduced to 750 ~ 950 ℃, 2 to 3 hours in a reducing atmosphere and molded and 1,000 ~ 1,300 ℃, 20 to 120 minutes 1 Thorium oxide-tungsten, comprising the steps of obtaining a sintered body by secondary sintering of the pre-sintered sintered body at 2,500 to 3,000 ° C. for 20 to 60 minutes, and swaging and drawing the sintered body. Method of manufacturing wire (ThO 2 -W Wire).
KR1019940010790A 1994-05-17 1994-05-17 Method of manufacturing tho2-w wire KR960012870B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
KR1019940010790A KR960012870B1 (en) 1994-05-17 1994-05-17 Method of manufacturing tho2-w wire

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
KR1019940010790A KR960012870B1 (en) 1994-05-17 1994-05-17 Method of manufacturing tho2-w wire

Publications (2)

Publication Number Publication Date
KR950031329A KR950031329A (en) 1995-12-18
KR960012870B1 true KR960012870B1 (en) 1996-09-25

Family

ID=19383258

Family Applications (1)

Application Number Title Priority Date Filing Date
KR1019940010790A KR960012870B1 (en) 1994-05-17 1994-05-17 Method of manufacturing tho2-w wire

Country Status (1)

Country Link
KR (1) KR960012870B1 (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111940753B (en) * 2020-08-27 2022-10-28 崇义章源钨业股份有限公司 System and method for preparing ultra-coarse tungsten powder

Also Published As

Publication number Publication date
KR950031329A (en) 1995-12-18

Similar Documents

Publication Publication Date Title
JP2005035885A (en) Niobium suboxide powder, niobium suboxide anode and solid-state electrolytic capacitor
JP2024518762A (en) METHOD FOR PRODUCING TANTALUM POWDER AND TANTALUM POWDER OBTAINED BY THE METHOD
US5590386A (en) Method of making an alloy of tungsten and lanthana
KR960012870B1 (en) Method of manufacturing tho2-w wire
EP0765949B1 (en) Tungsten-lanthana alloy wire for a vibration resistant lamp filament
US2798808A (en) Method of introducing zirconia into tungsten powder preliminary to forming electrodes
US3375109A (en) Process for preparing rheniumrefractory alloys
EP0523651B1 (en) Method for making high strength injection molded ferrous material
US3136039A (en) Tungsten alloy
JP2024515196A (en) Method for producing tantalum powder for capacitors by reducing tantalum oxide with alkaline earth metals
US1731255A (en) Alloy and its manufacture
JPS6033335A (en) Heat resistant molybdenum material
CN110983087B (en) Method for improving oxide distribution in yttrium oxide dispersion strengthening tungsten alloy
JP4256126B2 (en) Tungsten-rhenium material and method for producing the same, cathode heater for cathode ray tube made of this tungsten-rhenium material, tube filament, and probe pin for electrical property inspection
JP3121400B2 (en) Manufacturing method of tungsten sintered body
JP2730284B2 (en) Manufacturing method of Al-Si alloy sintered forged parts
JPH0762467A (en) Dispersion-strengthening type copper alloy and its production
JPH08120310A (en) Production of copper-tungsten mixed powder
US1760367A (en) Ductile chromium and method of producing the same
US1760413A (en) Zirconium and preparation thereof
JPS6026621A (en) Manufacture of heat resistant molybdenum material
JPS59177305A (en) Production of molybdenum powder and molybdenum material
JPH06128604A (en) Production of metallic material
CN114367664A (en) Process for preparing non-shrinking tungsten skeleton by wet method
JPH07188702A (en) Ag-base alloy powder and its production

Legal Events

Date Code Title Description
A201 Request for examination
E902 Notification of reason for refusal
G160 Decision to publish patent application
E701 Decision to grant or registration of patent right
GRNT Written decision to grant
LAPS Lapse due to unpaid annual fee