KR101243731B1 - Composition for semiconducting ceramic solid solution used for elimination of static electricity and the manufacturing method of the same - Google Patents

Composition for semiconducting ceramic solid solution used for elimination of static electricity and the manufacturing method of the same Download PDF

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KR101243731B1
KR101243731B1 KR1020110110348A KR20110110348A KR101243731B1 KR 101243731 B1 KR101243731 B1 KR 101243731B1 KR 1020110110348 A KR1020110110348 A KR 1020110110348A KR 20110110348 A KR20110110348 A KR 20110110348A KR 101243731 B1 KR101243731 B1 KR 101243731B1
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solid solution
static electricity
ceramic composition
camno
composition
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김태균
김윤한
이주식
김태원
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주식회사 대양신소재
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    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05FSTATIC ELECTRICITY; NATURALLY-OCCURRING ELECTRICITY
    • H05F1/00Preventing the formation of electrostatic charges
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/46Shaped 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 titanium oxides or titanates
    • C04B35/462Shaped 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 titanium oxides or titanates based on titanates
    • C04B35/465Shaped 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 titanium oxides or titanates based on titanates based on alkaline earth metal titanates
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/64Burning or sintering processes
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3262Manganese oxides, manganates, rhenium oxides or oxide-forming salts thereof, e.g. MnO
    • C04B2235/3268Manganates, manganites, rhenates or rhenites, e.g. lithium manganite, barium manganate, rhenium oxide

Abstract

PURPOSE: A solid solution-type semiconducting ceramic composition for eliminating static electricity is provided to facilitate a manufacture of solid solution-type semiconducting ceramics for eliminating static electricity with a firm and high strength, and to realize a stable change of resistivity in a wide domain. CONSTITUTION: A solid solution-type semiconducting ceramic composition is a ceramic composition of a solid solution comprising (1-x)CaMnO3 and xABO3. The A is Ca, Sr, or Ba; the B is Zr, Sn, or Ti; and the X is 0.4-0.8. A manufacturing method for the solid semiconducting ceramic composition for eliminating static electricity comprises the following steps of: (a) obtaining a mixture of CaMnO3 and ABO3(A is Ca,Sr, or Ba; B is Zr, Sn, or Ti) by taking salt or oxide including Mn, Ti, Zr, Ca, Sr, Ba, or Sn as a starting material; (b) manufacturing a solid solution by synthesizing the CaMnO3 and the ABO3; and (c) sintering the solid solution. The mole ratio of the CaMnO3 and the ABO3 is 0.2:0.8-0.6:0.4.

Description

정전기 제거용 고용형 반도성 세라믹 조성물 및 그 제조방법{Composition for semiconducting ceramic solid solution used for elimination of static electricity and the manufacturing method of the same}Composition for semiconducting ceramic solid solution used for elimination of static electricity and the manufacturing method of the same}

본 발명은 전자 및 광학산업의 장치 및 시스템의 제조공정 등에서 발생하는 정전기를 제거시킴으로써 불꽃방전이나 이물질의 오염 등을 방지할 수 있는 정전기 제거용 고용형 반도성 세라믹 조성물 및 그 제조방법에 관한 것으로, 비저항이 낮은 칼슘망간네이트(CaMnO3)에 같은 결정구조의 절연성 물질을 고용시킴으로써 넓은 영역에서 비저항의 변화를 안정적으로 구현시킴은 물론, 치밀하고 비교적 높은 강도의 정전기 제거용 고용형 반도성 세라믹 조성물을 용이하게 제조할 수 있다.The present invention relates to a solid solution semiconducting ceramic composition for removing static electricity and a method of manufacturing the same, which can prevent spark discharge and contamination of foreign matter by removing static electricity generated in manufacturing processes of devices and systems of the electronic and optical industries. By employing an insulating material of the same crystal structure in calcium manganate (CaMnO 3 ) having a low resistivity, it is possible to stably change the resistivity in a wide range, and to form a solid, semiconductive ceramic composition for removing static electricity of high density and relatively high strength. It can be manufactured easily.

정전기 제거용 재료는 정전기적으로 도전성을 가지나, 통상 전기적으로는 절연성을 나타내는 재료로서, 그 자신이 일정한 저항치를 가지기 때문에 정전기가 발생한 경우에도 불꽃 방전이 없이 신속하게 정전기를 제거시킴으로써 인체와 접촉하는 사물에 적용하는 경우 감전을 방지할 수 있고, 또한 기기나 장치에 적용하는 경우, 기기나 장치에 대한 단락을 방지하는 성질이 있을 뿐 아니라, 물체에 정전기적 인력이 발생하여 이물질이 부착되는 것을 방지할 수 있는 매우 유용한 재료이다. Static elimination material is electrostatically conductive, but generally electrically insulating material, because it has a certain resistance value, even in the event of static electricity, the object that comes into contact with human body by quickly removing static electricity without spark discharge. It can prevent electric shock when applied to the device, and when applied to the device or device, it has the property of preventing short circuit to the device or device, and also prevents the foreign matter from attaching due to the electrostatic attraction to the object. It can be a very useful material.

이러한 정전기 제거용 재료는 무엇보다도 적절한 저항치를 가져야 하는데, 예를 들면, 비저항이 102 내지 109ohm.cm 이고, 바람직하게는 103 내지 106ohm.cm 이어야 정전하를 제거하기 적합하고, 부가적으로 내구성을 위하여 충분히 높은 밀도와 강도가 요구되며, 값이 싸고 용이하게 제조할 수 있어야 한다.The material for removing static electricity should first of all have an appropriate resistance value, for example, a specific resistance of 10 2 to 10 9 ohm.cm, preferably 10 3 to 10 6 ohm.cm, to be suitable for removing the static charge, In addition, high density and strength are required for durability, and should be inexpensive and easy to manufacture.

현재 사용되고 있는 정전기제거용 재료로는 도전성물질/수지 복합재료와 반도성 세라믹재료가 있다. 대한민국 특허공고 제95-015027호에서는 입자나 플레이크, 위스커, 섬유상의 반도체 필러를 여러 종류의 수지와 혼합시킨 복합재료에서 적정한 저항률의 정전기제거용 재료를 제공하고 있으며, 제조가 용이하므로 이와 유사한 재료를 많이 활용하고 있으나, 수지의 경도가 약하여 사용중에 마모로 인한 이물질의 발생과 신뢰성이 문제되고 있다. Currently used static elimination materials include conductive / resin composite materials and semiconducting ceramic materials. Korean Patent Publication No. 95-015027 provides a material for removing static electricity of an appropriate resistivity in a composite material in which particles, flakes, whiskers, and fibrous semiconductor fillers are mixed with various resins. Although it is used a lot, the hardness of the resin is weak, the generation and reliability of foreign matters due to abrasion during use is a problem.

또한, 대한민국 등록특허 제10-0553118호에 의하면 산화이트륨을 첨가한 정방정계 지르코니아(Y-PSZ)에 도전성의 산화물, 탄화물, 질화물 등을 첨가시킨 혼합물을 고온 가압소결하여 적절한 저항율을 갖는 고밀도, 고강도의 세라믹스를 제공하고 있으나, 고가의 장비와 복잡한 공정으로 인해 대형부재의 제조가 어렵고, 제품의 가격도 매우 높을 수 밖에 없어 응용에 한계가 있다.In addition, according to the Republic of Korea Patent No. 10-0553118, high density and high strength having an appropriate resistivity by hot-sintering a mixture of conductive oxide, carbide, nitride, etc. added to tetragonal zirconia (Y-PSZ) to which yttrium oxide is added Although ceramics are provided, due to the expensive equipment and complicated processes, it is difficult to manufacture large members, and the price of the product is very high, and there is a limitation in application.

일반적으로 반도성 세라믹스를 제조하는 방법에는 TiO2나 BaTiO3등의 절연성 세라믹스에 첨가제를 소량 첨가하여 전자를 생성시키는 방법과 환원분위기 소성을 통하여 산소빈자리 발생에 의한 전자생성 방법이 있는데 불순물이나 제조공정에 따라 안정적인 저항의 변화가 심해 정전기 제거용 반도성 세라믹스를 제조하기 어렵다(전자재료 세라믹스, 윤상옥외 역, 반도출판사, 1993).Generally, semiconducting ceramics are prepared by adding small amounts of additives to insulating ceramics such as TiO 2 or BaTiO 3 to generate electrons and generating electrons by oxygen vacancies through reducing atmosphere firing. As a result, it is difficult to manufacture semiconducting ceramics for eliminating static electricity due to the severe change in resistance (electronic material ceramics, Sang-Yoon Yoon, semi-published publisher, 1993).

따라서, 정전기 제거용 재료의 적용이 확대되고 대형화되는 추세에 대응하기 위해서는 전술한 바와 같은 문제점의 해결과 새로운 요구조건이 만족될 수 있는 진보된 정전기 제거용 재료 조성물의 개발이 요구되고 있다.Accordingly, in order to cope with the trend of expanding and increasing the application of the static elimination material, it is required to solve the above-mentioned problems and to develop an advanced static elimination material composition in which new requirements can be satisfied.

본 발명은 전술한 바와 같은 문제점을 해결하기 위하여 안출된 것으로서, 본 발명은 비저항이 낮은 칼슘망간네이트(CaMnO3)에 같은 결정구조를 갖는 절연성 물질을 고용시킴으로써, 비저항의 변화가 급격하게 일어나지 않고 안정적으로 구현되도록 함은 물론, 수지 등 고분자 물질을 적용하지 아니하여 소결성이 우수하여 높은 밀도를 갖으며, 높은 강도특성을 갖는 정전기제거용 고용형 반도성 세라믹스를 제조할 수 있도록 하는 세라믹 조성물을 제공하는 것을 목적으로 한다.The present invention has been made to solve the problems described above, the present invention by employing an insulating material having the same crystal structure in calcium manganate (CaMnO 3 ) having a low specific resistance, it is stable without a sudden change in the specific resistance To provide a ceramic composition that can be implemented, as well as having a high density and excellent high sintering properties without applying a polymer material such as a resin, and to produce a solid-type semiconducting ceramics for removing static electricity having high strength characteristics For the purpose of

또한, 본 발명은 전자 및 광학산업의 장치 및 시스템의 제조공정에서 발생하는 정전기를 제거함으로써, 불꽃방전이나 이물질의 오염 등을 방지할 수 있는 정전기 제거용 고용형 반도성 세라믹 조성물을 제공하는 것을 다른 목적으로 한다.The present invention also provides a solid solution semiconducting ceramic composition for static electricity removal which can prevent spark discharge and contamination of foreign matters by removing static electricity generated in the manufacturing process of devices and systems in the electronic and optical industries. The purpose.

본 발명은 종래에는 제조가 어려운 대형부재를 제조하는데 있어서 고비용 구조를 유지하였던 문제점을 탈피하여, 대형부재임에도 불구하고, 이를 보다 용이하게 제조할 수 있도록 하는 정전기 제거용 고용형 반도성 세라믹 조성물을 제공하는 것을 다른 목적으로 한다.The present invention provides a solid solution semiconducting ceramic composition for removing static electricity, which makes it easier to manufacture, despite being a large member, thereby avoiding the problem of maintaining a high-cost structure in manufacturing a large member that is difficult to manufacture in the past. For other purposes.

본 발명은 전술한 목적을 달성하기 위하여, (1-x)CaMnO3와 xABO3의 고용체 세라믹 조성물로서, 상기 A는 Ca, Sr 또는 Ba이고, B는 Zr, Sn 또는 Ti이며, x는 0.4 내지 0.8 의 범위인 정전기 제거용 고용형 반도성 세라믹 조성물을 제공한다.In order to achieve the above object, the present invention provides a solid solution ceramic composition of (1-x) CaMnO 3 and xABO 3 , wherein A is Ca, Sr or Ba, B is Zr, Sn or Ti, and x is 0.4 to There is provided a solid solution semiconducting ceramic composition for electrostatic removal in the range of 0.8.

또한, 본 발명은 Mn, Ti, Zr, Ca, Sr, Ba, Sn을 포함하는 산화물 또는 염을 출발물질로 하여 CaMnO3와 ABO3(A는 Ca, Sr 또는 Ba이고, B는 Zr, Sn 또는 Ti)의 혼합물을 수득하는 단계; 상기 CaMnO3와 ABO3를 합성하여 고용체를 제조하는 단계; 및 상기 고용체를 소결하는 단계;를 포함하여 구성되며, CaMnO3와 ABO3는 0.2 : 0.8 ~ 0.6 : 0.4의 몰비의 범위가 되도록 하는 정전기 제거용 고용형 반도성 세라믹 조성물의 제조방법을 제공한다.In addition, the present invention is based on the oxide or salt containing Mn, Ti, Zr, Ca, Sr, Ba, Sn as CaMnO 3 and ABO 3 (A is Ca, Sr or Ba, B is Zr, Sn or Obtaining a mixture of Ti); Preparing a solid solution by synthesizing the CaMnO 3 and ABO 3 ; And sintering the solid solution; CaMnO 3 and ABO 3 provide a method of manufacturing a solid solution-type semiconducting ceramic composition for static elimination so that the molar ratio is in a range of 0.2: 0.8 to 0.6: 0.4.

상기 CaMnO3와 ABO3를 합성하여 고용체를 제조하는 단계에서는 1000 ~ 1100℃의 온도범위에서 1 ~ 3 시간 하소하며, 상기 고용체를 소결하는 단계에서는 1350 ~ 1400℃의 온도범위에서 1 ~ 3 시간 소결하는 것이 바람직하다.In the step of preparing the solid solution by synthesizing the CaMnO 3 and ABO 3 is calcined for 1 to 3 hours in the temperature range of 1000 ~ 1100 ℃, in the step of sintering the solid solution is sintered for 1 to 3 hours in the temperature range of 1350 ~ 1400 ℃ It is desirable to.

본 발명에 의한 정전기제거용 고용형 반도성세라믹 조성물은 전자 및 광학산업의 장치 및 시스템의 제조공정에서 발생하는 정전기를 제거시킴으로써, 불꽃방전이나 이물질의 오염 등을 방지할 수 있는 부재를 용이하게 제조할 수 있으며, 따라서, 이를 사용한 부품과 장치의 신뢰성 증진 및 적용확대에 기여하는 작용효과가 기대된다.The solid solution semiconductive ceramic composition for electrostatic removal according to the present invention can easily manufacture a member that can prevent spark discharge and contamination of foreign substances by removing static electricity generated in the manufacturing process of devices and systems in the electronic and optical industries. Therefore, the effect is expected to contribute to the increase of reliability and application of parts and devices using the same.

또한, 높은 상대밀도와 소기의 강도값을 갖는 정전기제거용 고용형 반도성 세라믹스를 간이한 공정에 의해 제조할 수 있어 세라믹스의 내구성 및 수명을 확보할 수 있는 작용효과가 기대된다.In addition, since the solid solution-type semiconducting ceramics for removing static electricity having a high relative density and a desired strength value can be manufactured by a simple process, the effect of securing the durability and lifespan of the ceramics is expected.

도 1은 본 발명의 일 실시예에 의한 칼슘망간네이트(CaMnO3)계 고용형 반도성 세라믹스의 비저항 변화를 나타내는 그래프,
도 2는 본 발명의 일 실시예에 의한 칼슘망간네이트(CaMnO3)계 고용형 반도성 세라믹스의 X-선 회절분석 그래프이다.
1 is a graph showing the change in specific resistance of calcium manganate (CaMnO 3 ) -based solid solution ceramics according to an embodiment of the present invention;
2 is an X-ray diffraction graph of calcium manganate (CaMnO 3 ) based solid solution ceramics according to one embodiment of the present invention.

이하에서는 본 발명을 첨부되는 도면 및 바람직한 실시예를 기초로 보다 상세히 설명한다. 다만, 본 발명의 범위가 이들 실시예에만 국한되는 것은 아니다.Hereinafter, the present invention will be described in detail with reference to the accompanying drawings and preferred embodiments. However, the scope of the present invention is not limited only to these Examples.

본 발명은 비저항이 낮은 칼슘망간네이트(CaMnO3)에 같은 결정구조의 절연성 물질을 고용시킴으로써, 넓은 영역에서 비저항의 변화를 안정적으로 구현시킴은 물론, 치밀하고 비교적 높은 강도를 갖는 정전기 제거용 고용형 반도성 세라믹스를 용이하게 제조할 수 있도록 하는 조성물에 관한 것이다.In the present invention, by employing an insulating material having the same crystal structure in calcium manganate (CaMnO 3 ) having a low specific resistance, it is possible to stably realize a change in specific resistance in a wide area, as well as to form a solid solution for removing static electricity having a dense and relatively high strength. The present invention relates to a composition that enables easy manufacture of semiconducting ceramics.

본 발명에 의한 정전기제거용 고용형 반도성 세라믹 조성물의 조성비를 구체적으로 나타내면 (1-x)CaMnO3 + x ABO3 (A = Ca, Sr 또는 Ba, B = Zr, Sn 또는 Ti)으로 표시되는 식 중, x는 0.4 내지 0.8이다. Specifically showing the composition ratio of the solid-state semiconducting ceramic composition for static elimination according to the present invention is represented by (1-x) CaMnO 3 + x ABO 3 (A = Ca, Sr or Ba, B = Zr, Sn or Ti) In the formula, x is 0.4 to 0.8.

CaMnO3와 ABO3는 모두 동일한 페로브스카이트 구조를 이룬다.
CaMnO 3 and ABO 3 both form the same perovskite structure.

- 제조예 및 평가예-Preparation and Evaluation Example

본 발명의 정전기 제거용 고용형 반도성 세라믹 조성물은 다음과 같은 일반적인 산화물 혼합 방법에 의해 용이하게 제조할 수 있다.The solid solution semiconducting ceramic composition for static elimination of the present invention can be easily produced by the following general oxide mixing method.

본 발명에서는 Mn, Ti, Zr, Ca, Sr, Ba, Sn을 포함하는 산화물 또는 염을 출발물질로 하여 CaMnO3와 ABO3(A는 Ca, Sr 또는 Ba이고, B는 Zr, Sn 또는 Ti)의 혼합물을 수득할 수 있다.In the present invention, CaMnO 3 and ABO 3 (A is Ca, Sr or Ba, and B is Zr, Sn or Ti) by using oxides or salts including Mn, Ti, Zr, Ca, Sr, Ba, and Sn as starting materials. A mixture of can be obtained.

구체적으로 본 실시예에서는 산화망간(MnO2), 산화티탄(TiO2), 산화지르코늄(ZrO2), 탄산칼슘(CaCO3), 탄산스트론튬(SrCO3) 그리고 탄산바륨(BaCO3)을 각각 이용하여 표 1에 나타낸 각 페로브스카이트 조성이 되도록 제조하기 위하여 칭량하고, 지르코니아 볼밀에서 증류수와 함께 잘 혼합하고 분쇄한다. 이 때, 산화망간을 대신하여 Mn2O3, MnO 그리고 MnCO3 등도 합성과정에서 분해와 원자가 변화를 통하여 동일한 역할이 가능하므로 대체하여 사용할 수 있다. 한편, 실시예에서는 나타내지 아니하였으나, ABO3를 생성하기 위하여 산화주석(SnO2)을 사용할 수도 있다.Specifically, in the present embodiment, manganese oxide (MnO 2 ), titanium oxide (TiO 2 ), zirconium oxide (ZrO 2 ), calcium carbonate (CaCO 3 ), strontium carbonate (SrCO 3 ) and barium carbonate (BaCO 3 ) are used, respectively. And weighed to produce each perovskite composition shown in Table 1, mixed well with distilled water in a zirconia ball mill and ground. In this case, instead of manganese oxide, Mn 2 O 3 , MnO and MnCO 3 may also be used in the synthesis process because they have the same role through decomposition and valence change. Although not shown in the examples, tin oxide (SnO 2 ) may be used to generate ABO 3 .

이와 같은 혼합방법은 위와 같은 지르코니아 볼밀에 의한 혼합 방법 이외에도 다양한 방법을 적용하여 실행할 수 있다.Such a mixing method can be carried out by applying various methods in addition to the mixing method by the zirconia ball mill as described above.

이와 같이 혼합한 원료는 1000 ~ 1100℃에서 약 2시간 동안 하소하여 합성하고, 이렇게 합성된 원료는 다시 증류수와 함께 볼밀로 재분쇄한 후, 원형의 금속몰드에서 100MPa의 압력으로 원판형 시편으로 성형하여 1350 ~ 1400℃의 온도에서 약 2시간 동안 소결하였다. 위와 같은 하소시간 및 소결시간은 약 2시간으로 한정되는 것은 아니며, 온도에 따라서 예를 들어 1 ~ 3시간으로 변동이 가능하다. 또한 금속몰드의 형상, 시편의 형상, 가압력 등도 변동이 가능하다.The mixed raw materials were calcined at 1000 to 1100 ° C. for about 2 hours, and the synthesized raw materials were again milled together with distilled water by ball milling, and then formed into circular specimens at a pressure of 100 MPa in a circular metal mold. Sintered at a temperature of 1350 ~ 1400 ℃ for about 2 hours. The calcination time and sintering time as described above are not limited to about 2 hours, and may vary, for example, from 1 to 3 hours depending on the temperature. In addition, the shape of the metal mold, the shape of the specimen, the pressing force, etc. can be varied.

만일 하소온도가 1000℃ 미만이거나, 소결온도가 1350℃ 미만인 경우에는 바람직한 비저항값보다 높은 수준의 비저항값이 도출되었으며, 하소온도가 1100℃를 초과하는 경우에는 불필요한 공정이라고 하거나 또는 분쇄에 어려울 정도로 응집체가 생성되어 바람직하지 않으며, 소결온도가 1400℃를 초과하는 경우에는 소결체의 미세구조가 변형되거나 또는 불필요하게 높은 온도로 소결하는 결과가 도출되므로 바람직하지 아니하다.If the calcination temperature is less than 1000 ℃ or the sintering temperature is less than 1350 ℃, the specific resistance value higher than the desired specific resistance value was derived. If the calcination temperature is more than 1100 ℃, it is called unnecessary process or it is hard to be pulverized. It is not preferable to produce the sintering temperature when the sintering temperature exceeds 1400 ° C., since the microstructure of the sintered body is deformed or the result of sintering to an unnecessarily high temperature is obtained.

이렇게 제조된 소결체는 소결성과 비저항 측정을 통하여 목적하는 특성들을 평가하였으며, 이와 같은 제조 공정을 통하여 정전기제거용 고용형 반도성 세라믹스를 용이하게 제조될 수 있다.
The sintered body thus prepared was evaluated for the desired properties by measuring the sinterability and resistivity, and through this manufacturing process, it is possible to easily produce a solid solution-type semiconducting ceramics for removing static electricity.

이와 같이 소결하여 제조한 시편은 선수축율과 아르키메데스법에 의한 밀도측정을 통하여 소결성을 평가하였으며, 양면에 은전극을 형성하여 2단자법으로 저항을 측정하고 비저항을 계산하여 전기적 특성을 평가하였다.The specimens prepared by sintering were evaluated for sinterability through the measurement of bow axial rate and density by Archimedes' method. The silver electrodes were formed on both sides to measure the resistance by two-terminal method, and the electrical resistance was evaluated.

실험 결과는 표 1에서 보는 바와 같다.The experimental results are as shown in Table 1.

(1-x)CaMnO3 + xABO3 (A = Ca, Sr 또는 Ba, B = Zr, Sn 또는 Ti) 반도성 세라믹 조성물의 특성Properties of (1-x) CaMnO 3 + xABO 3 (A = Ca, Sr or Ba, B = Zr, Sn or Ti) Semiconducting Ceramic Compositions 실시예
Example
CaMnO3
(mol)
CaMnO 3
(mol)
CaTiO3 (mol)CaTiO 3 (mol) SrTiO3 (mol)SrTiO 3 (mol) BaTiO3 (mol)BaTiO 3 (mol) CaZrO3 (mol)CaZrO 3 (mol) 상대
밀도(%)
opponent
density(%)
비저항 (ohm.cm)Resistivity (ohm.cm)
실시예1
Example 1
0.2
0.2
0.8
0.8
0
0
0
0
0
0
98.6
98.6
1.0x105
1.0x10 5
실시예2
Example 2
0.3
0.3
0.7
0.7
0
0
0
0
0
0
99.3
99.3
4.9x103
4.9 x 10 3
실시예3
Example 3
0.35
0.35
0.65
0.65
0
0
0
0
0
0
99.5
99.5
1.2x103
1.2 x 10 3
실시예4
Example 4
0.4
0.4
0.6
0.6
0
0
0
0
0
0
99.6
99.6
4.5x102
4.5 x 10 2
실시예5
Example 5
0.5
0.5
0.5
0.5
0
0
0
0
0
0
99.6
99.6
3.1x102
3.1 x 10 2
실시예6
Example 6
0.6
0.6
0.4
0.4
0
0
0
0
0
0
99.7
99.7
1.1x102
1.1 x 10 2
실시예7
Example 7
0.4
0.4
0
0
0.6
0.6
0
0
0
0
98.8
98.8
2.9x103
2.9 x 10 3
실시예8
Example 8
0.4
0.4
0
0
0
0
0.6
0.6
0
0
97.6
97.6
3.6x104
3.6 x 10 4
실시예9
Example 9
0.4
0.4
0
0
0
0
0
0
0.6
0.6
99.4
99.4
1.2x103
1.2 x 10 3
실시예10
Example 10
0.4
0.4
0.3
0.3
0.3
0.3
0
0
0
0
98.7
98.7
9.1x102
9.1 x 10 2
실시예11
Example 11
0.4
0.4
0.3
0.3
0
0
0.3
0.3
0
0
98.8
98.8
1.8x103
1.8 x 10 3
실시예12
Example 12
0.4
0.4
0.3
0.3
0
0
0
0
0.3
0.3
99.2
99.2
8.7x102
8.7 x 10 2
실시예13
Example 13
0.4
0.4
0.2
0.2
0.2
0.2
0.2
0.2
0
0
98.6
98.6
1.3x103
1.3 x 10 3
실시예14
Example 14
0.4
0.4
0.2
0.2
0.2
0.2
0
0
0.2
0.2
99.1
99.1
9.4x102
9.4 x 10 2

표 1에 나타낸 (1-x)CaMnO3 + xABO3 (A = Ca, Sr 또는 Ba, B = Zr, Sn 또는 Ti) 반도성 세라믹 조성물의 특성을 살펴보면, 도전성인 칼슘망간네이트 (CaMnO3)의 첨가량이 증가함에 따라 비저항을 감소시키고 있으며, 이러한 경향은 같은 결정구조의 절연성 다른 화합물에서도 다소 차이는 있으나 비슷한 특성을 나타냄을 알 수 있다.Looking at the properties of the (1-x) CaMnO 3 + xABO 3 (A = Ca, Sr or Ba, B = Zr, Sn or Ti) semiconducting ceramic composition shown in Table 1, the conductive calcium manganate (CaMnO 3 ) As the addition amount increases, the specific resistance decreases, and this tendency shows similar characteristics, although somewhat different from other insulating compounds having the same crystal structure.

이러한 결과는 도전성의 칼슘망간네이트(CaMnO3) 격자가 절연성의 다른 페로브스카이트 화합물 격자와 서로 균일하게 혼합되어 고용체를 형성함으로써 전도의 길(path)이 제어되어 비저항의 변화가 일어나는 현상으로 X-선 회절분석을 통하여 이들 화합물이 완전한 고용체가 이루어짐을 알 수 있었다.These results indicate that the conductive calcium manganate (CaMnO 3 ) lattice is uniformly mixed with other insulating perovskite compound lattice to form a solid solution, so that the path of conduction is controlled to change the resistivity. -Diffraction analysis showed that these compounds were completely solid solutions.

그러나, 도전성의 칼슘망간네이트(CaMnO3)의 함량이 0.2 mol 보다 작으면 전도의 길(path)이 너무 차단되어 높은 저항을 가지므로 정전기가 효율적으로 제거되지 못하며, 0.6 mol 보다 많이 첨가되면 전도의 길(path)이 너무 많아 낮은 저항을 가지므로 불꽃방전 등이 발생할 수 있어 적합하지 못하다. 따라서,정전기 제거용 고용형 반도성 세라믹 조성물에서 도전성의 칼슘망간네이트(CaMnO3)의 함량이 0.2 내지 0.6 mol인 경우, 1×105 ohm.cm 내지 1.1×102 ohm.cm의 범위의 저항값을 나타내는 바람직한 조성에 해당하며, 0.3 내지 0.4 mol인 경우, 5×104 ohm.cm 내지 2×103 ohm.cm 범위의 저항값을 나타내는 더욱 바람직한 조성에 해당된다.However, if the content of conductive calcium manganate (CaMnO 3 ) is less than 0.2 mol, the path of conduction is too blocked to have high resistance, and thus static electricity cannot be removed efficiently. It is not suitable because there are too many paths and have low resistance, so spark discharge may occur. Therefore, when the content of conductive calcium manganate (CaMnO 3 ) in the solid solution semiconducting ceramic composition for electrostatic removal is 0.2 to 0.6 mol, resistance in the range of 1 × 10 5 ohm.cm to 1.1 × 10 2 ohm.cm Corresponding to a preferred composition exhibiting a value, and from 0.3 to 0.4 mol, it corresponds to a more preferred composition exhibiting a resistance value in the range of 5 × 10 4 ohm.cm to 2 × 10 3 ohm.cm.

이때, 목적하는 상대밀도값은 95% 이상이며, 꺾임강도 측정기준으로 200MPa 이상의 값을 나타낸다.At this time, the desired relative density value is 95% or more, and indicates a value of 200 MPa or more as the bending strength measurement standard.

요컨대, 본 발명에 따르면, 도전성과 절연성으로 대표되는 동일한 페로브스카이트 결정구조를 합성한 것이므로, 합성이 매우 용이하여 합성 및 소결체가 저렴하게 제조될 수 있고, 또한, 세라믹 물질로 이루어져 있어 종래의 수지조성물을 포함한 예에 비하여 강도를 확보할 수 있으며, 조성의 변화에 따른 비저항의 변화를 조절하기 용이하므로, 정전기 제거용 세라믹스를 간이하게 제조할 수 있다. In short, according to the present invention, since the same perovskite crystal structure represented by conductivity and insulation is synthesized, the synthesis is very easy, and the synthesis and sintered body can be manufactured at low cost, and also made of a ceramic material. Compared with the example including the resin composition, the strength can be secured, and since the change of the specific resistance according to the change of the composition can be easily controlled, it is possible to easily manufacture the ceramics for removing static electricity.

즉, 본 발명에 따라 제조된 고용형 반도성 세라믹스는 비저항이 낮은 칼슘망간네이트(CaMnO3)에 같은 페로브스카이트 결정구조의 절연성 물질을 고용시킴으로써 넓은 영역에서 비저항의 변화를 안정적으로 구현시킴은 물론, 치밀하고 비교적 높은 강도를 갖는 정전기 제거용 부재들을 용이하게 제조할 수 있는 조성물을 제공한다.That is, the solid solution-type semiconducting ceramics prepared according to the present invention stably realize the change of the resistivity in a wide range by employing an insulating material of the same perovskite crystal structure in calcium manganate (CaMnO 3 ) having a low resistivity. Of course, there is provided a composition which can easily manufacture dense and relatively high strength static eliminating members.

이상과 같이 본 발명을 바람직한 실시예를 기초로 설명하였으나, 이는 실시예일 뿐, 이에 의하여 본 발명의 보호범위가 한정되는 것으로 해석되어서는 아니되며, 본 발명의 보호범위는 특허청구범위의 해석에 의하여야 함은 자명하다고 할 것이다. As described above, the present invention has been described based on preferred embodiments, which are only examples, and thus, the scope of protection of the present invention should not be construed as being limited, and the scope of protection of the present invention is based on the interpretation of the claims. Should be self-explanatory.

Claims (3)

(1-x)CaMnO3와 xABO3의 고용체 세라믹 조성물로서,
상기 A는 Ca, Sr 또는 Ba이고, B는 Zr, Sn 또는 Ti이며, x는 0.4 내지 0.8 의 범위인 것을 특징으로 하는 정전기 제거용 고용형 반도성 세라믹 조성물.
As a solid solution ceramic composition of (1-x) CaMnO 3 and xABO 3 ,
A is Ca, Sr or Ba, B is Zr, Sn or Ti, x is in the range of 0.4 to 0.8, the solid solution semiconducting ceramic composition for electrostatic removal.
Mn, Ti, Zr, Ca, Sr, Ba, Sn을 포함하는 산화물 또는 염을 출발물질로 하여 CaMnO3와 ABO3(A는 Ca, Sr 또는 Ba이고, B는 Zr, Sn 또는 Ti)의 혼합물을 수득하는 단계;
상기 CaMnO3와 ABO3를 합성하여 고용체를 제조하는 단계; 및
상기 고용체를 소결하는 단계;
를 포함하여 구성되며,
CaMnO3와 ABO3는 0.2 : 0.8 ~ 0.6 : 0.4의 몰비의 범위가 되도록 하는 것을 특징으로 하는 정전기 제거용 고용형 반도성 세라믹 조성물의 제조방법.
A mixture of CaMnO 3 and ABO 3 (A is Ca, Sr or Ba, and B is Zr, Sn or Ti), starting from an oxide or salt containing Mn, Ti, Zr, Ca, Sr, Ba, Sn as a starting material Obtaining;
Preparing a solid solution by synthesizing the CaMnO 3 and ABO 3 ; And
Sintering the solid solution;
And,
CaMnO 3 and ABO 3 is a method for producing a solid-state semiconducting ceramic composition for electrostatic removal, characterized in that in the range of molar ratio of 0.2: 0.8 ~ 0.6: 0.4.
제 2 항에 있어서,
상기 CaMnO3와 ABO3를 합성하여 고용체를 제조하는 단계에서는 1000 ~ 1100℃의 온도범위에서 1 ~ 3 시간 하소하며, 상기 고용체를 소결하는 단계에서는 1350 ~ 1400℃의 온도범위에서 1 ~ 3 시간 소결하는 것을 특징으로 하는 정전기 제거용 고용형 반도성 세라믹 조성물의 제조방법.
The method of claim 2,
In the step of preparing the solid solution by synthesizing the CaMnO 3 and ABO 3 is calcined for 1 to 3 hours in the temperature range of 1000 ~ 1100 ℃, in the step of sintering the solid solution is sintered for 1 to 3 hours in the temperature range of 1350 ~ 1400 ℃ Method for producing a solid solution semiconducting ceramic composition for electrostatic removal.
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CN107032763A (en) * 2017-04-11 2017-08-11 贵州大学 One kind prepares n-type CaMnO3The method of base thermoelectric ceramics
CN107056290A (en) * 2016-11-04 2017-08-18 西安交通大学 A kind of method of regulation and control ferroelectric ceramics Curie temperature

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KR100553118B1 (en) 2000-11-21 2006-02-22 생-고뱅 세라믹스 앤드 플라스틱스, 인코포레이티드 ESD dissipative ceramic components

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KR100553118B1 (en) 2000-11-21 2006-02-22 생-고뱅 세라믹스 앤드 플라스틱스, 인코포레이티드 ESD dissipative ceramic components

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CN107056290A (en) * 2016-11-04 2017-08-18 西安交通大学 A kind of method of regulation and control ferroelectric ceramics Curie temperature
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