KR940005087B1 - Process for preparation of machinable ceramics - Google Patents

Process for preparation of machinable ceramics Download PDF

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KR940005087B1
KR940005087B1 KR1019920004548A KR920004548A KR940005087B1 KR 940005087 B1 KR940005087 B1 KR 940005087B1 KR 1019920004548 A KR1019920004548 A KR 1019920004548A KR 920004548 A KR920004548 A KR 920004548A KR 940005087 B1 KR940005087 B1 KR 940005087B1
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fluorophlogopite
pyrophyllite
ceramics
present
machinable ceramics
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KR1019920004548A
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KR930019585A (en
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양삼열
정창주
정회준
김재국
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조선내화화학공업 주식회사
이화일
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/16—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay
    • C04B35/18—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay rich in aluminium oxide

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Materials For Medical Uses (AREA)
  • Compositions Of Oxide Ceramics (AREA)

Abstract

The machinable ceramics having the complex crystalline phase of sodium fluorophlogopite and cordierite consists of 65-75 wt.% pyrophyllite containing 70-80% silica, 4-10 wt.% alumina, 10-13 wt.% magnesia, 7-10 wt.% magnesium fluoride, 3-5 wt.% sodium oxide, 1-4 wt.% titania. The above materials are mixed and molded, and the formed body is heated at 850-950 deg.C for nucleation, and at 1,000-1,150 deg.C for crystallization.

Description

마시너블 세라믹스(machinable ceramics) 및 그 제조방법Machinable ceramics and manufacturing method thereof

제1도는 본 발명의 제조공정도.1 is a manufacturing process diagram of the present invention.

제2도는 결정화 열처리온도 곡선도로서, a도는 본 발명의 그래프, b도는 비교발명의 그래프.2 is a crystallization heat treatment temperature curve, a is a graph of the present invention, b is a graph of comparative invention.

제3도는 결정질 분포를 나타낸 그래프로서, a, b도는 본 발명의 그래프, c, d도는 비교발명의 그래프.3 is a graph showing the crystalline distribution, a, b is a graph of the present invention, c, d is a graph of comparative invention.

제4도는 결정화 조작상태를 나타낸 현미경 사진으로서, a, b는 본 발명의 현미경사진, c, d는 비교발명의 현미경사진.4 is a micrograph showing a crystallization operation state, a, b is a micrograph of the present invention, c, d is a micrograph of the comparative invention.

본 발명은 쾌삭성 마시너블 세라믹스(machinable ceramics)에 관한 것으로, 보다 상세하게는 기계가공성을 크게 떨어트리지 않으면서 내열충격성이 우수함과 함께 저렴한 제조원가를 갖는데 적합한 마시너블 세라믹 및 그 제조방법에 관한 것이다.BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to machinable ceramics, and more particularly, to a marshable ceramic suitable for having excellent thermal shock resistance and inexpensive manufacturing cost without significantly reducing machinability.

일반적으로 쾌삭성 세라믹스라 불리우는 마시너블 세라믹스는 주결정상이 합성 운모 결정인 플로로 플로고파이트(fluorophlogopite)(KMg3AlSi3O10F2)와 유리로된 복합체로서 이 운모결정립이 유리등의 결합제에 의해 고정되어 있는 조직을 갖고 있다.The marshable ceramics, commonly called free-cutting ceramics, are a composite of glass with fluorophlogopite (KMg 3 AlSi 3 O 10 F 2 ) whose main crystal phase is synthetic mica crystals. It has a fixed structure by.

이러한 마시너블 세라믹스는 기계가공등으로 사용시 균열의 발생이 우려되나 이런 균열은 유리질내에 미세하고 무질서한 배열로 인터록킹(interlocking)된 운모 결정에 의해 그 균열의 전파를 억제하기 때문에 천공, 절단, 선반가공등과 같은 기계가공성을 요하는데 널리 이용되고 있다.Such machinable ceramics may cause cracks when used in machining, but such cracks are suppressed by mica crystals interlocked in fine and disordered arrays in the glass material, so that the crack propagation, cutting, lathe machining It is widely used to require machinability, such as.

이와 같은 기계 가공성을 갖게하는 주결정상인 fluorophlogoplte를 얻기위한 방법으로서는 단성분 고품위의 원료를 사용하여야 하고 또한 제조시간이 길어 제조원가의 상승요인이 되고 있으며, 열적, 화학적 내구성이 충분하지 못하는 등의 문제점이 있어왔다.As a method for obtaining fluorophlogoplte, which is the main crystalline phase having such machinability, high quality raw materials of single components should be used, and the manufacturing cost is long, which is a factor of increase in manufacturing cost, and there are problems such as insufficient thermal and chemical durability. Has been.

이에 본출원인은 복합성분을 가지면서 불순물이 적은 저가 원료인 국내산 파이로필라이트(Pyrophyllite)계인 납석을 주원료로 하고 여기에 다른 원료를 혼합하여 용융, 결정화 처리하여 fluorophlogopite와 LAS계(Li2O3-Al2O3-SiO2계)인 베타-스포듀먼(β-spodumene)의 복합 결정체를 갖게함으로서, 상기한 문제점을 해결하기 위한 기술을 요업학회지에 발표한바 있고(Journal of the korea ceramics society Vol 28, no 9, PP 730-739, 1991) 이를 국내 특허출헌(출원번호 91-25537호)하였다.Therefore, the main applicant is a main raw material of domestic pyrophyllite-based feldspar, which is a low-cost raw material having a complex component and few impurities, mixed with other raw materials, and melted and crystallized to fluorophlogopite and LAS (Li 2 O 3 By having a complex crystal of β-spodumene, which is a -Al 2 O 3 -SiO 2 system, a technique for solving the above problems has been published in a ceramics journal (Journal of the Korea ceramics society Vol 28, no 9, PP 730-739, 1991). It is a Korean patent application (application number 91-25537).

상기와 같이 출원된 기술에서는 제조원가의 절감 및 기계 가공성, 내화학적 성질은 향상되고 있으나 만족할 열 팽창성을 얻을 수 없어 열충격 저항성을 갖는 용도 사용에는 한계가 있다.In the technology applied as described above, manufacturing cost reduction, machinability, and chemical resistance properties are improved, but satisfactory thermal expansion cannot be obtained, and thus there is a limit to use of the application having thermal shock resistance.

이에 본 발명은 상기에서 발표한바 있는 국내산 pyrophyllite계 납석을 사용하되 기타 원료와 그 조성비 및 열처리를 달리하여 결정질을 Fluorophlogopite와 MAS계(MgO-Al2O3-SiO2계)인 코디어라이트(cordierite)의 복합체로 함으로써 우수한 내충격성을 갖는 마시너블 세라믹스를 제공하고자 하는데 그 목적이 있다.Therefore, the present invention uses domestic pyrophyllite-based feldspar, which has been released above, but differs from other raw materials, its composition ratio, and heat treatment, so that the crystals are fluoride phlogopite and MAS-based cordierite (MgO-Al 2 O 3 -SiO 2 type ). By providing a composite of) to provide a marshable ceramics having excellent impact resistance.

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

본 발명은 pyrophllite 계 납석 60-75중량％에 Al2O34-10중량％, MgO 10-13중량％, MgF27-10중량％, Na2O 3-5중량％, TiO21-4중량％ 혼합조성되고 결정상이 Na-Flour-ophlogopite와 cordierite인 복합 결정질로 구성된 마시너블 세라믹스를 얻는다.The present invention is 60-75% by weight of pyrophllite-based feldspar, 4-10% by weight of Al 2 O 3 , 10-13% by weight of MgO, 7-10% by weight of MgF 2 , 3-5% by weight of Na 2 O, TiO 2 1- A marshable ceramics composed of 4 wt% of mixed crystalline and crystalline phase of Na-Flour-ophlogopite and cordierite is obtained.

상기와 같이 구성된 본 발명을 구체적으로 설명하면, 제1도는 본 발명의 제조공정도로서, SiO2전량과 Al2O3의 대부분을 차지하고 있는 표 1과 같은 국내산 납석을 65-70중량％로하고 여기에 Al2O3, MgO, MgF2, Na2O, TiO2를 상기 조성비로 하여 혼합한다.Referring to the present invention configured as described above in detail, Figure 1 is a manufacturing process diagram of the present invention, the domestic feldspar as shown in Table 1 which occupies most of SiO 2 and Al 2 O 3 to 65-70% by weight, Al 2 O 3 , MgO, MgF 2 , Na 2 O, and TiO 2 are mixed at the above composition ratio.

여기에서 Na2O는 그 양이 많으면 열팽창 계수가 큰 Na-fluorophlogopite가 많이 생성되어 열충격 저항이 나빠지므로 3-5중량％로 하였고, MgF2로 첨가한 F(fluorine)는 유리구조중의 가교 산소이온을 치환하여 유리의 망목구조를 약화시킴으로써 결정화 열처리에 의한 원자 배열이 보다 쉽게 일어나게 된다.In this case, Na 2 O has a large amount of Na-fluorophlogopite with a large coefficient of thermal expansion, resulting in poor thermal shock resistance, so it is 3-5% by weight.F (fluorine) added with MgF 2 is crosslinked oxygen in the glass structure. By substituting ions to weaken the network structure of the glass, atomic arrangement by crystallization heat treatment occurs more easily.

TiO₂는 MAS계 글라스에서 효과적인 핵형성제로 작용한다.TiO₂ acts as an effective nucleating agent in MAS glass.

이와 같이 혼합된 조성물을 전기로등과 같은 용융로 잠입하여 1,400℃까지 상승시켜 약 1-2시간 용해한 후 몰드(mold)에서 성형한다.The mixed composition is immersed in a melting furnace such as an electric furnace, and then raised to 1,400 ° C., dissolved for about 1-2 hours, and then molded in a mold.

그리고 제2도의 (a)도와 같이 결정화 열처리를 하게된다. 결정화 열처리는 1차로 약 850-950℃에서 핵 생성을 시킨다음 승온하여 2차로 결정성장 온도인 약 1,100℃에서 결정화 하는 2단계 열처리를 한다.And crystallization heat treatment is performed as shown in (a) of FIG. Crystallization heat treatment is first subjected to nucleation at about 850-950 ° C., and then heated to a second step of crystallization at about 1,100 ° C., which is the crystal growth temperature.

이때 1차 열처리 구간에서 850℃ 이하에서는 α-cordierite가 생성되지 않고 μ-cor-dierite만 생성되며 950℃ 이상에서는 불필요한 결정인 포스테라이트(forsterite)(2MgOSiO2)가 나타난다.At this time, α-cordierite is not produced at 850 ° C. or less, but only μ-cor-dierite is produced. At 950 ° C. or more, forsterite (2MgOSiO 2 ), which is an unnecessary crystal, appears.

1차 열처리후 2차 온도를 1,100℃까지 높혀서 2차 결정화 시켜도 포스테라이트 결정은 나타나지 않는다.After the first heat treatment, the secondary temperature is increased to 1,100 ° C. to make the second crystallization.

이하 실시예를 통하여 설명한다.It will be described through the following examples.

[원료혼합][Mix raw materials]

표 1과 같은 파이로필라이트계 납석에 표 2와 같이 다른 원료를 볼밀을 이용한 12시간 혼합한다.Pyrophyllite-based feldspar as shown in Table 1 is mixed with other raw materials as shown in Table 2 for 12 hours using a ball mill.

[표 1]TABLE 1

상기 표 1에서는 하나의 성분예만을 나타낸 것으로서 이는 각지역에 따라 성분상 다소의 차이가 있을 수 있으나 SiO₂와 Al₂O₃가 주공급원으로서 큰차이가 없어 적용가능함으로 표 1의 성분범위에만 국한하지 않는다.Table 1 shows only one component example, which may be slightly different depending on each region, but SiO 2 and Al 2 O 3 are not limited to the component range of Table 1 because they are applicable because there is no significant difference as a main source.

[표 2]TABLE 2

[용융, 결정화 처리][Melting, crystallization treatment]

(1) 용융처리(1) melt treatment

표 2의 혼합물을 전기로에서 1,450℃, 1시간 가열 용해한후 흑연 몰드를 사용하여 성형한다.The mixture of Table 2 is melted by heating at 1,450 ° C. for 1 hour in an electric furnace and then molded using a graphite mold.

(2) 결정화 처리(2) crystallization treatment

성형품을 열처리로 넣어 제2도에 나타난 바와 같이 비교발명인 (b)도에서는 800℃까지 가열하고 2시간 유지하여 핵생성시킨 후 다시 1100℃까지 승온하여 결정을 성장시켰으나, 본 발명인 (a)도는 1차로 900℃에서 핵생성 시킨다음 승온하여 1,100℃에서 4시간 2차 열처리하여 결정을 성장시킨다.As shown in FIG. 2, the molded article was subjected to a heat treatment, and in the invention (b), the invention was heated to 800 ° C., maintained for 2 hours, nucleated, and then heated up to 1100 ° C. to grow crystals. After nucleation at 900 ℃ by car, the temperature is raised to secondary heat treatment at 1,100 ℃ for 4 hours to grow crystals.

이렇게 함으로서 Na-fluororophlogopite와 cordierite가 복합된 결정체를 얻게된다.In this way, Na-fluororophlogopite and cordierite complexes are obtained.

제3도는 열처리후의 X-선 회절분석을 나타낸 결과인데, (a) 및 (b)도는 본 발명인 시료 1, 2의 것으로서 여기서는 Na-fluorophlogopite와 α-cordierite 두결정상의 피크가 나타났으며, TiO2가 많은 (b)의 경우는 상기의 각 결정간의 상대적인 피크 간격차이가 적었다.FIG. 3 shows the results of X-ray diffraction analysis after heat treatment. (A) and (b) are the samples 1 and 2 of the present invention, where Na-fluorophlogopite and α-cordierite peaks of two crystal phases were formed, and TiO 2 In the case of large (b), the difference in relative peak spacing between the above crystals was small.

이에 반해 (c)와 (d)도는 시료 3과 4의 경우로서, Na-fluorophlogopite와 β-eucryptite 또는 β-spodumena 결정구조를 갖는다.On the other hand, (c) and (d) are the case of Samples 3 and 4, which have Na-fluorophlogopite and β-eucryptite or β-spodumena crystal structure.

[현미경 사진에 의한 조직분석][Tissue Analysis by Micrograph]

제4도는 결정질 조직상태를 나타낸 현미경 사진으로서, 본 발명인 (a)와 (b)의 경우는 판상의 Na-fluorophlogopite 결정에 다각형 모양의 α-cordierite 결정이 연결되는 것으로 나타나고 있는데 이는 결정 성장 단계에서 각 결정이 연결되면서 이루어진 것으로 보여진다.4 is a micrograph showing the crystalline tissue state. In the case of the present inventors (a) and (b), a polygonal α-cordierite crystal is connected to the plate-shaped Na-fluorophlogopite crystal. The decision seems to have been made in conjunction.

이에 반해 (c)와 (d)인 종래의 경우는 무질서하게 인터록킹(interlocking)된 판상의 Na-fluorophlogopite 결정사이에 구형의 LAS계(Li2O-Al2O3-SiO2계)의 β-eucryptite β-spodumene 결정이 혼재되어 있다.On the other hand, in the conventional cases of (c) and (d), β of spherical LAS system (Li 2 O-Al 2 O 3 -SiO 2 system) is formed between disordered interlocked plate-shaped Na-fluorophlogopite crystals. -eucryptite β-spodumene crystals are mixed.

[물리적 성질][Physical properties]

표 3은 결정화 처리후의 열팽창 계수를 나타낸 결과로서, 본 발명(시료 1과 2)은 전온도구간에서 열팽창이 일어나지 않고 수축하는 매우 특이한 현상을 나타내고 있다.Table 3 shows the coefficient of thermal expansion after the crystallization treatment, and the present invention (Samples 1 and 2) shows a very peculiar phenomenon of shrinkage without thermal expansion in the entire temperature section.

[표 3]TABLE 3

표 4는 여러 가지 측정값을 나타낸 것으로서, 비교발명에 비해 본 발명은 결정화도가 높고 정도가 높은 특성을 나타내고 있다.Table 4 shows various measured values. The present invention shows a high degree of crystallinity and a high degree of accuracy compared to the comparative invention.

[표 4]TABLE 4

이상에서와 같이 본 발명은 저렴한 국내 납석을 사용하여 제조원가를 절감함과 함께 기계 가공성을 크게 해치지 않으면서도 특히 저열팽창 계수를 갖게됨으로서 내열 충격성을 갖는 마시너블 세라믹스를 얻을 수 있다.As described above, the present invention can obtain marshable ceramics having thermal shock resistance by having a low coefficient of thermal expansion, in particular, while reducing manufacturing cost by using inexpensive domestic feldspar without significantly degrading machinability.

Claims (2)

파이로 필라이트(pyrophyllite)계 납석 60-75중량％와 Al2O34-10중량％, MgO 10-13중량％, MgF27-10중량％, Na2O 3-5중량％, TiO21-4중량％로 조성되고 결정상이 나트륨-플로로플로고파이트(Na-fluorophlogopite)와 코디어라이트(cord-ierite)인 복합 결정질로 이루어짐을 특징으로 하는 마시너블 세라믹스(machinable ceramics).Pyrophyllite pyrophyllite 60-75 wt%, Al 2 O 3 4-10 wt%, MgO 10-13 wt%, MgF 2 7-10 wt%, Na 2 O 3-5 wt%, TiO 2 Machinable ceramics, characterized in that the composition is composed of 1 to 4% by weight of the complex crystals of Na-fluorophlogopite (Na-fluorophlogopite) and cordierite (cord-ierite). 파이로 필라이트(pyrophyllite)계 납석 60-75중량％와 Al2O34-10중량％, MgO 10-13중량％, MgF27-10중량％, Na2O 3-5중량％, TiO21-4중량％로 조성되게 용해한 혼합물을 몰드(mold)에서 성형후 850-950℃에서 열처리하여 핵생성시킨 다음 온도를 올려 1,000-1,150℃에서 결정화시켜 나트륨-플로로플로고파이트(Na-fluorophlogopite)와 코디어라이트(cordierite)인 복합 결정질로 구성되게 함을 특징으로 하는 마시너블 세라믹스(machinable ceramics)의 제조방법.Pyrophyllite pyrophyllite 60-75 wt%, Al 2 O 3 4-10 wt%, MgO 10-13 wt%, MgF 2 7-10 wt%, Na 2 O 3-5 wt%, TiO 2 The mixture dissolved in 1-4% by weight was formed in a mold, heat-treated at 850-950 ° C., nucleated, and then crystallized at 1,000-1,150 ° C. to crystallize sodium-fluorophlogopite (Na-fluorophlogopite). ) And cordierite composite crystalline (machinable ceramics) characterized in that consisting of.
KR1019920004548A 1992-03-19 1992-03-19 Process for preparation of machinable ceramics KR940005087B1 (en)

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KR20190111531A (en) * 2018-03-23 2019-10-02 주식회사 새한텅스텐 Machinable ceramic and manufacturing method of the same

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KR101154428B1 (en) * 2009-09-03 2012-06-15 (주) 구산솔루션 Filler being made from pyro-phyllite as main material and method manufacturing the same

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20190111531A (en) * 2018-03-23 2019-10-02 주식회사 새한텅스텐 Machinable ceramic and manufacturing method of the same

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