TWI751779B - Lio-alo-sio-based crystallized glass and lio-alo-sio-based crystalline glass - Google Patents
Lio-alo-sio-based crystallized glass and lio-alo-sio-based crystalline glass Download PDFInfo
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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
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/11—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen
- C03C3/112—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B32/00—Thermal after-treatment of glass products not provided for in groups C03B19/00, C03B25/00 - C03B31/00 or C03B37/00, e.g. crystallisation, eliminating gas inclusions or other impurities; Hot-pressing vitrified, non-porous, shaped glass products
- C03B32/02—Thermal crystallisation, e.g. for crystallising glass bodies into glass-ceramic articles
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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
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
- C03C1/004—Refining agents
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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
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
- C03C1/04—Opacifiers, e.g. fluorides or phosphates; Pigments
Abstract
Description
本發明係關於Li 2O-Al 2O 3-SiO 2系結晶化玻璃及Li 2O-Al 2O 3-SiO 2系結晶性玻璃。 [相關申請案之交互參照] The present invention relates to Li 2 O-Al 2 O 3 -SiO 2 based crystallized glass and Li 2 O-Al 2 O 3 -SiO 2 based crystallized glass. [Cross-reference to related applications]
本申請案主張於2020年6月22日提出之日本專利申請案第2020-107148號之優先權，其完整內容係併入本申請案中之參考資料。This application claims priority to Japanese Patent Application No. 2020-107148 filed on Jun. 22, 2020, the entire contents of which are incorporated herein by reference.
Li 2O-Al 2O 3-SiO 2系的低膨脹結晶化玻璃使用於石油暖爐、木材暖爐及其他暖爐之前窗、彩色濾光片及影像感應器等的電子製品用基板，電子零件煅燒用耐火板、微波爐棚板、電磁調理器用面板、防火建築用窗玻璃等的材料。例如，在日本特公昭39-21049號公報、日本特公昭40-20182號公報、日本特開平1-308845號公報、日本特開平6-329439號公報、日本特開平9-188538號公報、日本特開2001-48582號公報、日本特開2001-48583號公報中揭示析出以β-石英固溶體或者β-鋰輝石固溶體作為主結晶而成之Li 2O-Al 2O 3-SiO 2系結晶化玻璃。 Li 2 O-Al 2 O 3 -SiO 2- based low-expansion crystallized glass is used as substrates for electronic products such as oil stoves, wood stoves and other stove front windows, color filters and image sensors. Refractory board for parts calcination, microwave oven shelf, panel for electromagnetic conditioner, window glass for fireproof building, etc. For example, in Japanese Patent Publication No. 39-21049, Japanese Patent Publication No. 40-20182, Japanese Patent Publication No. Hei 1-308845, Japanese Patent Publication No. 6-329439, Japanese Patent Publication No. Hei 9-188538, Laid-Open No. 2001-48582 and Japanese Patent Laid-Open No. 2001-48583 disclose the precipitation of Li 2 O-Al 2 O 3 -SiO 2 with β-quartz solid solution or β-spodumene solid solution as the main crystal Department of crystallized glass.
析出β-石英固溶體或者β-鋰輝石固溶體而成的Li 2O-Al 2O 3-SiO 2系結晶化玻璃熱膨脹係數低、機械強度高，有優良的熱特性。還有，Li 2O-Al 2O 3-SiO 2系結晶化玻璃在結晶化過程中可以經由變更熱處理條件而使析出晶體改變，因此，可以從同一組成的原玻璃(亦即，結晶性玻璃)製造出透明結晶化玻璃和不透明結晶化玻璃兩者，可以依照用途分開製作。 [專利文獻] Li 2 O-Al 2 O 3 -SiO 2 crystallized glass obtained by precipitating β-quartz solid solution or β-spodumene solid solution has low thermal expansion coefficient, high mechanical strength and excellent thermal properties. In addition, Li 2 O-Al 2 O 3 -SiO 2 based crystallized glass can change the precipitation crystal by changing the heat treatment conditions during the crystallization process. ) produces both transparent crystallized glass and opaque crystallized glass, which can be produced separately according to the application. [Patent Literature]
[專利文獻1] 日本特公昭39-21049號公報 [專利文獻2] 日本特公昭40-20182號公報 [專利文獻3] 日本特開平1-308845號公報 [專利文獻4] 日本特開平6-329439號公報 [專利文獻5] 日本特開平9-188538號公報 [專利文獻6] 日本特開2001-48582號公報 [專利文獻7] 日本特開2001-48583號公報 [Patent Document 1] Japanese Patent Publication No. 39-21049 [Patent Document 2] Japanese Patent Publication No. 40-20182 [Patent Document 3] Japanese Patent Application Laid-Open No. 1-308845 [Patent Document 4] Japanese Patent Application Laid-Open No. 6-329439 [Patent Document 5] Japanese Patent Application Laid-Open No. 9-188538 [Patent Document 6] Japanese Patent Laid-Open No. 2001-48582 [Patent Document 7] Japanese Patent Laid-Open No. 2001-48583
[發明欲解決的課題][The problem to be solved by the invention]
近年來，由於電動車發展迅速，鋰離子二次電池需求量快速增加，隨著電動車的發展，鋰離子二次電池的正極材料的原料之碳酸鋰、和碳酸鋰的原料之含鋰礦物(例如：鋰輝石、葉長石、鋰雲母等)的價格係不斷上漲。In recent years, due to the rapid development of electric vehicles, the demand for lithium ion secondary batteries has increased rapidly. For example: spodumene, feldspar, lepidolite, etc.) prices are rising.
另一方面，以往製造上述Li 2O-Al 2O 3-SiO 2系結晶化玻璃時，為了取得構成結晶之成分，常常需要使用大量鋰輝石(LiAlSi 2O 6)、透鋰長石(LiAlSi 4O 10)、鋰雲母(K(Li,Al) 3(AlSi 3O 10)(OH,F) 2)等含鋰礦物，或者碳酸鋰化工原料。為了降低Li 2O-Al 2O 3-SiO 2系結晶化玻璃的製造成本，需要降低含鋰原料的使用量。但是，降低含鋰原料使用量將會使得Li 2O-Al 2O 3-SiO 2系結晶化玻璃的結晶成分減少，結晶的形成變得困難，使用與以往相同結晶化熱處理的溫度曲線處理後結晶化玻璃的結晶量相對的比較少。結晶化玻璃通常會隨著結晶量的減少降低衝擊強度和熱衝擊強度。 On the other hand, when the above-mentioned Li 2 O-Al 2 O 3 -SiO 2- based crystallized glass is conventionally produced, it is often necessary to use a large amount of spodumene (LiAlSi 2 O 6 ), spodumene (LiAlSi 4 ) in order to obtain the components constituting the crystal. O 10 ), lepidolite (K(Li,Al) 3 (AlSi 3 O 10 )(OH,F) 2 ) and other lithium-containing minerals, or lithium carbonate chemical raw materials. In order to reduce the manufacturing cost of Li 2 O-Al 2 O 3 -SiO 2 based crystallized glass, it is necessary to reduce the usage amount of the lithium-containing raw material. However, reducing the amount of lithium-containing raw materials used will reduce the crystal component of the Li 2 O-Al 2 O 3 -SiO 2 based crystallized glass, making it difficult to form crystals. Crystallized glass has a relatively small amount of crystallization. Crystallized glass generally reduces impact strength and thermal shock strength as the amount of crystallisation decreases.
本揭示的實施形態，係依上述狀況而生。 本揭示提供即使降低含鋰原料之使用量也能具有良好衝擊強度和熱衝擊強度的Li 2O-Al 2O 3-SiO 2系結晶化玻璃。 [為了解決課題的手段] The embodiment of the present disclosure is based on the above-mentioned situation. The present disclosure provides Li 2 O-Al 2 O 3 -SiO 2 based crystallized glass which can have good impact strength and thermal shock strength even if the usage amount of the lithium-containing raw material is reduced. [Means for solving problems]
本發明者經由各種實驗結果，發現藉由含有MnO 2時，Li 2O-Al 2O 3-SiO 2系結晶化玻璃的衝擊強度變高，可以達成上述目的。 The present inventors have found through various experimental results that when MnO 2 is contained, the impact strength of the Li 2 O-Al 2 O 3 -SiO 2- based crystallized glass is increased, and the above object can be achieved.
本發明的Li 2O-Al 2O 3-SiO 2系結晶化玻璃和Li 2O-Al 2O 3-SiO 2系結晶性玻璃，按質量百分比計，含有SiO 260.0~70.0%、Al 2O 315.0~25.0%、Li 2O 1.0~6.0%、TiO 21.0~4.0%、ZrO 20.5~3.0%、MnO 20.1~3.0%、Na 2O 0.1~2.0%、K 2O 0.1~2.0%、P 2O 50.1~2.0%、MgO 0.1~1.5%、ZnO 0.1~3.0%、BaO 0.1~2.5%、及As 2O 30.1~1.5%。 The Li 2 O-Al 2 O 3 -SiO 2 series crystallized glass and the Li 2 O-Al 2 O 3 -SiO 2 series crystallized glass of the present invention contain 60.0-70.0% SiO 2 , Al 2 O 3 15.0~25.0%, Li 2 O 1.0~6.0%, TiO 2 1.0~4.0%, ZrO 2 0.5~3.0%, MnO 2 0.1~3.0%, Na 2 O 0.1~2.0%, K 2 O 0.1~2.0 %, P 2 O 5 0.1-2.0%, MgO 0.1-1.5%, ZnO 0.1-3.0%, BaO 0.1-2.5%, and As 2 O 3 0.1-1.5%.
本發明的Li 2O-Al 2O 3-SiO 2系結晶化玻璃和Li 2O-Al 2O 3-SiO 2系結晶性玻璃的實施形態的一例為，另外含有0.1~1.0%的F。 An example of an embodiment of the Li 2 O-Al 2 O 3 -SiO 2 based crystallized glass and the Li 2 O-Al 2 O 3 -SiO 2 based crystallized glass of the present invention further contains 0.1 to 1.0% of F.
本發明的Li 2O-Al 2O 3-SiO 2系結晶化玻璃和Li 2O-Al 2O 3-SiO 2系結晶性玻璃的實施形態的一例為，更含有選自於由V 2O 5、CoO、Cr 2O 3、Fe 2O 3及NiO構成之群組中之至少一種著色劑。 An example of an embodiment of the Li 2 O-Al 2 O 3 -SiO 2 based crystallized glass and the Li 2 O-Al 2 O 3 -SiO 2 based crystallized glass of the present invention further contains V 2 O 5. At least one colorant selected from the group consisting of CoO, Cr 2 O 3 , Fe 2 O 3 and NiO.
本發明的Li 2O-Al 2O 3-SiO 2系結晶化玻璃具有以β-石英固溶體或者β-鋰輝石固溶體作為主結晶較理想。 [發明的效果] The Li 2 O-Al 2 O 3 -SiO 2 based crystallized glass of the present invention preferably has a β-quartz solid solution or a β-spodumene solid solution as a main crystal. [Effect of invention]
依照本發明，提供即使減少含鋰原料的使用量也能具有良好衝擊強度和熱衝擊強度的Li 2O-Al 2O 3-SiO 2系結晶化玻璃。 According to the present invention, there is provided a Li 2 O-Al 2 O 3 -SiO 2 based crystallized glass which can have good impact strength and thermal shock strength even when the amount of lithium-containing raw material used is reduced.
以下，說明本發明的實施形態。這些說明及實施例只是例示實施形態，而不是用來限制實施形態的範圍。Hereinafter, embodiments of the present invention will be described. These descriptions and examples merely illustrate the embodiments, and are not intended to limit the scope of the embodiments.
在本發明中用「~」表示數值範圍時，記載在「~」前後的數值代表含有量的最大值和最小值。 在本發明中某一階段記載的數值範圍，在一個數值範圍被記載的上限值或者下限值，也可換成其他階段記載的數值範圍的上限值或者下限值。還有，在本發明被記載的數值範圍中，其數值範圍的上限值或者下限值也可以換成實施例所示的數值。 In the present invention, when a numerical range is represented by "~", the numerical values described before and after the "~" represent the maximum value and the minimum value of the content. The numerical range described in a certain stage of the present invention, the upper limit value or the lower limit value described in one numerical range, may be replaced with the upper limit value or the lower limit value of the numerical range described in another stage. In addition, in the numerical range described in this invention, the upper limit or the lower limit of the numerical range may be replaced with the numerical value shown in an Example.
關於本發明的Li 2O-Al 2O 3-SiO 2系結晶化玻璃和Li 2O-Al 2O 3-SiO 2系結晶性玻璃，限定其組成範圍的理由如下： Regarding the Li 2 O-Al 2 O 3 -SiO 2 based crystallized glass and Li 2 O-Al 2 O 3 -SiO 2 based crystallized glass of the present invention, the reasons for limiting the composition range are as follows:
SiO 2是玻璃的網狀架構成分，也是構成結晶的成分，SiO 2的含量若低於60.0%則結晶化玻璃的膨脹係數變大，同時，機械強度變差，SiO 2的含量若高於70.0%，則玻璃熔融變得困難，且容易產生氣泡或者失透物等的缺陷。 SiO 2 is a network structure component of glass, and it is also a component that constitutes crystals. If the content of SiO 2 is less than 60.0%, the expansion coefficient of the crystallized glass will increase, and at the same time, the mechanical strength will deteriorate. If the content of SiO 2 is higher than 70.0 %, glass melting becomes difficult, and defects such as bubbles and devitrification are easily generated.
Al 2O 3是構成結晶的成分，Al 2O 3的含量若低於15.0%，則玻璃容易失透，同時，化學耐久性下降，另一方面，Al 2O 3的含量若高於25.0%，則熔融時黏性太高，不容易得到均勻的玻璃。 Al 2 O 3 is a component constituting crystals. When the content of Al 2 O 3 is less than 15.0%, the glass tends to devitrify and chemical durability decreases. On the other hand, when the content of Al 2 O 3 exceeds 25.0% , the viscosity during melting is too high, and it is not easy to obtain a uniform glass.
Li 2O是構成結晶的成分， Li 2O 的含量若低於1.0%，則含Li 2O 結晶的析出變成困難，同時，玻璃的熔融性下降。另一方面，Li 2O 的含量若高於6.0%，則玻璃的失透變強，成形困難。 Li 2 O is a component constituting crystals, and when the content of Li 2 O is less than 1.0%, precipitation of Li 2 O-containing crystals becomes difficult, and the meltability of the glass decreases. On the other hand, when the content of Li 2 O is higher than 6.0%, the devitrification of the glass becomes strong, and forming becomes difficult.
從減少含鋰原料使用量的觀點來說，係構成結晶之成分的SiO 2、Al 2O 3、及Li 2O的總量占原料總量的90%以下為好，88%以下較好，86%以下更好，從結晶化玻璃優良的衝擊強度和熱衝擊強度的觀點來說，80%以上為好，82%以上較好，84%以上更好。 From the viewpoint of reducing the amount of lithium-containing raw materials used, the total amount of SiO 2 , Al 2 O 3 , and Li 2 O, which are components constituting the crystal, is preferably 90% or less of the total raw material, preferably 88% or less. 86% or less is more preferable, and from the viewpoint of the excellent impact strength and thermal shock strength of the crystallized glass, 80% or more is more preferable, 82% or more is more preferable, and 84% or more is more preferable.
TiO 2係作為晶核形成劑添加，TiO 2的含量若低於1.0%，則得不到促進結晶化的效果，不容易得到希望的結晶，TiO 2的含量若多於4.0%，則液相溫度變高，成形作業變得困難。還有，TiO 2的含量若多於4.0%，則製造透明結晶化玻璃時，玻璃容易被著色成深褐色而損及透明性。 TiO 2 is added as a crystal nucleating agent. If the content of TiO 2 is less than 1.0%, the effect of promoting crystallization cannot be obtained, and it is difficult to obtain desired crystals. If the content of TiO 2 is more than 4.0%, the liquid phase As the temperature becomes high, the forming operation becomes difficult. In addition, when the content of TiO 2 is more than 4.0%, when a transparent crystallized glass is produced, the glass is likely to be colored dark brown to impair transparency.
ZrO 2係作為晶核形成劑，ZrO 2的含量若低於0.5%，則得不到促進結晶化的效果，不容易得到希望的結晶，ZrO 2的含量若多於3.0%，則容易殘留未熔物，玻璃中會有失透物。 ZrO 2 as nucleating agent system, when the content of ZrO 2 is less than 0.5%, can not be obtained an effect of promoting crystallization is not easy to obtain a desired crystal, if the content of ZrO 2 is more than 3.0%, it did not tend to remain Melt, there will be devitrification in the glass.
MnO 2有促進結晶化的效果，MnO 2的含量若低於0.1%，則得不到促進結晶化的效果，不容易得到希望的晶體，得不到提高結晶化玻璃衝擊強度和熱衝擊強度的效果。MnO 2含量宜為0.5%以上較佳，更宜為0.8%以上。還有，因為MnO 2有著色劑作用，所以，使用MnO 2可以減少高價的V 2O 5和CoO的使用量。另一方面，MnO 2的含量若高於3.0%，則玻璃容易失透，成形作業變得困難。 MnO 2 has the effect of promoting crystallization. If the content of MnO 2 is less than 0.1%, the effect of promoting crystallization cannot be obtained, the desired crystal cannot be easily obtained, and the impact strength and thermal shock strength of the crystallized glass cannot be improved. Effect. The MnO 2 content is preferably 0.5% or more, more preferably 0.8% or more. Also, since MnO 2 acts as a colorant, the use of MnO 2 can reduce the usage of expensive V 2 O 5 and CoO. On the other hand, when the content of MnO 2 is higher than 3.0%, the glass tends to devitrify and the forming operation becomes difficult.
Na 2O有改善玻璃熔融性的效果，Na 2O的含量若低於0.1%，則得不到改善玻璃熔融性的效果。Na 2O的含量若高於2.0%，則結晶化玻璃的膨脹係數和介電損失變大，還有，Na 2O的含量若高於2.0%，則衝擊強度和化學耐久性變差。 Na 2 O has the effect of improving the meltability of the glass, but when the content of Na 2 O is less than 0.1%, the effect of improving the meltability of the glass cannot be obtained. When the content of Na 2 O exceeds 2.0%, the expansion coefficient and dielectric loss of the crystallized glass increase, and when the content of Na 2 O exceeds 2.0%, the impact strength and chemical durability deteriorate.
K 2O有改善玻璃熔融性的效果，K 2O的含量若低於0.1%，則得不到改善玻璃熔融性的效果。K 2O的含量若高於2.0%，則結晶化玻璃的膨脹係數和介電損失變大，還有，K 2O的含量若高於2.0%，則衝擊強度和化學耐久性變差。 K 2 O has the effect of improving the meltability of the glass, but when the content of K 2 O is less than 0.1%, the effect of improving the meltability of the glass cannot be obtained. When the K 2 O content exceeds 2.0%, the expansion coefficient and dielectric loss of the crystallized glass increase, and when the K 2 O content exceeds 2.0%, the impact strength and chemical durability deteriorate.
P 2O 5對於ZrO 2的難熔融性有明顯的改善效果。P 2O 5的含量若低於0.1 %，則得不到改善效果，P 2O 5的含量若高於2.0%，則容易分相而無法獲得均勻的玻璃。還有，P 2O 5的含量若高於2.0%，則結晶量變多，不容易得到透明結晶化玻璃。 P 2 O 5 has obvious improvement effect on the refractoriness of ZrO 2 . When the content of P 2 O 5 is less than 0.1%, the improvement effect cannot be obtained, and when the content of P 2 O 5 is more than 2.0%, the phases are easily separated and a uniform glass cannot be obtained. In addition, when the content of P 2 O 5 exceeds 2.0%, the amount of crystals increases, and it becomes difficult to obtain transparent crystallized glass.
MgO為具有改善玻璃熔融性，同時，可以防止氣泡產生之成份。但是，MgO的含量若低於0.1%則得不到效果，變成容易產生氣泡。另一方面， MgO的含量若高於1.5%，則因熱膨脹係數變大使得熱特性不佳。還有，透明結晶化玻璃製造時，有時由於TiO 2的存在會使玻璃被著成黃色， MgO的含量若高於1.5%的話，會使著色變深而損及透明性。 MgO is a component that improves the melting property of glass and prevents the generation of bubbles. However, if the content of MgO is less than 0.1%, no effect is obtained, and bubbles are likely to be generated. On the other hand, when the content of MgO is higher than 1.5%, the thermal expansion coefficient becomes large, resulting in poor thermal characteristics. In addition, in the production of transparent crystallized glass, the glass may be colored yellow due to the presence of TiO 2 , and if the content of MgO is higher than 1.5%, the coloring will become darker and the transparency will be impaired.
ZnO為具有改善玻璃熔融性，同時，可以防止氣泡缺陷產生之成份。但是，ZnO的含量若低於0.1%則得不到效果，變成容易產生氣泡。另一方面，ZnO的含量高於3.0%的話，由於介電損失變大，用於微波爐時會發生熱點導致故障。還有，透明結晶化玻璃製造時，有時由於TiO 2的存在會使玻璃被著成黃色， ZnO的含量若高於3.0%的話，會使著色變深而損及透明性。 ZnO is a component that improves glass melting and prevents bubble defects. However, if the content of ZnO is less than 0.1%, the effect is not obtained, and bubbles are likely to be generated. On the other hand, when the content of ZnO is higher than 3.0%, since the dielectric loss becomes large, a hot spot occurs when used in a microwave oven, resulting in failure. In addition, in the production of transparent crystallized glass, the glass may be colored yellow due to the presence of TiO 2 , and if the content of ZnO is higher than 3.0%, the coloring will become darker and the transparency will be impaired.
BaO為具有改善玻璃熔融性，同時，可以防止氣泡缺陷產生之成份。但是，BaO的含量若低於0.1%則得不到效果，變成容易產生氣泡。另一方面， BaO的含量若高於2.5%的話，玻璃的熱膨脹係數變大，熱特性變差，還有，高於2.5%的話，玻璃的介電損失變大。BaO is a component that improves glass melting and prevents bubble defects. However, if the content of BaO is less than 0.1%, the effect is not obtained, and bubbles are likely to be generated. On the other hand, when the content of BaO is higher than 2.5%, the thermal expansion coefficient of the glass is increased, and the thermal characteristics are deteriorated, and when the content of BaO is higher than 2.5%, the dielectric loss of the glass is increased.
As 2O 3作為澄清劑作用，As 2O 3的含量若低於0.1%，則得不到促進玻璃熔融性、成形作業性和玻璃均一性的效果。另一方面，As 2O 3的含量若高於1.5%，則對環境的影響大。 As 2 O 3 functions as a fining agent, and when the content of As 2 O 3 is less than 0.1%, the effect of promoting glass meltability, forming workability, and glass uniformity cannot be obtained. On the other hand, when the content of As 2 O 3 exceeds 1.5%, the influence on the environment is large.
F有改善玻璃熔融的效果，本發明的結晶化玻璃和結晶性玻璃含有F時，含量為0.1~1.0%較好。F的含量為0.1%以上則可以得到它的效果， F的含量為1.0%以下，則可以抑制對熔融爐的侵蝕。F has the effect of improving glass melting, and when the crystallized glass and crystallizable glass of the present invention contain F, the content is preferably 0.1 to 1.0%. When the content of F is 0.1% or more, its effect can be obtained, and when the content of F is 1.0% or less, the erosion of the melting furnace can be suppressed.
V 2O 5、CoO、Cr 2O 3、Fe 2O 3和NiO作為著色劑作用，使用這些著色劑時，總含量為0.1~3.0%較好，總含量0.1%以上，則容易得到著色效果，總含量在3.0%以下可以控制成本。 V 2 O 5 , CoO, Cr 2 O 3 , Fe 2 O 3 and NiO act as colorants. When these colorants are used, the total content of these colorants is preferably 0.1 to 3.0%, and the total content of 0.1% or more can easily obtain coloring effects. , the total content of less than 3.0% can control the cost.
本發明的Li 2O-Al 2O 3-SiO 2系結晶性玻璃可以經由玻璃原料混合、熔融而得到熔融玻璃，將熔融玻璃予以成形而得。 本發明的Li 2O-Al 2O 3-SiO 2系結晶化玻璃可以經由本發明的Li 2O-Al 2O 3-SiO 2系結晶性玻璃加以結晶化熱處理而製造出來。結晶化熱處理的升溫速度、保持溫度及保持時間沒有特別限制，可以選擇能夠充分析出且成長目標結晶(較好為β-石英固溶體或者β-鋰輝石固溶體)的條件。 The Li 2 O-Al 2 O 3 -SiO 2- based crystallizable glass of the present invention can be obtained by mixing and melting through glass raw materials to obtain a molten glass, and can be obtained by molding the molten glass. Li 2 O-Al 2 O 3 -SiO 2 based crystallized glass of the present invention, the crystallization heat treatment may be manufactured via a Li 2 O-Al 2 O 3 -SiO 2 based crystallized glass of the present invention. The heating rate, holding temperature, and holding time of the crystallization heat treatment are not particularly limited, and conditions can be selected under which the target crystal (preferably a β-quartz solid solution or a β-spodumene solid solution) can be sufficiently precipitated and grown.
本發明的Li 2O-Al 2O 3-SiO 2系結晶化玻璃，從降低熱膨脹係數的觀點，具有以β-石英固溶體(Li 2O‧Al 2O 3‧nSiO 2n≧2)或者β-鋰輝石固溶體(Li 2O‧Al 2O 3‧nSiO 2n≧4)為主結晶較佳。 [實施例] Li 2 O-Al 2 O 3 -SiO 2 based crystallized glass of the present invention, from the viewpoint of reducing the coefficient of thermal expansion, having a β- quartz solid solution (Li 2 O‧Al 2 O 3 ‧nSiO 2 n ≧ 2) Alternatively, a β-spodumene solid solution (Li 2 O·Al 2 O 3 ·nSiO 2 n≧4) is preferable as the main crystal. [Example]
以下，根據實施例更具體說明本發明的Li 2O-Al 2O 3-SiO 2系結晶化玻璃及Li 2O-Al 2O 3-SiO 2系結晶性玻璃。 在以下的實施例中顯示的材料、使用量、配比、處理順序等，在不脫離本發明主旨下可以變更。因此，本發明的Li 2O-Al 2O 3-SiO 2系結晶化玻璃及Li 2O-Al 2O 3-SiO 2系結晶性玻璃的範圍不應該被解釋為限定在以下所示的具體例。 Hereinafter, the Li 2 O-Al 2 O 3 -SiO 2- based crystallized glass and the Li 2 O-Al 2 O 3 -SiO 2- based crystallized glass of the present invention will be described more specifically based on examples. The materials, usage amounts, compounding ratios, processing order, etc. shown in the following examples can be changed without departing from the gist of the present invention. Therefore, the scope of the Li 2 O-Al 2 O 3 -SiO 2 based crystallized glass and the Li 2 O-Al 2 O 3 -SiO 2 based crystallized glass of the present invention should not be construed as being limited to the specifics shown below. example.
表1及表2顯示本發明的Li 2O-Al 2O 3-SiO 2系結晶化玻璃的實施例(No.1~8)及比較例(No.9~10)。 Table 1 and Table 2 show Examples (No. 1 to 8) and Comparative Examples (No. 9 to 10) of the Li 2 O—Al 2 O 3 —SiO 2 based crystallized glass of the present invention.
[表1]
[表2]
表1和表2中的各個試樣依照以下的方法製備而成。 將玻璃原料調合成表1和表2所示的組成，均勻混合後，放入坩堝內，在1660℃熔融12小時。其次，將熔融後的玻璃倒在金屬製的平台上，用不銹鋼輥壓成4mm厚的玻璃板，然後，將玻璃板依照表1和表2所示的熱處理條件使玻璃板結晶化之後爐冷，取得試樣。 Each sample in Table 1 and Table 2 was prepared according to the following method. The glass raw materials were prepared into the compositions shown in Tables 1 and 2, mixed uniformly, and then put into a crucible and melted at 1660° C. for 12 hours. Next, the molten glass was poured onto a metal platform and rolled with stainless steel to form a glass plate with a thickness of 4 mm. Then, the glass plate was crystallized according to the heat treatment conditions shown in Tables 1 and 2, followed by furnace cooling. , get the sample.
對各個試樣觀察主結晶、外觀、色調、衝擊強度和熱衝擊強度。 主結晶是使用X射線繞射法鑑別。 外觀和色調是用肉眼觀察。 衝擊強度是使用衝擊器，以0.7j的運動能量衝擊300mm×300mm的玻璃板面的4個角和中心點，每個點衝擊3下，觀察玻璃板是否有裂紋或破裂，玻璃板沒有裂紋或破裂的為「合格」。 熱衝擊強度是將300mm×300mm玻璃板片放入爐內，在與常溫水溫差800℃(玻璃板為不透明的情況下，溫差500℃)的溫度下保持30分鐘後，將玻璃板丟入水中，觀察玻璃板是否有裂紋或破裂，玻璃板沒有裂紋或破裂的為「合格」。 The main crystals, appearance, color tone, impact strength and thermal shock strength were observed for each sample. Primary crystals were identified using X-ray diffraction. Appearance and shade are observed with the naked eye. The impact strength is to use an impactor to impact the 4 corners and center points of the 300mm × 300mm glass plate surface with a motion energy of 0.7j. Each point is impacted 3 times to observe whether the glass plate has cracks or cracks, and the glass plate has no cracks or cracks. The broken ones are "qualified". The thermal shock strength is measured by putting a 300mm×300mm glass plate into a furnace, and keeping it at a temperature difference of 800°C from the normal temperature water (if the glass plate is opaque, the temperature difference is 500°C) for 30 minutes, and then throwing the glass plate into the water. , observe whether the glass plate has cracks or cracks, and the glass plate without cracks or cracks is "qualified".
從表1和表2可以了解，取決於熱處理條件，可以得到以β-石英固溶體為主結晶之透明結晶化玻璃，和以β-鋰輝石固溶體為主結晶之不透明結晶化玻璃。As can be understood from Tables 1 and 2, depending on the heat treatment conditions, transparent crystallized glass mainly crystallized from β-quartz solid solution, and opaque crystallized glass mainly crystallized from β-spodumene solid solution can be obtained.
在實施例試樣No.1~8衝擊強度和熱衝擊強度都合格，但是，在比較例試樣No.9~10衝擊強度和熱衝擊強度都不合格。In Example Sample Nos. 1 to 8, the impact strength and thermal shock strength were all acceptable, but in Comparative Example Sample No. 9 to 10, the impact strength and thermal shock strength were unacceptable.
這些事實顯示，含有MnO 20.1~3.0%的Li 2O-Al 2O 3-SiO 2系結晶化玻璃，即使構成結晶的成分比較少也可以得到良好的衝擊強度和熱衝擊強度。 [產業利用性] These facts show that the Li 2 O-Al 2 O 3 -SiO 2 based crystallized glass containing 0.1 to 3.0% of MnO 2 can obtain good impact strength and thermal shock strength even if the components constituting the crystal are relatively small. [industrial availability]
本發明的Li 2O-Al 2O 3-SiO 2系結晶化玻璃具有良好的衝擊強度和熱衝擊強度。同時，本發明的Li 2O-Al 2O 3-SiO 2系結晶化玻璃組成如上所述，藉由特定組成，物理特性和化學特性都處於安定狀態。因此，可以做為電暖器前面窗玻璃、電子製品用基板、電子零件煅燒用棚板、微波爐棚板、電磁調理器用面板等多種的工業材料使用。 Li 2 O-Al 2 O 3 -SiO 2 based crystallized glass of the present invention have good impact strength and thermal impact strength. Meanwhile, the composition of the Li 2 O-Al 2 O 3 -SiO 2 based crystallized glass of the present invention is as described above, and both physical properties and chemical properties are stable due to the specific composition. Therefore, it can be used as a variety of industrial materials such as electric heater front window glass, substrates for electronic products, shelves for firing electronic parts, shelves for microwave ovens, and panels for electromagnetic conditioners.
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