KR100198244B1 - A semiconductor glass composition - Google Patents
A semiconductor glass composition Download PDFInfo
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- KR100198244B1 KR100198244B1 KR1019910008937A KR910008937A KR100198244B1 KR 100198244 B1 KR100198244 B1 KR 100198244B1 KR 1019910008937 A KR1019910008937 A KR 1019910008937A KR 910008937 A KR910008937 A KR 910008937A KR 100198244 B1 KR100198244 B1 KR 100198244B1
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/12—Silica-free oxide glass compositions
- C03C3/16—Silica-free oxide glass compositions containing phosphorus
- C03C3/21—Silica-free oxide glass compositions containing phosphorus containing titanium, zirconium, vanadium, tungsten or molybdenum
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/12—Silica-free oxide glass compositions
- C03C3/16—Silica-free oxide glass compositions containing phosphorus
- C03C3/19—Silica-free oxide glass compositions containing phosphorus containing boron
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Abstract
본 발명은 반도성 산화물 유리 특히, V2O5-P2O5계 반도성 산화물 유리 조성물에 관한 것으로, 좀 더 구체적으로는 60몰%≤V2O5≤90몰%, 0몰%Fe3O430몰% 및 P2O510몰%로 구성되는 것으로 325℃의 유리전이온도, 360℃의 유리연화점, 5.5x10-6/℃의 열팽창 계수 및 2.98의 비중을 갖는 유리를 제조할 수 있는 반도성 산화물 유리 조성물에 관한 것이다.The present invention relates to semiconducting oxide glass, in particular, to a V 2 O 5 -P 2 O 5 based semiconducting oxide glass composition, more specifically 60 mol% ≦ V 2 O 5 ≦ 90 mol%, 0 mol% Fe 30 mol% of 3 O 4 and 10 mol% of P 2 O 5 to prepare a glass having a glass transition temperature of 325 ° C., a glass softening point of 360 ° C., a thermal expansion coefficient of 5.5 × 10 −6 / ° C., and a specific gravity of 2.98. A semiconductive oxide glass composition can be obtained.
90몰% V2O5-10몰%P2O5반도성 세라믹 유리 조성물에 있어서, V2O5의 일부분을 0몰%Fe3O430몰%로 치환함으로서 유리의 결합력이 증가되어 유리전이온도, 연화점, 열팽창계수 및 밀도가 향상되었으며, 이로 인하여 종래 반도성 세라믹 유리의 강도 저하 문제점을 해결하였다.90 mol% V 2 O 5 -10 mol% P 2 O 5 In the semiconductive ceramic glass composition, the bonding strength of the glass is increased by substituting a portion of V 2 O 5 with 0 mol% Fe 3 O 4 30 mol%. The transition temperature, the softening point, the coefficient of thermal expansion and the density have been improved, thereby solving the problem of strength reduction of the conventional semiconducting ceramic glass.
Description
본 발명은 반도성 산화물 유리 특히, V2O5-P2O5계 반도성 산화물 유리 조성물에 관한 것으로, 좀 더 구체적으로는 60몰%≤V2O5≤90몰%, 0몰%Fe3O430몰% 및 P2O510몰%로 구성되는 것으로 325℃의 유리전이온도, 360℃의 유리연화점, 5.5x10-6/℃의 열팽창 계수 및 2.98의 비중을 갖는 유리를 제조할 수 있는 반도성 산화물 유리 조성물에 관한 것이다.The present invention relates to semiconducting oxide glass, in particular, to a V 2 O 5 -P 2 O 5 based semiconducting oxide glass composition, more specifically 60 mol% ≦ V 2 O 5 ≦ 90 mol%, 0 mol% Fe 30 mol% of 3 O 4 and 10 mol% of P 2 O 5 to prepare a glass having a glass transition temperature of 325 ° C., a glass softening point of 360 ° C., a thermal expansion coefficient of 5.5 × 10 −6 / ° C., and a specific gravity of 2.98. A semiconductive oxide glass composition can be obtained.
반도성 산화물 유리는 망목형성산화물(Net-Work Formation oxide)과 천이금속산화물로 이루어지며, 이 종류의 유리는 25℃에서 비저항이 109Ω.Cm 미만이고 NTCR(negative temperature coefficient resistance) 특성을 갖고 있으며, 제조가 간단하고, 조성에 따라 연속적인 반도성 특성을 나타내고, 대량 생산이 가능하고, 방사선에 노출시에도 특성 변화가 거의 없어 열적 센서인 온도센서와 스위치센서 등에 널리 사용되고 있다.Semiconducting oxide glass is composed of Net-Work Formation oxide and transition metal oxide. This type of glass has a resistivity of less than 10 9 Ω.Cm at 25 ° C and has a negative temperature coefficient resistance (NTCR) characteristic. In addition, it is simple to manufacture, exhibits continuous semiconducting properties depending on the composition, mass production is possible, and almost no change in characteristics even when exposed to radiation, and is widely used in thermal sensors such as temperature sensors and switch sensors.
1950년대초 망목형성 산화물에 천이금속산화물을 함유한 유리에서는 전자에 의한 전기전도특성을 나타낸다는 보고 이후로 V2O5-P2O5계 유리의 전기적 성질에 관한 연구가 활발히 진행되었다. V2O5-P2O5계 유리에서 천이금속 산화물인 V2O5의 함량이 증가할수록 전기전도도가 증가하는 이유는 유리내의 V5+/V4+의 비가 증가하기 때문인 것으로 보고되고 있다.In the early 1950's, the glass containing the transition metal oxide in the mesh forming oxide showed the electrical conduction characteristics by electrons, and since then, studies on the electrical properties of the V 2 O 5 -P 2 O 5 based glass have been actively conducted. It is reported that the electrical conductivity increases as the content of the transition metal oxide V 2 O 5 increases in the V 2 O 5 -P 2 O 5 glass, because the ratio of V 5+ / V 4+ in the glass increases. .
그러나, V2O5-P2O5계 반도성 산화물 유리는 우수한 전기적 특성을 지닌 것과는 반대로 산업상 이용하기 어려운 치명적인 문제점을 가지고 있다. 즉, V2O5-P2O5계 유리는 유리간의 결합력이 나빠 대기중에 오랜시간 방치해 두면 강도가 떨어져 물러지는 단점이 있었다.However, V 2 O 5 -P 2 O 5 -based semiconducting oxide glass has a fatal problem that is difficult to use industrially as opposed to having excellent electrical properties. In other words, V 2 O 5 -P 2 O 5- based glass has a disadvantage in that the bonding strength between the glass is bad, the strength falls off if left in the air for a long time.
따라서, 본 발명의 목적은 유리의 결합력을 향상시켜 물성의 향상 뿐만 아니라 강도를 증가시킬 수 있는 반도성 산화물 유리 조성물을 제공하는 데 있다.Accordingly, it is an object of the present invention to provide a semiconducting oxide glass composition capable of increasing the bonding strength of the glass and increasing the strength as well as the physical properties.
상술한 목적을 달성하기 위하여 본 발명에서는 V2O5-P2O5계 유리에 있어서 V2O5대신에 Fe3O4를 일부분 치환시켜 유리의 결합력을 증가시킴으로서 유리의 전이온도 및 연화점이 향상되었고, 열팽창력이 줄어들고 밀도가 향상됨에 따라 V2O5-P2O5계 유리의 문제점인 강도 저하의 단점을 해결하였다.The transition temperature and the softening point of glass was substituted in the present invention, part of the Fe 3 O 4 to V 2 O 5 instead of in the V 2 O 5 -P 2 O 5 based glass by increasing the bonding strength of the glass in order to achieve the above object As a result, the thermal expansion force is reduced and the density is improved, thereby solving the disadvantage of the strength reduction, which is a problem of the V 2 O 5 -P 2 O 5 glass.
본 발명을 좀 더 구체적으로 설명하면 다음과 같다.The present invention is described in more detail as follows.
V2O590몰%-P2O510몰%계 유리에 있어서 일부의 V2O5대신에 0몰%≤Fe3O4≤30몰%를 치환하여 균질하게 혼합시킴으로서 60몰%≤V2O5≤90몰%, 0몰%Fe3O430몰%, P2O510몰%로 구성되는 본 발명의 반도성 산화물 유리 조성물을 제조하였다.V 2 O 5 -P 2 O 5 90 mole% 10 mole% based glass 0 mol% ≤Fe 3 O 4 by substituting a homogeneous mixture ≤30 mol% sikimeuroseo 60 mol%, instead of a part of V 2 O 5 according to ≤ The semiconductive oxide glass composition of the present invention was prepared consisting of V 2 O 5 ≦ 90 mol%, 0 mol% Fe 3 O 430 mol%, and P 2 O 5 10 mol%.
상기 조성물을 백금도가니에 담아 전기로에서 용융시킨 다음, 200℃로 가열된 강판위에 용융물을 유출시켜 후막을 제조한 후에 200℃로 예열된 전기로에서 서냉시켜 반도성 산화물 유리를 제조하였다.The composition was put in a platinum crucible, melted in an electric furnace, and then melted on a steel plate heated to 200 ° C. to prepare a thick film, followed by slow cooling in an electric furnace preheated to 200 ° C. to prepare a semiconductive oxide glass.
본 발명의 반도성 산화물 유리 조성물에 있어서, Fe3O4를 30몰%이상 사용하였을 경우에는 실투(Vitrification)되어 유리를 제조 못하는 문제점이 있었다.In the semiconductive oxide glass composition of the present invention, when Fe 3 O 4 or more is used at 30 mol% or more, there is a problem in that the glass cannot be manufactured due to devitrification.
다음의 실시예는 본 발명의 반도성 산화물 유리 조성물 및 이의 효능, 효과를 좀 더 구체적으로 설명하는 것이지만, 본 발명의 범주를 한정하는 것은 아니다.The following examples further illustrate the semiconductive oxide glass composition of the present invention and its efficacy and effect, but do not limit the scope of the present invention.
[실시예1]Example 1
V2O580몰%, Fe3O410몰% 및 P2O510몰%의 비율로 평량하여 볼밀(ball mill)로 균질하게 될 때 까지 혼합한 후, 백금 도가니에 담아 전기로에서 용융시킨 다음, 용융물을 200℃로 가열된 강판위에 유출시켜 후막으로 제조하고 200℃로 예열된 전기로에 넣어 서냉하여 반도성 산화물 유리를 제조하였다.80 mol% of V 2 O 5 , 10 mol% of Fe 3 O 4, and 10 mol% of P 2 O 5 were mixed and mixed until homogeneous with a ball mill, and then melted in an electric furnace in a platinum crucible. Then, the melt was flowed out on a steel sheet heated to 200 ° C. to prepare a thick film, and was cooled in an electric furnace preheated to 200 ° C. to prepare a semiconductive oxide glass.
제조된 유리의 밀도를 아르키메데스의 원리를 이용한 수은 하이드로메터(mercury hydrometer)를 사용하여 측정하였으며, 제조된 유리를 3mmx20mm 크기의 막대로 가공한 후 팽창계(dilatometer)를 사용하여 유리의 열팽창 계수, 유리전이온도와 연화점을 측정하고, 그 결과를 표 1에 기재하였다.The density of the prepared glass was measured using a mercury hydrometer using the Archimedes principle. After processing the prepared glass into a rod of 3 mm x 20 mm, the coefficient of thermal expansion of the glass was measured using a dilatometer. The transition temperature and the softening point were measured, and the results are shown in Table 1.
[실시예2]Example 2
V2O570몰%, Fe3O420몰% 및 P2O510몰%로 한 것을 제외하고는 실시예1과 동일한 방법으로 반도성 세라믹 유리를 제조하고, 실시예1과 동일한 방법으로 물성치를 측정하여 그 결과를 표 1에 기재하였다.A semiconducting ceramic glass was prepared in the same manner as in Example 1, except that 70 mol% of V 2 O 5 , 20 mol% of Fe 3 O 4, and 10 mol% of P 2 O 5 were used to prepare a semiconductive ceramic glass. The physical properties were measured, and the results are shown in Table 1.
[비교예1]Comparative Example 1
V2O590몰%, P2O510몰%한 것을 제외하고는 실시예1과 동일한 방법으로 종래의 반도성 세라믹 유리를 제조하고, 실시예1과 동일한 방법으로 물성치를 측정하여 표 1에 기재하였다.Except for 90 mol% V 2 O 5 , 10 mol% P 2 O 5 A conventional semiconducting ceramic glass was prepared in the same manner as in Example 1, and the physical properties were measured in the same manner as in Example 1 It is described in.
표 1로부터 알 수 있는 바와 같이, 유리전이온도는 230℃에서 325℃로 향상되었고, 유리의 연화점이 250℃에서 360℃로 향상되었으며, 열팽창계수가 6.2x10 /℃에서 5.5x10 /℃로 향상되었고, 밀도는 2.96에서 2.98로 증가되었다.As can be seen from Table 1, the glass transition temperature was improved from 230 ℃ to 325 ℃, the softening point of the glass was improved from 250 ℃ to 360 ℃, the coefficient of thermal expansion 6.2x10 5.5x10 at / ℃ / ° C., density increased from 2.96 to 2.98.
상술한 바와 같이, 90몰% VO-10몰% PO반도성 세라믹 유리 조성물에 있어서, VO의 일부분을 0몰%≤FeO≤30몰%로 치환함으로서 유리의 결합력이 증가되어 유리전이온도, 연화점, 열팽창계수 및 밀도가 향상되었으며, 이로 인하여 종래 반도성 세라믹 유리의 강도 저하 문제점을 해결하였다.As described above, in the 90 mol% VO-10 mol% PO semiconducting ceramic glass composition, by replacing a part of VO with 0 mol% ≦ FeO ≦ 30 mol%, the bonding strength of the glass is increased to increase the glass transition temperature, softening point, The coefficient of thermal expansion and density have been improved, thereby solving the problem of strength reduction of conventional semiconducting ceramic glass.
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| KR1019910008937A KR100198244B1 (en) | 1991-05-30 | 1991-05-30 | A semiconductor glass composition |
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| KR1019910008937A KR100198244B1 (en) | 1991-05-30 | 1991-05-30 | A semiconductor glass composition |
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| KR100198244B1 true KR100198244B1 (en) | 1999-06-15 |
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| EP2468693A3 (en) * | 2010-12-24 | 2012-08-22 | Hitachi Ltd. | Thermoelectric Conversion Material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2468693A3 (en) * | 2010-12-24 | 2012-08-22 | Hitachi Ltd. | Thermoelectric Conversion Material |
| KR101357401B1 (en) * | 2010-12-24 | 2014-02-03 | 가부시키가이샤 히타치세이사쿠쇼 | Thermoelectric conversion material |
| US8802963B2 (en) | 2010-12-24 | 2014-08-12 | Hitachi, Ltd. | Thermoelectric conversion material |
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