KR100321295B1 - Ceramics-aluminum composite and its preparation method - Google Patents
Ceramics-aluminum composite and its preparation method Download PDFInfo
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- KR100321295B1 KR100321295B1 KR1019990024270A KR19990024270A KR100321295B1 KR 100321295 B1 KR100321295 B1 KR 100321295B1 KR 1019990024270 A KR1019990024270 A KR 1019990024270A KR 19990024270 A KR19990024270 A KR 19990024270A KR 100321295 B1 KR100321295 B1 KR 100321295B1
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- aluminum
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- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 63
- 239000002131 composite material Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title 1
- 239000000843 powder Substances 0.000 claims abstract description 58
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000000919 ceramic Substances 0.000 claims abstract description 33
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000009736 wetting Methods 0.000 claims abstract description 12
- 230000000704 physical effect Effects 0.000 claims abstract description 9
- 239000011248 coating agent Substances 0.000 claims abstract description 7
- 238000000576 coating method Methods 0.000 claims abstract description 7
- 239000012153 distilled water Substances 0.000 claims abstract description 6
- 229910000838 Al alloy Inorganic materials 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims description 25
- 229910052799 carbon Inorganic materials 0.000 claims description 21
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 15
- 239000012298 atmosphere Substances 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 2
- 239000012300 argon atmosphere Substances 0.000 abstract description 15
- 238000004381 surface treatment Methods 0.000 abstract description 8
- 239000002243 precursor Substances 0.000 abstract description 2
- 238000005470 impregnation Methods 0.000 description 27
- 238000006243 chemical reaction Methods 0.000 description 16
- 238000005452 bending Methods 0.000 description 12
- 230000005484 gravity Effects 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000005245 sintering Methods 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 239000011812 mixed powder Substances 0.000 description 4
- -1 cermets Chemical class 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000013001 point bending Methods 0.000 description 3
- 238000007088 Archimedes method Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 229910003481 amorphous carbon Inorganic materials 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 239000011195 cermet Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000010191 image analysis Methods 0.000 description 2
- 230000008595 infiltration Effects 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005242 forging Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 238000007542 hardness measurement Methods 0.000 description 1
- 230000002706 hydrostatic effect Effects 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000011505 plaster Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000007569 slipcasting Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D85/00—Containers, packaging elements or packages, specially adapted for particular articles or materials
- B65D85/70—Containers, packaging elements or packages, specially adapted for particular articles or materials for materials not otherwise provided for
- B65D85/72—Containers, packaging elements or packages, specially adapted for particular articles or materials for materials not otherwise provided for for edible or potable liquids, semiliquids, or plastic or pasty materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D25/00—Details of other kinds or types of rigid or semi-rigid containers
- B65D25/14—Linings or internal coatings
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D39/00—Closures arranged within necks or pouring openings or in discharge apertures, e.g. stoppers
- B65D39/08—Threaded or like closure members secured by rotation; Bushes therefor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D51/00—Closures not otherwise provided for
- B65D51/16—Closures not otherwise provided for with means for venting air or gas
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D51/00—Closures not otherwise provided for
- B65D51/24—Closures not otherwise provided for combined or co-operating with auxiliary devices for non-closing purposes
- B65D51/249—Closures not otherwise provided for combined or co-operating with auxiliary devices for non-closing purposes the closure being specifically formed for supporting the container
Abstract
본 발명은 세라믹스-알루미늄 복합체 및 그 제조방법에 관한 것으로서, 본 발명은 세라믹 분말을 알루미나 졸로 표면처리하여 알루미늄의 웨팅(wetting)을 향상시킴으로써 알루미늄을 완전하게 함침시킨 세라믹스-알루미늄 복합체를 제공한다. 또한 본 발명은 증류수에 분산된 세라믹 분말에 알루미나 졸을 첨가하여 세라믹 분말 표면을 알루미나 전구체로 코팅시키고, 상기 코팅에 의해 표면처리되어 알루미늄의 웨팅이 향상된 세라믹 분말의 성형체를 제조한 후, 상기 성형체를 1200℃ 이상의 고온으로 진공 또는 아르곤 분위기에서 미리 열처리 하거나, 이러한 전처리 없이 성형한 그대로 진공 또는 대기압의 아르곤 분위기에서 알루미늄 합금을 함침시키는 것을 특징으로 하는 세라믹스-알루미늄 복합체 제조방법을 제공한다. 본 발명에 의하면 균일한 내부구조를 갖고 불필요한 상들을 억제시킨 우수한 물성의 세라믹스-알루미늄 복합체를 얻을 수 있으며, 공정상 간단하고 용이하며 경제적인 세라믹스-알루미늄 복합체 제조가 가능하게 된다.The present invention relates to a ceramics-aluminum composite and a method of manufacturing the same. The present invention provides a ceramics-aluminum composite in which aluminum is completely impregnated by improving the wetting of aluminum by surface-treating the ceramic powder with an alumina sol. In addition, the present invention is to add alumina sol to the ceramic powder dispersed in distilled water to coat the surface of the ceramic powder with an alumina precursor, the surface treatment by the coating to produce a molded body of the ceramic powder with improved wetting of aluminum, the molded body Provided is a method for producing a ceramics-aluminum composite, characterized in that the aluminum alloy is impregnated in a vacuum or argon atmosphere at a high temperature of 1200 ° C. or higher in advance in a vacuum or argon atmosphere without being preformed. According to the present invention, it is possible to obtain a ceramic-aluminum composite of excellent physical properties having a uniform internal structure and suppressing unnecessary phases, and to manufacture a ceramic-aluminum composite which is simple, easy and economical in the process.
Description
본 발명은 세라믹스-알루미늄 복합체 및 그 제조방법에 관한 것이다.The present invention relates to a ceramic-aluminum composite and a method of manufacturing the same.
세라믹스는 비중이 작고, 강도는 높으나 깨지기 쉬운 단점이 있고, 금속은 깨지지는 않으나 강도가 낮은 단점이 있다. 다라서 서로의 단점을 보완하고, 장점을 살리기 위해 세라믹스와 금속간의 복합체 즉, 서멧(cermet)에 대한 연구가 많이 수행되어 오고 있다. 특히 가볍고 내산화성이 우수한 알루미늄과 세라믹스 사이의 복합체 연구가 활발히 진행되어오고 있다.Ceramics have a disadvantage of low specific gravity, high strength but brittleness, and metals that have low strength. Therefore, many researches have been conducted on composites between ceramics and metals, namely, cermets, in order to compensate each other's shortcomings and to make use of the advantages. In particular, research on composites between aluminum and ceramics, which are lightweight and excellent in oxidation resistance, has been actively conducted.
알루미늄 서멧 제조방법으로는 세라믹 성형체에 알루미늄을 함침(infiltration)시키는 방법, Lanxide와 같이 알루미늄을 산화시켜 Al/Al2O3복합체를 만드는 방법, 세라믹 성형체를 부분 소결시킨 후 용융알루미늄을 가압으로 기공사이에 스며들게 하는 방법 등이 있다.The aluminum cermet manufacturing method involves infiltration of aluminum into the ceramic formed body, oxidation of aluminum to form Al / Al 2 O 3 composites, such as Lanxide, and the sintering of the ceramic formed by pressing molten aluminum after partial sintering. There are ways to soak in.
가볍고 강도가 높은 B4C/Al 복합체의 경우 구조 재료외에 방탄재료로 각광을 받고 있어 많은 연구가 이루어져 왔다. 다른 세라믹, 예컨데 SiC, TiB2, Al2O3, TiC 등 과는 달리 B4C는 Al과 반응이 잘 일어나기 때문에 B4C와 Al 사이의 반응을 억제하고 Al의 함침을 유도하기 위해서는 B4C의 표면개질이 필요하며, 이를 위하여 복잡한 여러 공정들이 알려져 있다.Light and high strength B 4 C / Al composite has been spotlighted as a bulletproof material in addition to the structural material has been studied a lot. Another ceramic, for example SiC, TiB 2, Al 2 O 3, TiC, etc., because, unlike the B 4 C will take place well Al and reaction B 4 inhibit the reaction between C and Al and to lead to impregnation of the Al B 4 Surface modification of C is required, for which a number of complex processes are known.
일반적으로 세라믹스-알루미늄 복합체는 고온에서 반응의 제어가 용이하지 않고 원치 않는 반응생성물이 발생하여 우수한 성질을 갖는 복합체 제조에 어려움이 있다. B4C의 경우 Al과 450℃ 이상에서 반응하기 시작하는데, 온도가 올라갈수록 반응속도가 빨라지고, 반응성 함침(reactive infiltration)이 일어나 반응중에 함침이 이루어질 뿐만아니라 여러 가지 반응물, 예컨대 AlB2, Al4BC, AlB12C2, AlB12, Al4C3, Al3BC 등이 생성된다. 또한 상기 반응중 반응속도를 마음대로 조절할 수 없어 대부분의 Al이 소모되므로 B4C와 Al의 복합체를 제조하기가 용이하지 않다. 반면 SiO2, TiB2, Al2O3, TiC 의 경우에는 Al과의 반응이 없이 함침이 일어난다. 따라서 B4C/Al 복합체를 제조하기 위해서는 Al이 B4C와 반응하기 전에 함침이 먼저 일어나는 것이 바람직하다. 즉, Al이 B4C와 반응하기 전에 용융 알루미늄의 함침이 빠르게 일어나야 한다. 한편 함침이 일어나기 위해서는 우선 알루미늄의 웨팅이 일어나야만 한다. 따라서 세라믹스 성형체에 Al의 웨팅을 일어나게 하는 방법이 B4C/Al 복합체 제조의 주요 핵심기술이라 할 수 있고, 대부분의 특허는 이와 관련된 분야에 집중되고 있다.In general, ceramics-aluminum composites are not easy to control the reaction at high temperatures, and unwanted reaction products are generated, which makes it difficult to prepare a composite having excellent properties. In case of B 4 C, it starts to react with Al at 450 ° C or higher. As the temperature increases, the reaction rate increases, and reactive infiltration occurs to impregnate the reaction, and various reactants such as AlB 2 and Al 4. BC, AlB 12 C 2 , AlB 12 , Al 4 C 3 , Al 3 BC and the like are produced. In addition, the reaction rate during the reaction can not be adjusted at will, most Al is consumed, so it is not easy to prepare a complex of B 4 C and Al. On the other hand, in the case of SiO 2 , TiB 2 , Al 2 O 3 , TiC, impregnation occurs without reaction with Al. Therefore, in order to prepare a B 4 C / Al complex, it is preferable that impregnation occurs first before Al reacts with B 4 C. That is, impregnation of molten aluminum must occur quickly before Al reacts with B 4 C. In order for impregnation to occur, on the other hand, wetting of aluminum must occur first. Therefore, the method of causing the wetting of Al on the ceramic molded body can be said to be the main core technology for the production of B 4 C / Al composite, and most patents are focused on the related fields.
B4C/Al복합체를 들어 종래의 세라믹스-알루미늄 복합체 제조기술을 살펴보면 다음과 같다.Looking at the conventional ceramics-aluminum composite manufacturing technology for the B 4 C / Al composite as follows.
미국특허 3,864,154의 경우는 Al에 Si을 혼합함으로써 Si가 습윤제(wetting agent)의 역할이 되게 하였다. B4C 경우에는 구체적인 함침조건을 알 수 없으나, AlB12을 이용하였을 때에는 10-5torr에서 1×0.3 인치의 펠렛에 Al을 함침시키기 위해 1100℃에서 3시간 유지시켰으며, 미국특허 3,725,050에서는 B4C 분말에 열분해시 미량의 무정형 탄소를 남길 수 있는 유기물을 첨가하여 B4C 성형체를 제조하여 Al의 함침이 일어나도록 하였다. 또한, 미국특허 3,718,441에서는 Al 표면의 산화막을 진공하에서 열처리로 제거하여 웨팅을 촉진시켰으며, 미국특허 2,612,443에서는 성형체를 약하게 소결한 후 용융금속을 가압하에서 기공사이로 밀어넣는 방법을 이용하였다.In the case of US Pat. No. 3,864,154, Si is mixed with Al so that Si becomes a wetting agent. In the case of B 4 C, specific impregnation conditions are not known, but when AlB 12 is used, it is maintained at 1100 ° C. for 3 hours to impregnate 1 × 0.3 inch pellets at 10 −5 torr, and in US Pat. No. 3,725,050, B The 4 C powder was added with an organic material that can leave a trace of amorphous carbon when pyrolyzed to prepare a B 4 C molded product to cause impregnation of Al. In addition, US Pat. No. 3,718,441 promotes wetting by removing the oxide film on the Al surface by heat treatment under vacuum, and US Pat. No. 2,612,443 uses a method in which the molten metal is pressed into the pores under pressure after weakly sintering the molded body.
한편, 미국특허 4,605,440에서는 B4C 분말과 Al 분말을 알코올에서 혼합한 후 석고몰드에서 슬립 캐스팅(Slip casting)하여 성형체를 얻은 후 1050℃ ∼ 1200℃에서 10분간 열처리하고 온도를 800℃로 낮추어 24시간 동안 후열처리하여 B4C/Al복합체를 제조하였는데, B4C와 Al함량이 감소하는 반면, B4C와 Al사이의 여러 반응생성물, 예컨대, AlB2, Al4BC, AlB12C2, AlB12, Al4C3등이 생성되었다. 그 중 1200℃의 온도에서 열처리한 것은 Al4BC가 34 vol%로 가장 많다고 한다. 비중에 대한 자료가 없어 정확히 알 수 없으나, 완전한 소결은 일어나지 못한 것으로 생각된다. PCT WO87/00557에서는 B4C성형체에는 순수 Al의 함침이 일어나지 못하지만, 유기물의 열분해로 생성되는 잔류탄소가 Al에 대한 웨팅을 촉진시킨다는 앞의 자료에 착안하여 B4C 성형체를 탄소로(graphite furnace)를 사용하여 진공하에 1800℃ ∼ 2250℃의 온도에서 열처리하여 약간의 잉여탄소가 남아있는 부분소결된 B4C성형체를 제조하여 B4C와 Al 사이의 심한 반응을 억제시킴으로써, B4C와 Al 사이의 반응 생성물이 적게 포함된B4C/Al복합체를 제조하는 것이다. 예컨대, B4C 성형체는 석고몰드에 슬립 캐스팅하여 제조하고 이것을 진공로를 이용하여 2150℃에서 30분간 열처리하여 약64%의 밀도를 가진 B4C 성형체를 제조한 후 이것을 용융 Al에 넣어 10-2torr 압력하에 1190℃에서 30분간 유지하여 B4C/Al복합체를 제조하는 것으로, Al(31%)과 B4C(64%)가 대부분을 차지하며, 나머지는 Al4BC, AlB12, AlB12C2가 소량 생성된다. 즉 약간의 잉여 탄소와 부분소결로 인해 B4C와 Al의 반응이 억제되는 것을 알 수 있다. 함침온도는 진공하에 1150℃ ∼ 1250℃, 열처리 온도는 자유 탄소(free C)가 있는 곳에서 1800℃ ∼ 2250℃을 주장하고 있다. 미국특허 4,718,941과 유럽특허 0 250 210 A2에서는 B4C 분말을 알코올 등의 유기용매에 침지하여 분말의 표면화학 성질을 변화시켜 알루미늄의 함침을 촉진시키는 것인 바, 함침은 진공하에 1050℃ ∼ 1180℃의 온도에서 일어난다고 한다. 미국특허 4,744,943과 5,298,468에서는 B4C(0.1 ∼ 3㎛)와 Al (<325 mesh)을 건식 혹은 습식으로 혼합한 후 제조한 성형체를 저탄소함유 강관(low carbon steel can)에 넣고 성형체와 강관 사이를 Al 분말로 채우고 600℃로 가열 한 후 단조용 프레스로 옮겨 120,000 psi(8270기압)에서 30초간 가압하여 성형하는 것이다. 이 방법에서는 98%의 이론 밀도를 얻을 수 있으며, Al의 양이 처음에 넣은 30%에서 16 ∼ 22%로 줄어 든다. 이렇게 제조된 B4C/Al 복합체는 열처리 조건을 변화시킴으로써 조금씩 다른 조성의 복합체를 만들 수 있으며, 그에 따라 물성도 달라진다고 한다. 또한, PCT WO 94/02655 에서는 B4C 성형체를 먼저 진공하에 1250℃ ∼ 1800℃의 온도에서 30분 이상 열처리하면, Al의 함침속도를 촉진시킴과 동시에 완전한 함침이 이루어진다고 한다. 1300℃에서 30분간 열처리한 B4C 성형체에 Al 조각을 올려놓고 10-1torr 하에 1180℃의 온도에서 105분간 열처리하여 Al이 3.6 vol% 로 낮고 대신 AlB2가 17.0vol%, Al4BC가 18.6vol%의 B4C/Al복합체를 제조할 수 있으며, 이 방법에서는 원치않는 Al4C3(< 1 wt%)가 생성된다고 한다.On the other hand, US Patent 4,605, 440 is mixed with B 4 C powder and Al powder in alcohol and then slip cast in gypsum mold to obtain a molded product, and then heat treated at 1050 ℃ ~ 1200 ℃ for 10 minutes and lowered the temperature to 800 ℃ 24 After heat treatment for a time to prepare a B 4 C / Al complex, while the content of B 4 C and Al decrease, while several reaction products between B 4 C and Al, such as AlB 2 , Al 4 BC, AlB 12 C 2 , AlB 12 , Al 4 C 3 and the like were produced. Among them, the most heat treated at a temperature of 1200 ℃ Al 4 BC is said to be the most 34 vol%. Although no specific data are available on specific gravity, complete sintering is not believed to occur. In PCT WO87 / 00557, the B 4 C molded product is not impregnated with pure Al, but the B 4 C molded product is converted into carbon by focusing on the previous data that residual carbon generated by pyrolysis of organic materials promotes wetting on Al. ) and by heat treatment at a temperature of 1800 ℃ ~ 2250 ℃ under vacuum to manufacture the parts of sintered B 4 C shaped body with a slight excess carbon remains to inhibit severe reaction between B 4 C and Al, B 4 C and using It is to prepare a B 4 C / Al complex containing less reaction product between Al. For example, B 4 C shaped bodies were prepared by slip casting in a plaster mold and to do this by using a vacuum heat treatment at 2150 ℃ 30 bungan producing a B 4 C shaped body having a density of about 64% to put it in a molten Al 10 - A B 4 C / Al composite was prepared by maintaining the mixture at 1190 ° C. for 30 minutes under 2 torr pressure. Al (31%) and B 4 C (64%) accounted for the majority, and Al 4 BC, AlB 12 , A small amount of AlB 12 C 2 is produced. In other words, it can be seen that the reaction of B 4 C and Al is suppressed due to some excess carbon and partial sintering. The impregnation temperature insisted at 1,150 to 1250 ° C under vacuum and the heat treatment temperature at 1800 to 2250 ° C in the presence of free C. In US Patent 4,718,941 and European Patent 0 250 210 A2, B 4 C powder is immersed in an organic solvent such as alcohol to change the surface chemical properties of the powder to promote aluminum impregnation. The impregnation is performed at 1050 ° C to 1180 under vacuum. It is said to occur at a temperature of ℃. In US Pat. Nos. 4,744,943 and 5,298,468, a molded product prepared by mixing B 4 C (0.1-3 μm) and Al (<325 mesh) in a dry or wet manner is placed in a low carbon steel can and is placed between the molded body and the steel pipe. It is filled with Al powder, heated to 600 ° C, and then transferred to a forging press for 30 seconds at 120,000 psi (8270 atm) for molding. In this method, a theoretical density of 98% can be obtained, and the amount of Al is reduced from the first 30% to 16-22%. The B 4 C / Al composite thus prepared can be made a composite of a slightly different composition by changing the heat treatment conditions, the physical properties are also changed accordingly. In PCT WO 94/02655, the B 4 C molded body is first heat-treated under vacuum at a temperature of 1250 ° C. to 1800 ° C. for 30 minutes or more to accelerate the impregnation rate of Al and to achieve complete impregnation. The Al piece was placed on a B 4 C molded body which was heat-treated at 1300 ° C. for 30 minutes, and heat-treated at 105 ° C. at 10 ° C. for 10 minutes at 10 to 1 torr, whereby Al was 3.6 vol% and AlB 2 was 17.0 vol% and Al 4 BC was An 18.6 vol% B 4 C / Al complex can be prepared, which produces an undesirable Al 4 C 3 (<1 wt%).
이와 같이 종래의 공지된 방법으로 제조한 B4C/Al복합체는 고온에서의 성형체 전열처리, 진공에서의 함침, 특수한 공정이 수행되는 등 공정상의 어려움이 있었다. 뿐만아니라 B4C와 Al의 계면(interface)구조와 B4C의 내부(bulk)구조가 상이하며, 제조된 복합체의 미세구조가 일반적으로 균일하지 못하여 물성에도 크게 영향을 미치고 있다. 또한 공정에 따라, B4C와 Al 외에 AlB2, Al4BC, AlB24C4, Al4C3, AlB12과 같은 많은 상들이 동반되어 물성 제어에 문제점이 있었다. 특히 Al4C3는 공기 중의 수분과 작용하여 분해하므로, 이 물질이 생성되지 않도록 주의해야 할 필요가 있었다.As described above, the B 4 C / Al composite prepared by a conventionally known method has difficulty in processing, such as heat treatment of a molded body at a high temperature, impregnation in a vacuum, and a special process. In addition, the interface structure of B 4 C and Al and the bulk structure of B 4 C are different, and the microstructure of the manufactured composite is generally not uniform, which greatly affects physical properties. In addition, depending on the process, in addition to B 4 C and Al, there are many phases such as AlB 2 , Al 4 BC, AlB 24 C 4 , Al 4 C 3 , AlB 12 has a problem in controlling the properties. In particular, Al 4 C 3 is decomposed by working with water in the air, it was necessary to be careful not to produce this material.
본 발명은 상기의 문제점을 해결하여, 세라믹 분말의 표면에 알루미나 전구체를 코팅하여 알루미늄의 함침을 용이하게 하고 균일한 미세구조를 가지며 불필요한 상의 형성을 억제시킨 우수한 물성의 세라믹스-알루미늄 복합체 및 공정상 간단하고 용이하며 경제적인 세라믹스-알루미늄 복합체 제조방법을 제공하는 것을 목적으로 한다.The present invention solves the above problems, coating the alumina precursor on the surface of the ceramic powder to facilitate the impregnation of aluminum, has a uniform microstructure and suppressed the formation of unnecessary phases and ceramics-aluminum composite of excellent physical properties and process simple An object of the present invention is to provide a method for producing a ceramics-aluminum composite, which is easy and economical.
도 1은 본 발명에 의한 알루미나졸로 표면처리된 B4C/Al 복합체의 단면을 광학현미경으로 관찰한 사진이다.Figure 1 is a photograph of the cross-sectional view of the B 4 C / Al composite surface-treated with alumina sol according to the present invention.
도 2는 알루미나졸로 표면처리되지 않은 B4C/Al 복합체의 단면을 광학현미경으로 관찰한 사진이다.Figure 2 is a photograph of the cross-sectional view of the B 4 C / Al composite surface not treated with alumina sol by optical microscope.
본 발명은 세라믹스-알루미늄 복합체 및 그 제조방법에 관한 것으로서, 본 발명은 세라믹 분말의 표면을 알루미나(Al2O3) 졸로 표면처리하여 알루미늄의 웨팅을 향상시킴으로써 알루미늄을 완전하게 함침시킨 세라믹스-알루미늄 복합체를 제공한다.The present invention relates to a ceramics-aluminum composite and a method of manufacturing the same. The present invention relates to a ceramics-aluminum composite in which aluminum is completely impregnated by improving the wetting of aluminum by treating the surface of the ceramic powder with an alumina (Al 2 O 3 ) sol. To provide.
또한 본 발명은 증류수에 분산된 세라믹 분말에 알루미나 졸을 첨가하여 세라믹 분말 표면을 코팅시키고, 상기 코팅에 의해 표면개질된 세라믹 분말을 건조시켜 성형체를 제조한 후, 상기 성형체를 1200℃ 이상의 고온으로 진공 또는 불활성가스 분위기에서 미리 열처리 하거나, 이러한 전처리 없이 성형한 그대로 진공 또는 대기압의 불활성가스 분위기에서 알루미늄 합금을 함침시키는 것을 특징으로 하는 세라믹스-알루미늄 복합체 제조방법을 제공한다.In addition, the present invention is to add alumina sol to the ceramic powder dispersed in distilled water to coat the surface of the ceramic powder, and to dry the surface-modified ceramic powder by the coating to prepare a molded body, and then vacuum the molded body at a high temperature of 1200 ℃ or more Alternatively, the present invention provides a method for producing a ceramics-aluminum composite, characterized in that the aluminum alloy is impregnated in an inert gas atmosphere under vacuum or atmospheric pressure as it is pre-heated in an inert gas atmosphere or molded without such pretreatment.
상기 알루미늄을 함침시킨 세라믹스에는 B4C, TiB2, TiC, B4C-TiB2또는 B4C-Al2O3등의 구조재료용 세라믹스가 포함된다. 한편, 본 발명에 의한 세라믹스-알루미늄 복합체 제조방법은 알루미늄을 함침시킨 후 후열처리에 의해 복합체의 물성을 변화시키는 단계가 추가될 수 있다.Ceramics impregnated with aluminum include ceramics for structural materials such as B 4 C, TiB 2 , TiC, B 4 C-TiB 2, or B 4 C-Al 2 O 3 . On the other hand, in the method of manufacturing a ceramics-aluminum composite according to the present invention, after impregnating aluminum, a step of changing physical properties of the composite by post-heat treatment may be added.
일반적으로 사용되는 B4C(HP grade, H. C. Starck사, 독일) 분말의 제타 포텐셜(zeta potential)은 슬러리 농도에 따라 다소 차이가 있으나 pH3∼pH10의 범위에서는 -40 ∼ -60 mV이다. 이러한 상기 B4C 슬러리에 0.5 wt%의 알루미나 졸을 첨가하고, 몇 분 동안 교반하면 제타 포텐셜이 -58 mV에서 12mV로 급격히 변화하며, 2.0 wt%의 알루미늄 졸을 첨가하면 30 mV에 이른다. 그러나, 알루미나 졸을 3.0wt%첨가하면 33mV에 이르고 큰 증가는 나타나지 않는다. 이는 알루미나 졸이 B4C 분말 표면에 흡착되어 B4C 분말 표면의 화학성질을 변화시키는 것으로 사료된다. 상기의 알루미나 졸은 특허공고 제 1993-5318호에 나타난 바와 같이 고분자 알루미나 졸이며 열처리조건에 따라 미량의 탄소가 함유될 수 있는 알루미나로 변한다. 이 졸은 세라믹스 분말을 알루미나로 코팅시켜 표면개조에 유용하게 사용할 수 있다.Zeta potential of commonly used B 4 C (HP grade, HC Starck, Germany) powder varies slightly depending on slurry concentration, but is -40 to -60 mV in the range of pH 3 to pH 10. 0.5 wt% of alumina sol was added to the B 4 C slurry, followed by stirring for several minutes, and the zeta potential rapidly changed from -58 mV to 12 mV, and to 2.0 mV of aluminum sol to 30 mV. However, addition of 3.0 wt% of alumina sol reaches 33 mV and no significant increase appears. It is believed that the alumina sol is adsorbed by the B 4 C powder surfaces change the chemical properties of the B 4 C powder surface. The alumina sol is a polymer alumina sol, as shown in Patent Publication No. 1993-5318 and is converted into alumina which may contain a trace amount of carbon depending on the heat treatment conditions. This sol can be useful for surface modification by coating ceramic powder with alumina.
상기 알루미나 졸은 20 ~ 70몰의 증류수를 약 60℃로 가열하고, 포름산을 1 ~ 4몰 넣어 섞은 후 가열속도를 낯추고 1몰의 알콕사이드를 천천히 가하며 교반을 계속하고, 첨가가 끝난 후 60 ~ 80℃에서 0.5 ~ 30시간 반응시키는 방법으로 얻는다.The alumina sol is heated 20 ~ 70 moles of distilled water to about 60 ℃, 1 ~ 4 moles of formic acid is mixed, the heating rate is slowed down and slowly adding 1 mole of alkoxide to continue stirring, 60 ~ after the addition is complete It is obtained by the reaction at 80 ° C. for 0.5 to 30 hours.
반응성 함침이 일어나는 경우인 B4C와 Al의 경우에는 B4C분말표면을 알루미나로 코팅시켜 Al과의 반응을 억제시키려 하였다. 이때 알루미나 분말을 사용하는 것보다 알루미나 졸을 사용하여 코팅하는 것이 첨가제로서의 성능을 크게 한다. 또한 단결정 알루미나에 미량의 무정형 탄소를 입혔을 때 알루미늄의 웨팅 각이 낮아지고, B4C 분말에 과잉의 탄소(C rich B4C)가 Al의 함침을 촉진시킨다는 사실이 앞에서 인용한 공지 특허들에 보고되었다.In case of B 4 C and Al, which are reactive impregnations, the surface of B 4 C powder was coated with alumina to suppress the reaction with Al. In this case, coating with alumina sol rather than using alumina powder increases the performance as an additive. In addition, the fact that a small amount of amorphous carbon is applied to single crystal alumina lowers the wetting angle of aluminum, and that the excess carbon (C rich B 4 C) in the B 4 C powder promotes the impregnation of Al in the above-mentioned patents. Reported.
상기 사실들을 근거로 하여, 본 발명은 Al을 함침시켜 세라믹스-알루미늄 복합체를 제조할 때, 세라믹스와 Al의 반응을 억제시키고 용융 Al의 함침을 촉진시키기 위하여 알루미나 졸을 사용함으로써 세라믹 분말을 미리 표면처리하는 것에 특징을 두고있다. 또한 Al을 함침시키기 위하여 고온에서 일정시간 열처리할 뿐만아니라 일정온도에서 일정시간 후열처리하여 복합체의 물성을 변화시키는 것에 특징을 두고 있다.Based on the above facts, the present invention provides a surface treatment of the ceramic powder in advance by using alumina sol to suppress the reaction of Al and promote the impregnation of molten Al when impregnating Al to produce a ceramic-aluminum composite. It is characterized by doing. In addition, in order to impregnate Al, it is characterized by not only heat treatment at a high temperature for a certain time, but also post-heat treatment at a constant temperature for changing the physical properties of the composite.
본 발명에 있어서 첨가되는 알루미나 졸의 양은 세라믹 분말에 대하여 0.1 ~ 3wt%의 범위가 적당하다. 또한 함침시키는 알루미늄 합금의 양은 세라믹 성형체에 대하여 35 ~ 50vol%가 적당하다. 함침 조건에 있어서는, 세라믹스의 경우 분말의 입도가 작을수록 보다 낮은 온도에서 함침이 일어나는데, 대기압의 불활성분위기보다는 진공 중에서 함침시키는 것이 세라믹 분말의 크기와 종류에 따라 30 ~ 50℃정도 낮게 일어나므로 진공 중에서 알루미늄의 함침온도는 1000 ∼ 1200℃의 범위로 하고, 불활성가스분위기(예를 들어 아르곤분위기)에서는 1000 ~ 1250℃의 범위로 하는 것이 적당하다. 함침시간은 온도와 성형체 종류에 따라 다소 차이가 있으나 상기 온도범위에서 20분 이내가 바람직하다. 또한 본 발명에 의한 제조방법에서 진공도는 10-1torr 이하가 적당하다. 한편 본 발명에 의한 세라믹스-알루미늄 복합체의 미세구조와 물성은 후열처리에 의해 변화시킬 수 있는데, B4C의 경우를 예로 들면 Al이 B4C와 반응하여 구성성분인 B4C, Al, Al3BC의 상대비가 달라지고, Al의 양을 5wt% 이하로 낮출 수도 있다. 후열처리의 온도는 700℃ ∼ 1000℃의 범위가 적당하다.The amount of alumina sol added in the present invention is suitably in the range of 0.1 to 3 wt% based on the ceramic powder. In addition, the amount of aluminum alloy to be impregnated is appropriately 35 to 50 vol% with respect to the ceramic formed body. In the impregnation conditions, in the case of ceramics, the smaller the particle size of the powder, the impregnation occurs at a lower temperature.In the vacuum, since impregnation occurs in a vacuum rather than an inert atmosphere at atmospheric pressure, depending on the size and type of the ceramic powder, it is about 30 to 50 ° C. The impregnation temperature of aluminum is suitably in the range of 1000 to 1200 캜, and in the inert gas atmosphere (for example, argon atmosphere) in the range of 1000 to 1250 캜. The impregnation time is slightly different depending on the temperature and the type of the molded body, but is preferably within 20 minutes in the above temperature range. In addition, in the production method according to the present invention, the degree of vacuum is suitably 10 −1 torr or less. The ceramic according to the present invention there microstructure and physical properties of the aluminum composite material can be changed by the post-heat treatment, for the case of B 4 C Examples Al is B 4 C and the reaction with component B 4 C, Al, Al The relative ratio of 3 BC is changed, and the amount of Al may be lowered to 5 wt% or less. The temperature of post-heat treatment is suitable for the range of 700 degreeC-1000 degreeC.
본 발명에 의하여, 세라믹 분말에 알루미나 졸을 첨가함으로써 세라믹 분말 표면을 코팅시키고 상기 코팅에 의해 표면처리되어 웨팅이 향상된 세라믹 분말에 알루미늄을 함침시키면, 반응성 함침을 억제하여 강도 특성 등이 우수한 복합체를 얻을 수있게 된다. 또한 본 발명에 의한 B4C/Al복합체의 경우 XRD상에는 이제까지 알려진 B4C/Al복합체와는 달리 B4C, Al, Al3BC로 되어 있으며 Al4C3는 물론 다른 상도 나타나지 않는다. 또한 알루미나 졸로 표면처리한 경우에는 표면처리하지 않은 경우 보다 균일한 미세구조를 보이고 있다.According to the present invention, when alumina sol is added to the ceramic powder to coat the surface of the ceramic powder, and the aluminum powder is impregnated into the ceramic powder which is surface treated by the coating to improve the wetting, a composite having excellent strength characteristics and the like can be obtained by suppressing reactive impregnation. It becomes possible. In addition, unlike the B 4 C / Al composite material known so far formed on the case of B 4 C / Al composite XRD according to the present invention is a B 4 C, Al, Al 3 BC and Al 4 C 3, as well as other top coat does not appear. In addition, the surface treatment with alumina sol shows a more uniform microstructure than without the surface treatment.
다음 실시예는 본 발명을 더욱 상세히 예증하여 줄 것이나, 본 발명의 범위가 이에 국한하는 것은 아니다.The following examples will illustrate the invention in more detail, but the scope of the invention is not limited thereto.
[실시예 1]Example 1
B4C(HP Grade, 독일 H. C. Starck사 제품, d100<10 ㎛, d50= 3.5 ㎛, d10<0.7 ㎛)를 폴리프로필렌통에 SiC볼과 함께 넣고, 1시간 볼 밀링한 후, 2wt%의 알루미나에 해당하는 알루미나 졸을 첨가하고 1시간 더 볼 밀링 한 다음 얻어진 슬러리를 건조하여 표면처리된 B4C 분말을 얻었다. 이 분말을 40 × 65 × ∼10mm 크기로 성형압력을 500 kg/㎤로 건식 일축 성형한 후 20,000 psi로 CIP(냉간정수압)하여 성형밀도 약 63%의 성형체를 얻었다.B 4 C (HP Grade, manufactured by HC Starck, Germany, d 100 <10 μm, d 50 = 3.5 μm, d 10 <0.7 μm) was placed in a polypropylene container with SiC balls, ball milled for 1 hour, and then 2wt An alumina sol corresponding to% alumina was added and ball milled for another 1 hour, and the obtained slurry was dried to obtain a surface-treated B 4 C powder. The powder was dry uniaxially formed at a size of 40 × 65 × 10 mm to 500 kg / cm 3, followed by CIP (cold hydrostatic pressure) at 20,000 psi to obtain a molded body having a molding density of about 63%.
이 성형체를 먼저 진공(10-5torr)에서 1300℃/1시간 열처리하고, 기공에 알루미늄이 다 채워졌을 때 필요한 알루미늄 양의 계산치 보다 10wt% 많은 Al 6061 조각을 열처리한 B4C 성형체 위에 올려놓고 아르곤 분위기에서 1080℃/10분간 열처리하여 B4C/Al복합체를 얻었다.The molded body was first heat treated at 1300 ° C./1 hour in a vacuum (10 −5 torr), and then placed on a heat treated B 4 C molded body with 60 60 pieces of Al 6061 pieces more than the calculated amount of aluminum required when the pores were filled with aluminum. B 4 C / Al composite was obtained by heat treatment at 1080 ° C./10 min in argon atmosphere.
얻어진 이 복합체로 부터 제조된 MOR 시편(3 × 4 × 45mm)을 일정조건하 (span 길이 20/40 mm와 cross head 속도 0.5mm/min)에서 4점 굽힘 강도를 시험(MILSTD - 1942)한 결과, 굽힘 강도가 490 MPa이었고, 비중(He-Pycnometer 로 측정)은 2.63 g/㎤이었으며, 물에서 아르키메데스 방법으로 측정한 비중은 2.62 g/㎤이었다. 경도시험(Rockwell경도측정, A scale 60 kg 하중)에서는 경도가 77이었다. 영율은 ∼10 × 50 × 1mm 시편으로 측정한 결과 265 GPa 이었다. 그리고 DSC로 정량한 알루미늄의 양은 8.16wt%이었다. 광학사진으로부터 XRD상 분석에서는 B4C, Al, Al3BC로 되어 있으며, AlB2, Al4BC, AlB10등은 XRD상에서 검출되지 않았다. 아르곤 분위기하에서 800℃로 8시간 열처리한 시편의 영률은 298 GPa, 굽힘 강도는 369 MPa, Al의 양은 3.88wt%를 나타내었고, 800℃로 16시간 열처리한 시편의 경우 영률이 296.5 GPa, 굽힘강도는 344 MPa, Al의 양은 2.93wt%이었다.The MOR specimen (3 × 4 × 45 mm) prepared from the obtained composite was tested for four-point bending strength under constant conditions (span length 20/40 mm and cross head speed 0.5 mm / min) (MILSTD-1942). The bending strength was 490 MPa, the specific gravity (measured by He-Pycnometer) was 2.63 g / cm 3, and the specific gravity measured by the Archimedes method in water was 2.62 g / cm 3. In the hardness test (Rockwell hardness measurement, A scale 60 kg load), the hardness was 77. The Young's modulus was 265 GPa when measured with a -10 x 50 x 1 mm specimen. The amount of aluminum quantified by DSC was 8.16 wt%. In the XRD image analysis from the optical photograph, B 4 C, Al, Al 3 BC, and AlB 2 , Al 4 BC, AlB 10 and the like were not detected on the XRD image. The Young's modulus was 298 GPa, the bending strength was 369 MPa, and the amount of Al was 3.88 wt%. The specimen had the Young's modulus of 296.5 GPa and the bending strength. Was 344 MPa, and the amount of Al was 2.93 wt%.
[실시예 2]Example 2
실시예 1과 같은 방법으로 제조된 성형체를 진공에서 열처리하지 않고, 그 위에 적정량의 Al 6061 조각을 놓고 아르곤 분위기에서 1150℃로 10분간 열처리하여 B4C/Al복합체를 제조하였다. 이를 실시예 1에 서술된 방법으로 물성으로 측정하였는 바, 굽힘 강도가 480 MPa, 비중(pycnometer)은 2.64 g/㎤, 물에서 아르키메데스 방법으로 측정한 비중은 2.63 g/㎤, 경도는 78, 영율은 254 GPa이었다. XRD상 분석은 실시예 1에서 제조된 B4C/Al의 XRD와 정성적으로는 같았으나, 다만 회절 피이크의 강도만 차이를 보였다. 아르곤 분위기에서 800℃로 8시간 열처리한 시편의 영율은 288 GPa, 굽힘강도는 328MPa이고, 800℃로 16시간 열처리한 시편의 영율은 282 GPa, 굽힘강도는 344 MPa이었다.A molded article prepared in the same manner as in Example 1 was not heat treated in vacuo, and an appropriate amount of Al 6061 pieces was placed thereon, followed by heat treatment at 1150 ° C. for 10 minutes in an argon atmosphere to prepare a B 4 C / Al composite. The physical properties were measured by the method described in Example 1, and the bending strength was 480 MPa, the pycnometer was 2.64 g / cm 3, the specific gravity measured by the Archimedes method in water was 2.63 g / cm 3, the hardness was 78, and the Young's modulus. Was 254 GPa. XRD image analysis was qualitatively the same as XRD of B 4 C / Al prepared in Example 1, but only the intensity of the diffraction peak showed a difference. The Young's modulus of the specimen heat-treated at 800 ° C. at 800 ° C. for 8 hours was 288 GPa, the bending strength was 328 MPa. The Young's modulus of the specimen heat-treated at 800 ° C. for 16 hours was 282 GPa, and the bending strength was 344 MPa.
[실시예 3]Example 3
실시예 1에 기술된 방법으로 제조된 성형체를 진공에서 전열처리하지 않고 그 위에 적정량의 Al 6061 조각을 놓고 진공 또는 아르곤 분위기에서 1150℃로 60분간 열처리하여 B4C/Al복합체를 제조하였다. 경도시험에서 진공에서 함침한 경도가 88, 아르곤분위기에서 함침한 경도가 90이었고, 이들의 XRD는 정성적으로는 같았으나, 다만 회절 피이크의 강도만 차이를 보였다.A molded article prepared by the method described in Example 1 was placed on an appropriate amount of Al 6061 pieces without vacuum heat treatment in vacuo and heat-treated at 1150 ° C. for 60 minutes in a vacuum or argon atmosphere to prepare a B 4 C / Al composite. In the hardness test, the hardness impregnated in vacuum was 88 and the hardness impregnated in argon atmosphere was 90. Their XRD was qualitatively the same, but only the intensity of diffraction peak was different.
[실시예 4]Example 4
B4C 분말 (SHS 방법으로 제조된 분말, d100< 50 ㎛, d10< 1 ㎛, d50 15㎛)을 폴리프로필렌통에 SiC볼과 증류수를 함께 넣고 4시간 동안 볼 밀링한 다음 0.8 wt% Al2O3에 해당하는 알루미나 졸을 첨가하고 1시간 더 밀링하고 건조하였다. 이 분말에 물을 약간 첨가하여 과립하였다. 이 B4C 과립분말로 만든 40 × 65 × ∼ 10 mm크기의 B4C성형체를 실시예 1에 기술된 방법으로 진공에서 열처리한 후 아르곤 분위기에서 1150℃로 20분간 열처리하여 Al를 함침시켜 B4C/Al 복합체를 제조하였다. 이 복합체는 굽힘 강도가 350 MPa, 비중(pycnometer)은 2.59 g/㎤이고, 물에서 측정한 비중은 2.57g/㎤, 경도가 74, 영율은 249 GPa였다. 아르곤 분위기에서 800℃로 8시간 열처리한 시편의 영율은 274 GPa, 굽힘강도는 290MPa이고, 800℃로 16시간 열처리한 시편의 영율은 285 GPa, 굽힘강도는 279 MPa이었다.B 4 C powder (powder prepared by SHS method, d 100 <50 μm, d 10 <1 μm, d 50 SiC ball and distilled water were put together in a polypropylene barrel and ball milled for 4 hours, followed by addition of alumina sol corresponding to 0.8 wt% Al 2 O 3 , followed by further milling and drying for 1 hour. The powder was granulated with a little water. The B 4 C made with the granular powder 40 × 65 × ~ a B 4 C shaped body of 10 mm in size in the manner described in Example 1 was heat-treated in a vacuum heat-treated for 20 minutes in an argon atmosphere at 1150 ℃ was impregnated to Al B 4 C / Al complex was prepared. The composite had a bending strength of 350 MPa, a pycnometer of 2.59 g / cm 3, a specific gravity of 2.57 g / cm 3 measured in water, a hardness of 74, and a Young's modulus of 249 GPa. The Young's modulus of the specimen heat-treated at 800 ° C. for 8 hours at 800 ° C. was 274 GPa, the bending strength was 290 MPa. The Young's modulus of the specimen heat-treated at 800 ° C. for 16 hours was 285 GPa, and the bending strength was 279 MPa.
[실시예 5]Example 5
실시예 4에서 제조한 B4C 성형체를 열처리 없이 성형체 위에 Al 6061 조각을 올려놓고 아르곤 분위기에서 1200℃에서 20분간 열처리하여 Al이 완전히 함침된 B4C/Al복합체를 제조하였다. 이 복합체의 굽힘 강도가 440 MPa, 비중(pycnometer)이 2.62 g/㎤, 물에서 측정한 비중은 2.61g/㎤ 이었으며, 경도는 76 그리고 영율은 240 GPa 이었다. 이의 XRD는 실시예 3의 복합체와 정성적으로 같고, 피이크의 세기만 차이를 보였다. 아르곤 분위기에서 800℃로 8시간 열처리한 시편의 영율은 268 GPa, 굽힘강도는 353MPa이고, 800℃로 16시간 열처리한 시편의 영율은 266 GPa, 굽힘강도는 295 MPa이었다.The B 4 C molded body prepared in Example 4 was placed on an Al 6061 piece on the molded body without heat treatment, and heat-treated at 1200 ° C. for 20 minutes in an argon atmosphere to prepare a B 4 C / Al composite material in which Al was completely impregnated. The composite had a bending strength of 440 MPa, a pycnometer of 2.62 g / cm 3, a specific gravity of 2.61 g / cm 3 measured in water, a hardness of 76 and a Young's modulus of 240 GPa. Its XRD was qualitatively identical to the composite of Example 3, only the peak intensity was different. The Young's modulus of the specimen heat-treated at 800 ° C. at 800 ° C. for 8 hours was 268 GPa, the bending strength was 353 MPa. The Young's modulus of the specimen heat-treated at 800 ° C. for 16 hours was 266 GPa, bending strength was 295 MPa.
[실시예 6]Example 6
실시예 1의 표면처리된 B4C 분말을 700 kg/㎤ 로 일축 가압하여 직경 20 mm 높이 8 mm의 성형체를 만들었다. 여기에 Al 6061조각을 올려놓고 아르곤 분위기에서 분당 10℃로 1080℃까지 승온한 후, 일정시간 유지하지 않고 분당 10℃로 냉각하여 Al이 완전히 함침된 B4C/Al 복합체를 제조하였다.The surface-treated B 4 C powder of Example 1 was uniaxially pressed at 700 kg / cm 3 to form a molded body having a diameter of 20 mm and a height of 8 mm. A piece of Al 6061 was placed thereon and then heated up to 1080 ° C. at 10 ° C. per minute in an argon atmosphere, and then cooled to 10 ° C. per minute without maintaining a predetermined time to prepare a B 4 C / Al composite completely impregnated with Al.
[실시예 7]Example 7
실시예 1의 표면처리된 B4C 분말을 700 kg/㎤로 일축 가압하여 직경 20 mm 높이 8mm의 성형체를 만들었다. 여기에 Al 6061 조각을 올려놓고 진공(10-1torr)에서 분당 10℃로 1025℃까지 승온한 후, 일정시간 유지하지 않고 10℃로 냉각하여 Al이 완전히 함침된 B4C/Al복합체를 제조하였다.The surface-treated B 4 C powder of Example 1 was uniaxially pressed at 700 kg / cm 3 to form a molded body having a diameter of 20 mm and a height of 8 mm. A piece of Al 6061 was placed thereon, and the temperature was raised to 1025 ° C. at 10 ° C. per minute in a vacuum (10 −1 torr), followed by cooling to 10 ° C. without maintaining a predetermined time to prepare a B 4 C / Al complex impregnated with Al. It was.
[실시예 8]Example 8
B4C(Electro Abrasive사 미국, grade 400, 입도< 38㎛) 분말을 증류수로 세척한 후 사용하였다. 이 분말을 1.0wt%의 알루미나졸로 표면처리하였다. 표면처리 후 건조된 B4C분말을 700kg/cm2로 일축가압하여 20×8mm의 성형체를 만들었다. 여기에 Al6061 디스크를 올려놓고, 아르곤 분위기에서 분당 10℃로 승온하여 1200℃/20min 로 열처리한 후 분당 10℃로 냉각하여 Al이 완전히 함침된 B4C/Al 복합체를 제조하였다. 이 복합체의 단면을 자르고 그 표면을 연마한 후, 광학현미경으로 500배 확대한 미세구조를 관측하였다. 이 구조가 도 1에 나타나있다. 도면상에 나타난 미세구조를 보면 B4C와 Al 상들이 매우 균일하게 분포되어 있는 것을 볼 수 있다.B 4 C (Electro Abrasive, USA, grade 400, particle size <38 ㎛) powder was used after washing with distilled water. This powder was surface treated with 1.0 wt% alumina sol. After the surface treatment, the dried B 4 C powder was uniaxially pressurized to 700 kg / cm 2 to form a compact of 20 × 8 mm. The Al6061 disk was placed thereon, heated to 10 ° C. per minute in an argon atmosphere, heat treated at 1200 ° C./20 min, and then cooled to 10 ° C. to prepare a B 4 C / Al composite in which Al was completely impregnated. After cutting the cross section of the composite and polishing the surface, the microstructure magnified 500 times with an optical microscope was observed. This structure is shown in FIG. In the microstructure shown in the figure, it can be seen that B 4 C and Al phases are very uniformly distributed.
[비교예 1]Comparative Example 1
실시예 8에서 세척한 B4C분말을 알루미나졸로 표면처리 없이 실시예 8과 동일한 방법으로 B4C/Al 복합체를 제조하였다. 이 복합체의 단면을 광학현미경으로 관측하여 그 미세구조를 도 2에 나타내었다. 도 1에 나타난 표면처리된 B4C/Al 복합체와 달리 B4C와 Al의 반응이 많이 진행되어 아래쪽 부분에 매우 작은 그래인(grain)들이 몰려 있는 Al3BC 상이 많이 생성되어 있음을 알 수 있다.The B 4 C powder washed in Example 8 was prepared in the same manner as in Example 8 without surface treatment with alumina sol to prepare a B 4 C / Al composite. The cross section of the composite was observed with an optical microscope and its microstructure is shown in FIG. 2. Unlike the surface-treated B 4 C / Al composite shown in FIG. 1, the reaction of B 4 C and Al proceeded a lot, indicating that many Al 3 BC phases having very small grains gathered at the lower part were generated. have.
[실시예 9]Example 9
실시예 1과 같은 방법으로 TiB2(H.C.Starck) 분말의 슬러리에 1.0wt%에 해당하는 알루미나 졸을 첨가하여 얻은 표면처리된 TiB2분말을 사용하여 700Kg/cm2으로 일축 가압하여 직경 20mm 높이 8mm의 성형체를 만들었다. 여기에 적정량의 Al 6061 디스크를 올려놓고 아르곤 분위기에서 분당 10℃로 1250℃까지 승온한 후, 20분을 유지하고 분당 10℃로 냉각하여 Al이 완전히 함침된 TiB2/Al복합체를 얻었다. XRD상에는 TiB2와 Al의 패턴만 나타났으며, 광학현미경에서는 TiB2와 Al의 두 상만 나타났다. 그러나 표면처리되지 않은 TiB2분말의 성형체는 1300℃에서도 Al의 함침이 일어나지 않았다.In the same manner as in Example 1, using a surface-treated TiB 2 powder obtained by adding 1.0 wt% of alumina sol to a slurry of TiB 2 (HCStarck) powder, uniaxially pressurized at 700 Kg / cm 2 to a diameter of 20 mm and a height of 8 mm. A molded article was made. A proper amount of Al 6061 disc was placed thereon, and the temperature was raised to 1250 ° C. at 10 ° C. per minute in an argon atmosphere, and then maintained for 20 minutes and cooled to 10 ° C. per minute to obtain a TiB 2 / Al complex impregnated with Al. The XRD image showed only TiB 2 and Al patterns, and the optical microscope showed only two TiB 2 and Al phases. However, the impregnated of Al did not occur in the molded article of the surface-treated TiB 2 powder even at 1300 ° C.
[실시예 10]Example 10
실시예 9과 같은 방법으로 TiC(H.C.Starck) 분말을 1.0wt%의 알루미나 졸로 표면처리하여 얻은 TiC성형체에 Al 디스크를 올려놓고 아르곤 분위기에서 1250℃/20분 열처리하여 Al이 완전히 함침된 TiC/Al복합체를 얻었다. XRD와 광학현미경에서는 TiC와 Al의 두 상만 나타났다. 그러나 알루미나 졸로 표면처리되지 않은 TiC는 1300℃에서도 Al의 함침이 일어나지 않았다.In the same manner as in Example 9, the TiC (HCStarck) powder was surface-treated with 1.0 wt% of alumina sol, and the Al disc was placed on the TiC molded body, followed by heat treatment at 1250 ° C./20 minutes in an argon atmosphere to completely impregnate TiC / Al. The complex was obtained. XRD and optical microscope showed only two phases, TiC and Al. However, TiC not surface-treated with alumina sol did not impregnate Al even at 1300 ° C.
[실시예 11]Example 11
B4C(H.C.Starck HP grade)와 TiB2(H.C.Starck)을 2:1의 몰비로 혼합한 슬러리에 1.0wt%에 해당하는 알루미나 졸을 첨가하여 실시예 9과 같은 방법으로 표면처리된 분말을 얻고 이 분말로 직경 20mm의 펠릿(pellet)을 만들어 Al 6061을 올려놓고1250℃에서 20분간 열처리하여 Al이 함침된 B4C-TiB2/Al복합체를 제조하였다. XRD상에는 TiB2패턴과 B4C/Al서멧(cermet)에서 생기는 패턴이 같이 나타났다. 그러나 알루미나 졸로 표면처리되지 않은 분말의 성형체는 1300℃의 열처리에서도 Al의 함침이 일어나지 않았다. 또한 1:1의 몰비로 B4C-TiB2의 혼합분말을 위와 같은 방법으로 처리하였을 때는 Al의 함침이 1300℃의 열처리에서도 일어나지 않았다.1.0 wt% of alumina sol was added to a slurry containing B 4 C (HCStarck HP grade) and TiB 2 (HCStarck) in a molar ratio of 2: 1 to obtain a surface-treated powder in the same manner as in Example 9. A pellet of 20 mm in diameter was made of powder, Al 6061 was placed thereon, and heat-treated at 1250 ° C. for 20 minutes to prepare Al-impregnated B 4 C-TiB 2 / Al composite material. On XRD, TiB 2 pattern and B 4 C / Al cermet pattern appeared. However, the impregnated of Al did not occur in the molded article of the powder which was not surface treated with an alumina sol even at a heat treatment at 1300 ° C. In addition, when the mixed powder of B 4 C-TiB 2 in a molar ratio of 1: 1 was treated as described above, impregnation of Al did not occur even at a heat treatment at 1300 ° C.
[실시예 12]Example 12
SHS 반응으로 생성된 B4C-Al2O3의 혼합분말(325메쉬이하)에 B4C(실시예 4와 같이 SHS방법으로 제조)분말을 더하여 몰비가 2:1이 되게 한 후, 실시예 11과 같은 방법으로 알루미나 졸 1wt%로 표면처리하여 얻은 분말의 성형체를 제조하였다. 이 성형체에 Al 6061 디스크를 올려놓고 아르곤 분위기에서 1250℃로 20분간 열처리하여 Al이 완전히 함침된 B4C-Al2O3/Al복합체를 얻었다. 그러나 알루미나 졸로 표면처리되지 않은 B4C-Al2O3의 혼합분말의 성형체는 1300℃의 열처리에서도 Al의 함침이 일어나지 않았다. 또한 1:2의 몰비로 B4C-Al2O3의 혼합분말을 위와 같은 방법으로 처리하였을 때는 Al의 함침이 1300℃의 열처리에서도 일어나지 않았다.B 4 C (manufactured by SHS method as in Example 4) powder was added to a mixed powder of B 4 C-Al 2 O 3 produced by the SHS reaction so as to have a molar ratio of 2: 1. In the same manner as in Example 11, a molded body of a powder obtained by surface treatment with 1 wt% of alumina sol was prepared. An Al 6061 disc was placed on the molded body and heat-treated at 1250 ° C. for 20 minutes in an argon atmosphere to obtain a B 4 C-Al 2 O 3 / Al complex impregnated with Al. However, the molded body of the mixed powder of B 4 C-Al 2 O 3 , which was not surface treated with an alumina sol, did not impregnate Al even after the heat treatment at 1300 ° C. In addition, when the mixed powder of B 4 C-Al 2 O 3 in a molar ratio of 1: 2 was treated in the same manner as described above, impregnation of Al did not occur even at a heat treatment at 1300 ° C.
본 발명에서는 사용하는 B4C 분말의 순도 및 입도 분포에 따라 비중이 2.56 ∼ 2.64g/㎤, 4점 굽힘 강도는 350 ∼ 490 MPa, 영율이 237 ∼ 265 GPa, 경도가 74 ∼ 90인 B4C/Al 복합체를 제조하였다. 이 B4C/Al 복합체를 아르곤 분위기하에서 후열처리하여 구성성분의 비가 변함에 따라 미세구조도 달라지고 따라서 기계적 물성도 변화하여 4점굽힘강도는 290 ~ 370 MPa 로 변하고, 영률도 266 ~ 300 GPa 로 변화시킬 수 있었다. 이상의 기계적 특성은 알루미나 졸로 표면처리함으로써 B4C 분말의 웨팅을 향상시키고 따라서 알루미늄 함침을 더욱 용이하게 한 결과이다. 또한 본 발명에 의하여 상기 강도특성 등의 기계적 특성 뿐만아니라 복합체의 미세구조에서도 균일한 구조를 보여 종래 기술보다 매우 우수한 구조재료용 B4C/Al 복합체를 간단하고 경제적인 공정으로 제공할 수 있게 되었다.Depending on purity and particle size distribution of the B 4 C powder to be used in the present invention, a specific gravity of 2.56 ~ 2.64g / ㎤, 4-point bending strength is 350 ~ 490 MPa, Young's modulus is 237 ~ 265 GPa, a hardness of 74 ~ 90 of B 4 C / Al complexes were prepared. The B 4 C / Al composite was post-heated under argon atmosphere to change the microstructure as the constituent ratio changed, thus changing the mechanical properties, resulting in four-point bending strength of 290 to 370 MPa and Young's modulus of 266 to 300 GPa. Could be changed to The above mechanical properties are the result of improving the wetting of the B 4 C powder by surface treatment with alumina sol and thus making aluminum impregnation easier. In addition, the present invention shows a uniform structure in the microstructure of the composite as well as the mechanical properties such as the strength properties, it is possible to provide a B 4 C / Al composite for structural materials in a simple and economical process very superior to the prior art. .
이러한 현상은 반응성 함침이 일어나지 않는 TiB2, TiC의 경우와 B4C-TiB2, B4C-Al2O3와 같은 복합체의 경우에도 적용되어 알루미나로 표면개질된 분말이 표면처리되지 않은 분말에 비하여 보다 균일한 미세구조를 보여준다.This phenomenon is also applied to TiB 2 and TiC where reactive impregnation does not occur, and to composites such as B 4 C-TiB 2 and B 4 C-Al 2 O 3 so that the surface-modified powder is not surface treated with alumina. Compared to the more uniform microstructure.
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| KR20080078096A (en) * | 2007-02-22 | 2008-08-27 | 한국과학기술연구원 | Fabrication method of alumina coating layer |
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| US4935296A (en) * | 1986-09-26 | 1990-06-19 | Advanced Technology Materials, Inc. | Metal coated fibers containing a sol gel formed porous polysilicate, titania or alumina interlayer and composite material articles reinforced therewith |
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| WO1998030725A1 (en) * | 1997-01-10 | 1998-07-16 | Nils Claussen | Cermet structural element, its construction and production |
| JPH11209834A (en) * | 1998-01-22 | 1999-08-03 | Toshiba Ceramics Co Ltd | Production of alumina-aluminum composite material formed body |
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| US4935296A (en) * | 1986-09-26 | 1990-06-19 | Advanced Technology Materials, Inc. | Metal coated fibers containing a sol gel formed porous polysilicate, titania or alumina interlayer and composite material articles reinforced therewith |
| JPH03229876A (en) * | 1989-12-11 | 1991-10-11 | Sumitomo Electric Ind Ltd | Method for coating with ceramics and material coated with ceramics |
| JPH09227969A (en) * | 1996-02-16 | 1997-09-02 | Nils Claussen | Production of metal ceramic composite material molding, constituting members consisting of this molding in machine production, device production, motor use under corrosion condition and/or oxidation condition |
| WO1998030725A1 (en) * | 1997-01-10 | 1998-07-16 | Nils Claussen | Cermet structural element, its construction and production |
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