JP5701500B2 - Transparent glass ceramic with low density - Google Patents
Transparent glass ceramic with low density Download PDFInfo
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- JP5701500B2 JP5701500B2 JP2009278536A JP2009278536A JP5701500B2 JP 5701500 B2 JP5701500 B2 JP 5701500B2 JP 2009278536 A JP2009278536 A JP 2009278536A JP 2009278536 A JP2009278536 A JP 2009278536A JP 5701500 B2 JP5701500 B2 JP 5701500B2
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- 239000002241 glass-ceramic Substances 0.000 title claims description 31
- 239000011521 glass Substances 0.000 claims description 22
- 239000013078 crystal Substances 0.000 claims description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000010453 quartz Substances 0.000 claims description 11
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 9
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 9
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 7
- 229910018068 Li 2 O Inorganic materials 0.000 claims description 7
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 7
- 239000006025 fining agent Substances 0.000 claims description 6
- 229910008556 Li2O—Al2O3—SiO2 Inorganic materials 0.000 claims description 5
- 239000000919 ceramic Substances 0.000 claims description 4
- 239000004065 semiconductor Substances 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 description 7
- 238000002468 ceramisation Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 238000004031 devitrification Methods 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 239000002667 nucleating agent Substances 0.000 description 4
- 238000002834 transmittance Methods 0.000 description 4
- 238000005352 clarification Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910000500 β-quartz Inorganic materials 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000005357 flat glass Substances 0.000 description 2
- 229910021495 keatite Inorganic materials 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000000053 physical method Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 239000006094 Zerodur Substances 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000009970 fire resistant effect Effects 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000005355 lead glass Substances 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 229910052611 pyroxene Inorganic materials 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000000411 transmission spectrum Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Classifications
-
- 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
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
- C03C10/0036—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and a divalent metal oxide as main constituents
-
- 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
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
- C03C10/0054—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing PbO, SnO2, B2O3
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Glass Compositions (AREA)
Description
本発明は、低い密度を有する透明なガラスセラミックに関する。 The present invention relates to a transparent glass ceramic having a low density.
主結晶相として高温石英混晶（β−石英固溶体）を有するＬｉ2Ｏ−Ａｌ2Ｏ3−ＳｉＯ2系のガラスセラミックの密度が、同一の組成および同一の結晶相割合の場合でも、僅かな範囲で変化される理由は、セラミック化の最中に出発ガラスが晒される収縮がセラミック化プログラムによって僅かな程度影響を受けるからであることが知られている。しかしながら、主結晶相として高温石英混晶を有しかつＬｉ2Ｏ−Ａｌ2Ｏ3−ＳｉＯ2系からなる従来のガラスセラミックの密度は、あらゆる処置にもかかわらず、常に２．５ｇ・ｃｍ-3を上回っている。例えば、ショット社によって特に光学用途のためのゼロデュア（登録商標）の名前で販売されているガラスセラミックは、２．５３ｇ・ｃｍ-3の密度を有する。 Even when the density of the Li 2 O—Al 2 O 3 —SiO 2 -based glass ceramic having a high-temperature quartz mixed crystal (β-quartz solid solution) as the main crystal phase is the same composition and the same crystal phase ratio, it is slight. It is known that the range varies because the shrinkage to which the starting glass is exposed during ceramization is affected to some extent by the ceramization program. However, the density of a conventional glass ceramic having a high-temperature quartz mixed crystal as a main crystal phase and made of the Li 2 O—Al 2 O 3 —SiO 2 system is always 2.5 g · cm − regardless of any treatment. Exceeds 3 . For example, a glass ceramic sold by Schott under the name Zerodur® for optical applications in particular has a density of 2.53 g · cm −3 .
主結晶相として高温石英混晶を有し、２．５ｇ・ｃｍ-3より低い密度を有するＬｉ2Ｏ−Ａｌ2Ｏ3−ＳｉＯ2系のガラスセラミックを製造しようとする場合、このガラスセラミックのために、新たな組成を見出さねばならない。ＥＰ１８４００９３Ａ１から、β−リチア輝石の主結晶相を有するガラスセラミックが既知であるが、これでは、２．５ｇ・ｃｍ-3より低い密度を達成することができない。 When an Li 2 O—Al 2 O 3 —SiO 2 -based glass ceramic having a high-temperature quartz mixed crystal as a main crystal phase and a density lower than 2.5 g · cm −3 is to be produced, Therefore, a new composition must be found. From EP1840093A1, glass ceramics having a main crystal phase of β-lithia pyroxene are known, but this cannot achieve a density lower than 2.5 g · cm −3 .
本発明の課題は、主結晶相として高温石英混晶（β−石英固溶体）を有し、２．５ｇ・ｃｍ-3より低い密度を有するＬｉ2Ｏ−Ａｌ2Ｏ3−ＳｉＯ2系のガラスセラミックを見出すことである。更に、ガラスセラミックが、高い透過率および少ない固有着色（Eigenfaerbung）を有することが意図される。 An object of the present invention is to provide a Li 2 O—Al 2 O 3 —SiO 2 glass having a high-temperature quartz mixed crystal (β-quartz solid solution) as a main crystal phase and a density lower than 2.5 g · cm −3. It is to find a ceramic. Furthermore, it is intended that the glass ceramic has a high transmittance and a low Eigenfaerbung.
上記課題は、酸化物ベースの重量％で、
Ｌｉ2Ｏ ３〜４．５
Ａｌ2Ｏ3 １８〜２４
ＳｉＯ2 ５５〜７０
ＴｉＯ2 ０．１〜＜２．３
ＺｒＯ2 ＜１．８
ΣＴｉＯ2＋ＺｒＯ2 ０．２〜４
ＢａＯ ０〜１．５
ΣＭｇＯ＋ＺｎＯ ＞１〜６
Ｂ2Ｏ3 ＞５〜１０
ΣＮａ2Ｏ＋Ｋ2Ｏ ０〜＜１
通常の清澄剤（ＳｎＯ2、Ａｓ2Ｏ3、Ｓｂ2Ｏ3、ＣｅＯ2） ０〜１．５
を含むガラスセラミックによって解決される。
The problem is weight percent oxide based,
Li 2 O 3-4.5
Al 2 O 3 18-24
SiO 2 55~70
TiO 2 0.1 <2.3
ZrO 2 <1.8
ΣTiO 2 + ZrO 2 0.2-4
BaO 0-1.5
ΣMgO + ZnO> 1-6
B 2 O 3 > 5-10
ΣNa 2 O + K 2 O 0 <1
Conventional fining agents (SnO 2, As 2 O 3 , Sb 2 O 3, CeO 2) 0~1.5
Solved by a glass-ceramic containing.
酸化物Ｌｉ2Ｏ、Ａｌ2Ｏ3およびＳｉＯ2は、高温石英混晶（β−石英固溶体）および／またはキータイト混晶（キータイト固溶体）を有するガラスセラミックの必要な成分である。Ｌｉ2Ｏの含量が３重量％未満である場合、結晶相割合が、意図された使用にとって余りにも低い（高温石英混晶の所望の割合は、＜６０体積％である）。４．５重量％を超えるＬｉ2Ｏの含量は、結晶成長速度を高め、失透安定性を危うくする。Ｌｉ2Ｏの含量は、３〜４重量％であることが好ましい。何故ならば、この範囲では、達成可能な結晶相含量と、十分な失透安定性との間の特に好都合な妥協があるからである。Ａｌ2Ｏ3の含量は１８〜２４重量％である。この範囲では、溶融物は、良好な加工性を保証すべく十分に低い粘性を有する。Ａｌ2Ｏ3の含量が１８重量％未満である場合、達成可能なセラミック化速度が下がり、透明度は余りに低いであろう。 The oxides Li 2 O, Al 2 O 3 and SiO 2 are necessary components of a glass ceramic having a high-temperature quartz mixed crystal (β-quartz solid solution) and / or a keatite mixed crystal (keatite solid solution). When the content of Li 2 O is less than 3% by weight, the crystal phase proportion is too low for the intended use (the desired proportion of high temperature quartz mixed crystals is <60% by volume). A Li 2 O content exceeding 4.5% by weight increases the crystal growth rate and jeopardizes devitrification stability. The content of Li 2 O is preferably 3 to 4% by weight. This is because in this range there is a particularly favorable compromise between the achievable crystalline phase content and sufficient devitrification stability. The content of Al 2 O 3 is 18 to 24% by weight. In this range, the melt has a sufficiently low viscosity to ensure good processability. If the Al 2 O 3 content is less than 18% by weight, the achievable ceramization rate will be reduced and the transparency will be too low.
Ａｌ2Ｏ3の含量は１９．５〜２１．５重量％の範囲にあることが好ましい。 The content of Al 2 O 3 is preferably in the range of 19.5 to 21.5% by weight.
ＳｉＯ2の含量は５５〜７０重量％である。ＳｉＯ2の含量が高ければ、密度は一層低くなる。しかしながら、ＳｉＯ2の含量が、７０重量％の、好ましくは６６重量％の上限を上回らないほうがよい。何故ならば、上回れば、未処理ガラス（Gruenglas）を処理するための温度範囲が、＞１５５０℃の値を有し、このような温度では、ガラスを処理するためには技術的に一層難しくなるからである。 The content of SiO 2 is 55 to 70% by weight. The higher the SiO 2 content, the lower the density. However, the SiO 2 content should not exceed the upper limit of 70% by weight, preferably 66% by weight. This is because, above that, the temperature range for processing untreated glass (Gruenglas) has a value of> 1550 ° C., and at such temperatures it becomes technically more difficult to process the glass. Because.
ＳｉＯ2の含量が５５重量％の下限を下回ると、セラミック化速度が下がる。ＳｉＯ2の含有量は、少なくとも５６重量％であることが好ましい。 When the SiO 2 content is below the lower limit of 55% by weight, the ceramization rate decreases. The content of SiO 2 is preferably at least 56% by weight.
アルカリ酸化物Ｎａ2ＯおよびＫ2Ｏの存在によって、ガラスの溶融性および失透挙動が、製造の際に、改善されることが知られている。しかしながら、Ｎａ2ＯおよびＫ2Ｏの含量が合計で１重量％より低いことが意図される。何故ならば、これらの酸化物の１重量％より高い割合が、ガラスセラミックの熱膨張係数を高めるからである。Ｎａ2ＯおよびＫ2Ｏの含量は、合計で、０〜０．９重量％、特に０．３〜０．５重量％であることが好ましい。 It is known that the presence of the alkali oxides Na 2 O and K 2 O improves the meltability and devitrification behavior of the glass during production. However, it is contemplated that the Na 2 O and K 2 O content is less than 1% by weight in total. This is because a proportion higher than 1% by weight of these oxides increases the thermal expansion coefficient of the glass ceramic. The total content of Na 2 O and K 2 O is preferably 0 to 0.9% by weight, particularly 0.3 to 0.5% by weight.
アルカリ土類酸化物ＣａＯおよびＢａＯも、一般的に、溶融挙動への同様に好ましい効果を示す。しかしながら、本発明の組成物では、ＣａＯはないほうが好ましいが、最大限０．５重量％が許容され得る。本発明の組成物では、ＣａＯはセラミック化の最中に異物相の形成をもたらすので、回避されることが意図される。ＢａＯも、溶融挙動への類似の効果を示す。しかしながら、ＢａＯの高い割合は、密度の増大をもたらす。それ故に、ＢａＯの割合は、最大１．５重量％である。溶融性および透明性を改善するためには、ＢａＯを０．１〜０．８重量％の量で添加することが好ましい。本発明の組成物はＢａＯを全く含まないことが特に好ましい。しかしながら、このことは、溶融性（Einschmeltzbarkeit）の理由から、必ずしも実現されるわけではない。 Alkaline earth oxides CaO and BaO also generally have a similarly favorable effect on the melting behavior. However, in the compositions of the present invention, it is preferred not to have CaO, but a maximum of 0.5% by weight can be tolerated. In the compositions of the present invention, CaO is intended to be avoided as it results in the formation of a foreign phase during ceramization. BaO also shows a similar effect on the melting behavior. However, a high proportion of BaO results in an increase in density. Therefore, the proportion of BaO is a maximum of 1.5% by weight. In order to improve the meltability and transparency, BaO is preferably added in an amount of 0.1 to 0.8% by weight. It is particularly preferred that the composition according to the invention does not contain any BaO. However, this is not always realized for reasons of meltability (Einschmeltzbarkeit).
ＴｉＯ2およびＺｒＯ2は、知られるように、成核剤として作用する。この場合、ＴｉＯ2の含量は２．３重量％未満であり、ＺｒＯ2の含量は１．８重量％未満であり、ＴｉＯ2＋ＺｒＯ2の合計は、０．２〜４重量％である。ＴｉＯ2およびＺｒＯ2が、これらの限界を上回りおよび下回るとき、成核剤の析出速度と、結果として生じる高温石英混晶の含量と、透明性とは、不満足なほどに低い。ＴｉＯ2およびＺｒＯ2の好ましい最低限量は、それぞれ、１重量％のＴｉＯ2および１重量％のＺｒＯ2である。ＴｉＯ2およびＺｒＯ2の合計は２〜４重量％であることが好ましい。 TiO 2 and ZrO 2 act as nucleating agents, as is known. In this case, the content of TiO 2 is less than 2.3% by weight, the content of ZrO 2 is less than 1.8% by weight, and the total of TiO 2 + ZrO 2 is 0.2-4% by weight. When TiO 2 and ZrO 2 are above and below these limits, the nucleating agent precipitation rate, the resulting high-temperature quartz mixed crystal content, and transparency are unsatisfactoryly low. Preferred minimum amounts of TiO 2 and ZrO 2 are each 1 wt% of TiO 2 and 1% by weight of ZrO 2. The total of TiO 2 and ZrO 2 is preferably 2 to 4% by weight.
Ｆｅ2Ｏ3の微量濃度に関連したガラスセラミックの増大する着色の故に、ＭｇＯおよびＺｎＯの割合は、合計１ないし６重量％に限定されねばならない。この合計内では、ＭｇＯの量は０．５重量％を、ＺｎＯの量は２．５重量％を上回らないことが好ましい。ＭｇＯおよびＺｎＯの含量は、合計で、１重量％ないし２．５重量％であることが特に好ましい。 Due to the increased coloration of the glass ceramic associated with the trace concentration of Fe 2 O 3 , the proportion of MgO and ZnO must be limited to a total of 1 to 6% by weight. Within this total, the MgO amount is preferably 0.5% by weight and the ZnO amount preferably does not exceed 2.5% by weight. The total content of MgO and ZnO is particularly preferably 1% to 2.5% by weight.
低い密度を得るために重要な成分は、Ｂ2Ｏ3である。何故ならば、この成分は、微細構造を緩ませ、セラミック化の最中にガラスセラミックの圧縮を減じるからである。Ｂ2Ｏ3は、５重量％を超え、１０重量％までの量で、存在する。しかしながら、Ｂ2Ｏ3がより高い場合には、ガラスセラミックの透過率が低下し、あるいは、失透傾向が、成形（成形温度（Ｖａ））の際に、増大するという危険性が存する。Ｂ2Ｏ3の含量は５重量％を超え、９重量％までであることが好ましい。 An important component for obtaining low density is B 2 O 3 . This is because this component relaxes the microstructure and reduces the compression of the glass ceramic during ceramization. B 2 O 3 is present in an amount greater than 5% by weight and up to 10% by weight. However, when B 2 O 3 is higher, there is a risk that the transmittance of the glass ceramic decreases or the tendency of devitrification increases during molding (molding temperature (Va)). The content of B 2 O 3 is preferably more than 5% by weight and up to 9% by weight.
ＳｎＯ2は、ガラス系の中で、０〜１重量％の量で存在し得る。ＳｎＯ2が、清澄剤および成核剤として作用することが可能である。しかしながら、ＳｎＯ2が存在しないことが好ましい。 SnO 2 can be present in the glass system in an amount of 0 to 1% by weight. SnO 2 can act as a fining and nucleating agent. However, it is preferred that SnO 2 is not present.
成分ＺｎＯおよびＭｇＯにおいて記述した色の問題の故に、Ｆｅ2Ｏ3の含量は２００重量ｐｐｍ未満、好ましくは１３０重量ｐｐｍ未満であるべきである。対応して、鉄の含有量の少ない原料が用いられることに注意しなければならない。更に、ガラスは、ＣａＯ、Ｆ、Ｐｂ酸化物および着色性酸化物を有しないことが好ましい。 Because of the color problems described in the components ZnO and MgO, the content of Fe 2 O 3 should be less than 200 ppm by weight, preferably less than 130 ppm by weight. Correspondingly, it should be noted that raw materials with a low iron content are used. Furthermore, it is preferable that glass does not have CaO, F, Pb oxide, and a coloring oxide.
ガラスセラミックの製造は、原料のそれ自体知られた溶融、続いてのガラスの清澄および成形によってなされる。清澄は、化学的または物理的方法によってなされ得る。Ａｓ2Ｏ3、Ｓｂ2Ｏ3、ＣｅＯ2、ＳｎＯ2、硫酸塩化合物または塩化物化合物のようなそれ自体既知の清澄剤が用いられる場合、これらの清澄剤は、０．１ないし１．５重量％の通常の量で用いられる。物理的方法は、例えば、減圧清澄または高温清澄である。 The production of glass-ceramics takes place by known melting of the raw materials, followed by glass refining and shaping. Clarification can be done by chemical or physical methods. When fining agents known per se, such as As 2 O 3 , Sb 2 O 3 , CeO 2 , SnO 2 , sulfate compounds or chloride compounds are used, these fining agents are 0.1 to 1.5 Used in the usual amount of wt%. The physical method is, for example, vacuum clarification or high temperature clarification.
ガラスを成形して、例えば板ガラスに形成した後に、ガラスのそれ自体知られたセラミック化がなされて、ガラスセラミックが形成される。そのためには、ガラスセラミックは、好ましい成核剤相ＴｉＺｒＯ4の高い核密度を析出させるために、それ自体既知の手法で、例えば、６３０℃〜７７０℃の温度で、１５分を超える時間処理され、続いて、高温石英混晶ガラスセラミックを形成するための結晶化が、７００℃〜９５０℃の温度範囲で、少なくとも５分の滞留時間で実行される。かくして、ガラスセラミックにおける高温石英混晶の微結晶（Kristallit）の大きさは、１００ｎｍ未満、特に、８０ｎｍ未満である。このことは、優れた透明性をもたらす。２０℃〜３００℃の範囲でのガラスセラミックの熱膨張係数は、＋０．３〜０．６・１０-6Ｋ-1未満、好ましくは０．５・１０-6Ｋ-1未満である。 After the glass has been formed and formed into, for example, a sheet glass, the glass is known to be ceramized to form a glass ceramic. For this purpose, the glass ceramic is treated in a manner known per se, for example at a temperature of 630 ° C. to 770 ° C., for more than 15 minutes, in order to precipitate the high nucleating density of the preferred nucleating agent phase TiZrO 4. Subsequently, crystallization to form a high temperature quartz mixed crystal glass ceramic is carried out in the temperature range of 700 ° C. to 950 ° C. with a residence time of at least 5 minutes. Thus, the size of the high-temperature quartz mixed crystal Kristallit in the glass ceramic is less than 100 nm, in particular less than 80 nm. This provides excellent transparency. The thermal expansion coefficient of the glass ceramic in the range of 20 ° C. to 300 ° C. is +0.3 to less than 0.6 · 10 −6 K −1 , preferably less than 0.5 · 10 −6 K −1 .
ＤＩＮ５０３１に従って測定されたガラスセラミックの輝度値Ｙ（Ａ／２°）は、４ｍｍの厚さの板ガラスについて、８０を超え、好ましくは８７を超える。ＣＩＥ−ｘｙＹ表色系の輝度値Ｙは、常に、２°の視角での透過標準光Ａについて特定され、個々の波長において分解された透過スペクトルから、ＣＩＥで定められた視覚感度曲線（三刺激曲線）によって、算出される。輝度値は、しばしば、分光透過率とも呼ばれる。未処理ガラスからガラスセラミックを製造するための１つの好ましいセラミック化方法は、未処理ガラスを、１０〜１５Ｋ・ｍｉｎ-1の加熱速度で、６５０±１０℃の温度に加熱し、続いて、１〜５Ｋ・ｍｉｎ-1の加熱速度で、７１０±５０℃の温度に更に加熱し、核を形成すべく、この温度で６０±３０分放置し、続いて、０．５〜５Ｋ・ｍｉｎ-1の加熱速度で、８５０±５０℃の結晶化温度に加熱し、未処理ガラスを、この温度に２０±１５分保って、結晶化することである。この後、任意の冷却速度で、しかし、一般的には、１〜２０Ｋ・ｍｉｎ-1の冷却速度で冷却を行なう。 The luminance value Y (A / 2 °) of the glass ceramic measured according to DIN 5031 is greater than 80, preferably greater than 87, for a sheet glass with a thickness of 4 mm. The luminance value Y of the CIE-xyY color system is always specified for the transmission standard light A at a viewing angle of 2 °, and the visual sensitivity curve (tristimulus) defined by the CIE is determined from the transmission spectrum resolved at each wavelength. Curve). The luminance value is often referred to as spectral transmittance. One preferred method of ceramizing to produce glass ceramic from untreated glass is to heat the untreated glass at a heating rate of 10-15 K · min −1 to a temperature of 650 ± 10 ° C., followed by 1 Further heating to a temperature of 710 ± 50 ° C. at a heating rate of ˜5 K · min −1 , leaving at this temperature for 60 ± 30 minutes to form nuclei, followed by 0.5 to 5 K · min −1 Is heated to a crystallization temperature of 850 ± 50 ° C. at a heating rate of 5 ° C., and the untreated glass is kept at this temperature for 20 ± 15 minutes for crystallization. Thereafter, cooling is performed at an arbitrary cooling rate, but generally at a cooling rate of 1 to 20 K · min −1 .
本発明を、実施例を参照してさらに詳述する。 The invention is further described in detail with reference to examples.
出発ガラスを、ガラス産業で通常の原料を用いて、１６２０℃の温度で溶融しかつ清澄した。焼結されたシリカガラス（クォーザル（登録商標）、ショット社）で作られた坩堝において溶融した後に、溶融物を、白金坩堝に移し変え、１６００℃の温度で、３０分間、撹拌によって均質化した。１６４０℃で２時間の放置後に、１４０×１００×３０ｍｍの寸法の鋳込み成形品を鋳込み成形し、熱応力を緩和するために、冷却炉で、６５０℃から始めて室温まで冷却した。これらの鋳込み成形品から、試験サンプル、例えば、熱膨張係数を測定するための棒、透過率を測定するための小板を作製した。ついで、ガラスセラミックの検査のために必要な大きさのガラス状のサンプルを、以下に挙げる核形成条件および結晶化条件を用いて、ガラスセラミックに変換した。この目的のために、サンプルを、１０Ｋ・ｍｉｎ-1の加熱速度で、６５０℃の温度に加熱し、この温度に達した後に、約５Ｋ・ｍｉｎ-1の加熱速度でＴg＋２０Ｋの温度に加熱し、核形成のために、この温度で３０分放置した。続いて、サンプルを、１０Ｋ・ｍｉｎ-1の加熱速度で、高温石英混晶に関する示差熱分析器（ＤＴＡ）によって測定された生成の最大速度(Ausscheidungsmaximum)の範囲における温度に加熱し、この温度で１０分間放置し、続いて、５Ｋ・ｍｉｎ-1の平均冷却速度で、室温まで冷却した（空気中で）。 The starting glass was melted and clarified at a temperature of 1620 ° C. using raw materials common in the glass industry. After melting in a crucible made of sintered silica glass (Quazar®, Schott), the melt was transferred to a platinum crucible and homogenized by stirring at a temperature of 1600 ° C. for 30 minutes. . After standing at 1640 ° C. for 2 hours, a cast molded product having a size of 140 × 100 × 30 mm was cast and then cooled to room temperature in a cooling furnace starting from 650 ° C. From these cast products, test samples, for example, rods for measuring the thermal expansion coefficient and platelets for measuring the transmittance were prepared. Subsequently, a glassy sample having a size required for the inspection of the glass ceramic was converted into the glass ceramic by using the nucleation conditions and the crystallization conditions described below. For this purpose, the sample is heated to a temperature of 650 ° C. at a heating rate of 10 K · min −1 and, after reaching this temperature, to a temperature of T g +20 K at a heating rate of about 5 K · min −1. Heated and left at this temperature for 30 minutes for nucleation. Subsequently, the sample is heated at a heating rate of 10 K · min −1 to a temperature in the range of the maximum rate of production (Ausscheidungsmaximum) measured by a differential thermal analyzer (DTA) for high temperature quartz mixed crystals, at this temperature. It was allowed to stand for 10 minutes, and then cooled to room temperature (in air) at an average cooling rate of 5 K · min −1 .
出発ガラスおよび製造されたガラスセラミックについて、密度ρ［ｇ・ｃｍ-3］と、結晶相割合ＫＰｈＡと、輝度値Ｙ（Ａ／２°）とを測定した。 The density ρ [g · cm −3 ], the crystal phase ratio KPhA, and the luminance value Y (A / 2 °) were measured for the starting glass and the produced glass ceramic.
例が、表１に纏められている。
僅かな固有色および高い輝度値（高いスペクトル光透過率）Ｙ（Ａ／２°）の故に、ガラスセラミックは、多様なシステム、例えば、レンジ上面、煙突用視界窓、半導体基板、またはガラスコンポーネント、例えば耐火性ガラス、高温用途のための視界窓等に使用するために、特によく適している。特に、ガラスセラミックは、破壊、銃撃作用または圧力波作用に対して保護するための耐衝撃性の硬いガラス系におけるコンポーネントとして適している。当然ながら、ガラスセラミックまたは未処理ガラスは、必要な場合には、特に美的な効果を上げるために、通常の着色酸化物によって着色することもできる。 Because of the slight intrinsic color and high brightness value (high spectral light transmission) Y (A / 2 °), glass ceramics can be used in a variety of systems such as range tops, chimney viewing windows, semiconductor substrates, or glass components, For example, it is particularly well suited for use in fire resistant glass, viewing windows for high temperature applications, and the like. In particular, glass ceramics are suitable as components in impact-resistant hard glass systems to protect against destruction, shooting action or pressure wave action. Of course, the glass ceramic or untreated glass can also be colored with conventional colored oxides, if necessary, in order to increase the aesthetic effect in particular.
Claims (6)
３〜４．５ Ｌｉ2Ｏ
１８〜２４ Ａｌ2Ｏ3
５５〜７０ ＳｉＯ2
０．１〜２．３未満 ＴｉＯ2
１．８未満 ＺｒＯ2
０．２〜４ ΣＴｉＯ2＋ＺｒＯ2
０〜１．５ ＢａＯ
０〜０．５ ＣａＯ
１〜６ ΣＭｇＯ＋ＺｎＯ
＞５〜１０ Ｂ2Ｏ3
０〜＜１ ΣＮａ2Ｏ＋Ｋ2Ｏ
０〜１．５ 通常の清澄剤（ＳｎＯ2、Ａｓ2Ｏ3、Ｓｂ2Ｏ3、ＣｅＯ2）
を含む、Ｌｉ2Ｏ-Ａｌ2Ｏ3-ＳｉＯ2系のガラスセラミック。 It has a high-temperature quartz mixed crystal as the main crystal phase, has a density ρ of less than 2.5 g · cm −3 ,
3 to 4.5 Li 2 O
18-24 Al 2 O 3
55-70 SiO 2
0.1 to less than 2.3 TiO 2
Less than 1.8 ZrO 2
0.2-4 ΣTiO 2 + ZrO 2
0 to 1.5 BaO
0-0.5 CaO
1-6 ΣMgO + ZnO
> 5-10 B 2 O 3
0 to <1 ΣNa 2 O + K 2 O
0-1.5 conventional fining agents (SnO 2, As 2 O 3 , Sb 2 O 3, CeO 2)
Li 2 O—Al 2 O 3 —SiO 2 -based glass ceramic containing
３〜４ Ｌｉ2Ｏ
１９．５〜２１．５ Ａｌ2Ｏ3
５６〜６６ ＳｉＯ2
２〜４ ΣＴｉＯ2＋ＺｒＯ2
０．１〜０．８ ＢａＯ
０〜２．５ ＺｎＯ
０〜０．５ ＭｇＯ
１〜２．５ ΣＺｎＯ＋ＭｇＯ
＞５〜９ Ｂ2Ｏ3
０〜０．９ ΣＮａ2Ｏ＋Ｋ2Ｏ
０〜１．５ 通常の清澄剤（ＳｎＯ2、Ａｓ2Ｏ3、Ｓｂ2Ｏ3、ＣｅＯ2）
を含む請求項１に記載のガラスセラミック。 % By weight based on oxide,
3-4 Li 2 O
19.5 to 21.5 Al 2 O 3
56-66 SiO 2
2-4 ΣTiO 2 + ZrO 2
0.1-0.8 BaO
0 to 2.5 ZnO
0-0.5 MgO
1 to 2.5 ΣZnO + MgO
> 5-9 B 2 O 3
0-0.9 ΣNa 2 O + K 2 O
0-1.5 conventional fining agents (SnO 2, As 2 O 3 , Sb 2 O 3, CeO 2)
The glass ceramic according to claim 1, comprising:
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