JPH0676230B2 - Manufacturing method of crystalline glass - Google Patents
Manufacturing method of crystalline glassInfo
- Publication number
- JPH0676230B2 JPH0676230B2 JP63300322A JP30032288A JPH0676230B2 JP H0676230 B2 JPH0676230 B2 JP H0676230B2 JP 63300322 A JP63300322 A JP 63300322A JP 30032288 A JP30032288 A JP 30032288A JP H0676230 B2 JPH0676230 B2 JP H0676230B2
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- Prior art keywords
- glass
- crystals
- crystalline glass
- needle
- precipitation
- Prior art date
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Description
【発明の詳細な説明】 （産業上の利用分野） 本発明はソーダ石灰系ガラスに針状結晶を析出させた結
晶質ガラス、すなわち結晶質泡ガラス並びに緻密結晶質
ガラスの製造法に関する。TECHNICAL FIELD The present invention relates to a method for producing crystalline glass in which needle-like crystals are deposited on soda-lime glass, that is, crystalline foam glass and dense crystalline glass.
（従来技術およびその問題点） ソーダ石灰ガラスはガラス化し易いこと、低廉で容易に
製造できることから建築物その他の窓材、容器等に汎用
される。(Prior Art and Problems Thereof) Soda-lime glass is commonly used for buildings, other window materials, containers, etc. because it is easily vitrified and can be manufactured easily at low cost.
これらの材料を製造するに際しては失透すなわち結晶の
析出を避け透視性を保つことがきわめて重要視される
が、その点において当該ソーダ石灰系は各種成分系のな
かでも失透し難い最良の部類に属し、旧来より賞用され
ている。When manufacturing these materials, it is extremely important to avoid devitrification, that is, to prevent precipitation of crystals, and to maintain transparency. In that respect, the soda-lime type is the best devitrifying class among various component systems. Belongs to and has been prized since ancient times.
一方、ソーダ石灰等のガラス粉に炭酸カルシウムや炭酸
マグネシウム等のアルカリ土類金属炭酸塩を発泡剤とし
て添加し、加熱発泡させることは例えば特開昭61-21974
2号に開示されるように公知である。しかし泡ガラスを
製造するためには多量の発泡剤を添加する必要はなく、
多量の添加はむしろ泡径を不均一にしたり、異常発泡に
よる空洞を生じたりすることが指摘されている。また該
先行例に限らず、当該発泡剤を針状結晶析出促進剤とし
て採用する試みはない。On the other hand, it is possible to add an alkaline earth metal carbonate such as calcium carbonate or magnesium carbonate as a foaming agent to glass powder such as soda lime and heat-foam it.
It is known as disclosed in No. 2. However, it is not necessary to add a large amount of foaming agent to produce foam glass,
It has been pointed out that the addition of a large amount rather makes the bubble diameter non-uniform or causes cavities due to abnormal foaming. Further, not limited to the preceding example, there is no attempt to employ the foaming agent as an acicular crystal precipitation accelerator.
他方、ソーダ石灰系ガラスに核成形剤を添加し、熱処理
により強制的に結晶化させ、装飾性を付与しあるいは機
械的強度を向上させ、建材等に使用しようとする試みが
ある。On the other hand, there is an attempt to add a nucleating agent to soda-lime glass and forcibly crystallize it by heat treatment to impart decorative properties or improve mechanical strength and use it for building materials and the like.
特公昭42-2271号にはソーダ石灰系原料にフッ素分ある
いはさらに酸化チタニウムまたは酸化ジルコニウムを、
特公昭45-3554号にはソーダ石灰系原料に重金属硫化物
を、特開昭49-69730号には同様に硫化鉄あるいは硫化マ
ンガンを添加し、夫々溶融ガラス化し熱処理により結晶
化することが開示されている。In Japanese Examined Patent Publication No. 42-2271, soda lime-based raw material contains fluorine or further titanium oxide or zirconium oxide,
JP-B-45-3554 discloses that heavy metal sulfide is added to a soda-lime-based raw material, and JP-A-49-69730 discloses that iron sulfide or manganese sulfide is added in the same manner, and molten glass is crystallized by heat treatment. Has been done.
これらの方法ではウォラストナイト等の針状結晶以外に
クリストバライト、トリジマイト等のシリカ結晶が優先
析出する。しかしシリカ結晶は低温加熱域において転移
による異常体積変化があり、製品に歪を与えあるいは崩
壊をもたらすので好ましくない。In these methods, in addition to acicular crystals such as wollastonite, silica crystals such as cristobalite and tridymite are preferentially precipitated. However, silica crystals are not preferable because they have an abnormal volume change due to the transition in the low temperature heating region, which gives distortion or collapse to the product.
また核形成剤の均一分散には原料調合から溶融調製に亘
り高度な技術を要する。概して核形成剤は高比重、極微
細粉のものが用いられるからその偏析には細心の注意が
払われ、相応の技術が要求される。Further, the uniform dispersion of the nucleating agent requires a high level of technology from the raw material preparation to the melt preparation. In general, a nucleating agent having a high specific gravity and an ultrafine powder is used, so that the segregation of the nucleating agent should be carefully performed and a corresponding technique is required.
さらに一たんガラス成形し、再度熱処理結晶化する方法
は製造効率が悪く、あるいは熱処理過程で変形をもたら
す等の弊害もある。Furthermore, the method of once forming glass and re-crystallizing by heat treatment has a bad effect such as poor production efficiency or deformation in the heat treatment process.
また、核形成剤なしに結晶を析出させた開示例もある。There is also a disclosed example in which crystals are precipitated without a nucleating agent.
特公昭36-16729号にはソーダ石灰ガラスの微粉末にナト
リウム、カリウム等のリン酸塩を結合剤として集積一体
化し失透温度領域で失透乳白化せしめた乳白ガラスが開
示されている。しかし、リン酸塩の添加は前記同様にシ
リカ結晶を優先的に析出するために機械的強度、耐熱衝
撃性の向上には到らない。Japanese Examined Patent Publication No. 36729/36 discloses opalescent glass obtained by devitrifying and opacifying in the devitrification temperature region by integrating phosphates such as sodium and potassium as a binder into fine powder of soda-lime glass. However, the addition of phosphate does not lead to improvement in mechanical strength and thermal shock resistance because silica crystals are preferentially precipitated similarly to the above.
本発明は前記問題点を解消し、ソーダ石灰ガラス中に針
状結晶を特定量の範囲で析出させたことにより、機械的
強度や耐熱衝撃性に優れた結晶質ガラス、すなわち緻密
結晶質ガラスまたは結晶質泡ガラスを提供すること、さ
らにこれら結晶質ガラスの好適な製法を提供することを
目的とする。The present invention eliminates the above problems, by depositing needle-shaped crystals in soda-lime glass in a specific amount range, crystalline glass excellent in mechanical strength and thermal shock resistance, that is, dense crystalline glass or It is an object of the present invention to provide crystalline foam glass, and further to provide a suitable method for producing these crystalline glasses.
なお、本出願人は先に出願した特願昭63-216143号にお
いて、ソーダ石灰ガラス粉と、針状結晶析出促進剤であ
るアルカリ金属類の炭酸塩あるいは水酸化物を前駆原料
とし、耐熱衝撃性や機械的強度に優れた結晶質ガラスに
ついて提唱したが、本発明者はこれを更に検討した結
果、新たな針状結晶析出促進剤を採用した耐水性や耐熱
性を向上させた結晶質ガラスを見出し、本発明を達成し
たものである。In addition, in the Japanese Patent Application No. 63-216143 filed earlier by the present applicant, soda lime glass powder and a needle-shaped crystal precipitation accelerator alkali metal carbonate or hydroxide are used as precursor raw materials, and thermal shock resistance Although the inventors have proposed a crystalline glass having excellent properties and mechanical strength, the present inventor further examined this, and as a result, a crystalline glass having a new needle-shaped crystal precipitation promoter adopted to improve water resistance and heat resistance. That is, the present invention has been achieved.
（問題点を解決するための手段） 本発明は、針状結晶を20〜50wt％含有した結晶質ガラス
の製法において、ソーダ石灰系ガラス粉に対しアルカリ
土類金属類の炭酸塩、硝酸塩、水酸化物、またはアルカ
リ金属類の硝酸塩より選択された１種以上からなる針状
結晶析出促進剤を酸化物換算で10wt％添加した混合粉末
または混合スラッジを予備成形し、次いで該ソーダ石灰
シリカ系ガラスの軟化点ないし流動点間の適宜温度で10
分ないし60分加熱維持し、針状結晶を析出含有せしめる
ようにしたこと、前記針状結晶がウォラストナイト、デ
ビトライト、ディオプサイド、SrSiO3、Ba2Si3O8、BaSi
O3またはNa2CaSi3O8の１種以上であること、前記加熱維
持するとともに、または加熱維持した後に圧密化せしめ
るようにしたこと、からなる。(Means for Solving Problems) The present invention is a method for producing crystalline glass containing 20 to 50 wt% of needle-shaped crystals, wherein carbonate of soda-lime glass powder, carbonate of alkaline earth metal, nitrate, water Oxide or a mixed powder or sludge obtained by adding 10 wt% of acicular crystal precipitation accelerator consisting of at least one selected from nitrates of alkali metals in terms of oxide is preformed, and then the soda lime silica glass 10 at an appropriate temperature between the softening point and pour point of
It is heated and maintained for 60 minutes to 60 minutes to allow acicular crystals to be contained, and the acicular crystals are wollastonite, devitrite, diopside, SrSiO 3 , Ba 2 Si 3 O 8 , BaSi.
And at least one of O 3 and Na 2 CaSi 3 O 8 and maintaining the heating, or after heating and consolidating.
本発明においては出発原料として板ガラス、容器ガラス
等に多用されるソーダ石灰ガラスの廃棄物（ガラスカレ
ットと称する）が用いられ、これを150メッシュ（100μ
ｍφ）以下に粉砕調製する。後述する針状結晶析出促進
剤と良好に反応するためには、その比表面積が大きく、
したがって細粒であるのが望ましく、特に上記粒度以下
とするのが好ましい。In the present invention, waste of soda-lime glass (referred to as glass cullet), which is often used for plate glass, container glass, etc., is used as a starting material, and this is used as 150 mesh (100 μ
mφ) to be pulverized and prepared. In order to react well with the needle-shaped crystal precipitation accelerator described later, its specific surface area is large,
Therefore, it is desirable that the particles are fine particles, and it is particularly preferable that the particle size is not more than the above-mentioned particle size.
他方の出発原料として針状結晶析出促進剤（以下単に析
出促進剤という）を用いる。針状結晶とはウォラストナ
イト、デビトライト、ディオプサイド、SrSiO3、Ba2Si3
O8、BaSiO3、Na2CaSi3O8等の針状に発達する結晶をい
う。As the other starting material, an acicular crystal precipitation accelerator (hereinafter simply referred to as a precipitation accelerator) is used. What are acicular crystals? Wollastonite, devitrite, diopside, SrSiO 3 , Ba 2 Si 3
O 8, BaSiO 3, Na 2 CaSi 3 O 8 or the like refers to a needle crystal of development.
これらは針状結晶の選択的な析出を促進する成分として
アルカリ土類金属の炭酸塩、硝酸塩、水酸化物またはア
ルカリ金属の硝酸塩より適宜１種類以上採用する。These are appropriately selected as one or more kinds from alkaline earth metal carbonates, nitrates, hydroxides or alkali metal nitrates as a component for promoting the selective precipitation of needle crystals.
これらは熱処理により融化し、前記ガラス粉との反応に
より急速に針状結晶を析出するものであり、ガラスカレ
ット粉同様150メッシュ（100μｍφ）以下のものを用い
る。These are those which are melted by heat treatment and rapidly precipitate acicular crystals by the reaction with the glass powder, and those having a mesh of 150 mesh (100 μmφ) or less are used like the glass cullet powder.
前記ガラスカレット粉に対し析出促進剤を酸化物換算で
1wt％ないし10wt％添加し、湿式または乾式混合のう
え、所望の形状にプレス成形しまたはスラッジ状として
鋳込成形する。添加量が1wt％未満の場合は針状結晶の
析出作用は小さく、10wt％を越えると結晶析出成分領域
を変化させ、針状結晶以外の結晶が析出し易くなる。Precipitation accelerator in oxide conversion for the glass cullet powder
1 wt% to 10 wt% is added, and the mixture is wet- or dry-mixed and then press-molded into a desired shape or cast as sludge. If the addition amount is less than 1 wt%, the precipitation action of needle-like crystals is small, and if it exceeds 10 wt%, the crystal precipitation component region is changed, and crystals other than needle-like crystals are likely to precipitate.
なお、本出願人が先に出願した特願昭63-216143号にお
いて、析出促進剤としてアルカリ金属炭酸塩あるいは水
酸化物を用いた場合は、低融点のデビトライト、Na2CaS
i3O8等アルカリ金属を多く含有する結晶を多量に析出し
たり、あるいは比較的高融点のウオラストナイトを多量
に析出する一方、アルカリ金属に富んだ低温溶融性のガ
ラスマトリックスを形成する場合があるが、いずれの場
合においても結晶質ガラスの耐熱性が劣り、耐水性も劣
化させる。本発明におけるアルカリ土類金属化合物を用
いた場合は高融点のアルカリ土類金属珪酸塩よりなる針
状結晶を析出し易く、ガラスマトリックスもアルカリ土
類金属を比較的多く含有して耐熱、耐水性に優れた結晶
質ガラスとなる。In addition, in Japanese Patent Application No. 63-216143 filed by the applicant of the present invention, when an alkali metal carbonate or hydroxide is used as a precipitation accelerator, devitrite, Na 2 CaS having a low melting point is used.
When a large amount of crystals containing a large amount of alkali metal such as i 3 O 8 or a large amount of wollastonite with a relatively high melting point is formed, while forming a low temperature melting glass matrix rich in alkali metals However, in any case, the heat resistance of the crystalline glass is poor and the water resistance is also deteriorated. When the alkaline earth metal compound in the present invention is used, needle-like crystals made of a high-melting alkaline earth metal silicate are easily deposited, and the glass matrix also contains a relatively large amount of alkaline earth metal and is heat and water resistant. It becomes an excellent crystalline glass.
本発明において、析出促進剤のより好ましい添加範囲は
5wt％ないし10wt％である。また予備成形は形状維持と
ともにカレット粉と析出促進剤を密に接触させるうえで
必要である。In the present invention, the more preferable addition range of the precipitation accelerator is
It is 5 wt% to 10 wt%. Preforming is necessary to maintain the shape and to bring the cullet powder into close contact with the precipitation promoter.
次いで原ガラスの軟化点（粘度において107.65ポイズ、
通例の板ガラスにおいて720℃）以上、流動点（同様に1
05ポイズ、900℃）以下の範囲の適宜温度に昇温し10分
ないし60分保持する。なお、ガラス軟化点未満では析出
促進剤との反応が不充分であり、流動点を越えると液相
温度すなわちガラス化温度に近接し結晶析出傾向が弱ま
る。また10分未満では針状結晶の析出が不充分であり、
60分を越えると析出促進剤にもよるが結晶相とガラス相
が再度反応して新たなガラス相を形成したり、針状結晶
析出が終焉に達し、クリストバライト等耐熱性に悪影響
を与える結晶が析出し易い。Then the softening point of the raw glass ( 10.65 poise in viscosity,
720 ℃ above normal glass, pour point (also 1
The temperature is raised to an appropriate temperature within the range of 0 5 poise, 900 ° C.) or less and kept for 10 to 60 minutes. If it is less than the glass softening point, the reaction with the precipitation accelerator is insufficient, and if it exceeds the pour point, the tendency of crystal precipitation is weakened by approaching the liquidus temperature, that is, the vitrification temperature. Further, if less than 10 minutes, the precipitation of needle-shaped crystals is insufficient,
If it exceeds 60 minutes, depending on the precipitation accelerator, the crystal phase and the glass phase will react again to form a new glass phase, or the needle-shaped crystal precipitation will reach the end, and crystals such as cristobalite that adversely affect the heat resistance will be formed. Easy to deposit.
当該温度域で軟化したガラスと分解溶融した析出促進剤
が反応し、分解したガス成分の一部は反応粘稠液中に捕
捉されて泡ガラス状となり、他方でガラスカレット粉の
粒界や反応ガラス相中に結晶の析出が始まる。なお、よ
り好ましい熱処理温度時間の範囲は、800〜850℃、30〜
60分である。In the temperature range, the softened glass reacts with the decomposed and melted precipitation accelerator, and some of the decomposed gas components are trapped in the reaction viscous liquid and become foamy glass, while on the other hand, the grain boundaries and the reaction of the glass cullet powder. Crystal precipitation begins in the glass phase. A more preferable heat treatment temperature time range is 800 to 850 ° C, 30 to
60 minutes.
析出促進剤は当該針状結晶の析出に適した融液成分、粘
度を付与するものであって、いわゆる核形成剤のように
溶融拡散が困難ないわば異質物として存在してそれを元
に結晶を析出させる類のものとは異なる。The precipitation accelerator is a melt component suitable for the precipitation of the needle-like crystals, which imparts a viscosity, and exists as a so-called heterogeneous substance that is difficult to melt and diffuse like a so-called nucleating agent and crystallizes based on it. Is different from the type that precipitates.
針状結晶を析出させる作用はアルカリ土類金属類のうち
でマグネシウム、カルシウムが大きく、ストロチウム、
バリウムはこれに比べ若干劣る。なお同じアルカリ土類
金属系においても炭酸塩、硝酸塩、水酸化物の作用が著
しい。ただし、分解温度が著しく高い炭酸ストロンチウ
ムや炭酸バリウムはその作用が劣る。なお硫酸塩、塩化
物等はその作用が殆ど示さない。またリン酸塩は耐熱性
や機械的強度に弊害を生じ易いシリカ結晶が優先析出す
るので好ましくない。アルカリ土類金属により、あるい
は同一アルカリ土類金属系でも化合物の種類により析出
傾向が異なる理由について解明していないが、一因とし
てアルカリ土類金属イオンの拡散速度や、化合物の解離
温度等が影響しているものと推察される。Among the alkaline earth metals, magnesium and calcium have a large effect of precipitating acicular crystals, and strontium,
Barium is slightly inferior to this. Even in the same alkaline earth metal system, the action of carbonate, nitrate and hydroxide is remarkable. However, strontium carbonate and barium carbonate, which have extremely high decomposition temperatures, are inferior in their action. It should be noted that sulfate, chloride and the like have almost no effect. Phosphate is also not preferred because silica crystals preferentially precipitate, which are likely to cause adverse effects on heat resistance and mechanical strength. The reason why the precipitation tendency differs depending on the alkaline earth metal or the type of compound even in the same alkaline earth metal system has not been elucidated, but one factor is the diffusion rate of alkaline earth metal ions and the dissociation temperature of the compound. It is presumed that it is doing.
ソーダ石灰系ガラスにおいてはその成分領域からウォラ
ストナイト、デビトライト、Na2CaSi3O8針状結晶のほ
か、クリストバライト、トリジマイト等のシリカ結晶が
析出するが、析出促進剤を添加した系ではシリカ結晶の
析出は抑制される。析出促進剤の添加量や熱処理条件に
もよるが、カルシウム化合物を添加した場合は、前記針
状結晶が、マグネシウム化合物の場合はさらにディオプ
サイドが、ストロンチウム化合物の場合はSrSiO3が、バ
リウム化合物の場合はBa2Si3O8、BaSiO3が析出し易い。In soda-lime glass, wollastonite, devitrite, Na 2 CaSi 3 O 8 acicular crystals from the component region, as well as silica crystals such as cristobalite and tridymite, are precipitated, but in the system where a precipitation accelerator is added, silica crystals are formed. Precipitation is suppressed. Depending on the amount of precipitation accelerator added and heat treatment conditions, when a calcium compound is added, the needle crystals are further diopside in the case of a magnesium compound, and SrSiO 3 in the case of a strontium compound is a barium compound. In this case, Ba 2 Si 3 O 8 and BaSiO 3 are likely to precipitate.
本発明においては前記針状結晶をガラス中に20〜50wt％
含有させたことにより機械的強度や耐熱性が格段と向上
する。20wt％未満ではそれらの効果が小さい。50wt％を
超えて析出させようとすると成分領域上当然ではあるが
シリカ結晶も発生し、機械的強度や耐熱衝撃性を阻害す
るので好ましくない。より好ましくは23〜45wt％の範囲
である。In the present invention, the needle crystals are contained in the glass in an amount of 20 to 50% by weight.
By including it, mechanical strength and heat resistance are remarkably improved. If it is less than 20 wt%, those effects are small. When attempting to deposit more than 50% by weight, silica crystals are naturally generated in the component region, which impairs mechanical strength and thermal shock resistance, which is not preferable. More preferably, it is in the range of 23 to 45 wt%.
このようにして製造された結晶質ガラスは無数の泡を残
留した結晶質泡ガラスを形成し、徐冷工程を経ることに
より泡も均一化された製品となる。The crystalline glass produced in this manner forms a crystalline foam glass in which numerous bubbles remain, and becomes a product in which the bubbles are made uniform by the slow cooling process.
一方、熱処理時または熱処理後の熱軟化状態において圧
縮手段、例えば一対のロール間を通過させ該ロール間で
挟圧する等の手段を講ずれば適度に泡を逸出しかさ比重
がコントロールされた結晶質泡ガラス、あるいは泡を殆
ど逸出した緻密な結晶質ガラスとなる。さらに徐冷する
ことにより製品を得る。On the other hand, when heat treatment or in a heat softened state after heat treatment, if a means for compressing, for example, a means of passing between a pair of rolls and pinching between the rolls is taken, a bubble is appropriately escaped and a crystal having a controlled bulk density is controlled. It becomes a high quality glass or a dense crystalline glass with almost no bubbles. The product is obtained by further slow cooling.
（実施例） 板ガラスカレット粉として重量％でSiO271％、Al2O31.6
％、CaO 11％、MgO 2.1％、Na2O13％、K2O0.8％の組成
を有する粒度200メッシュ以下に調整したものを準備し
た。析出促進剤として市販のマグネシウム、カルシウ
ム、ストロンチウム、バリウの炭酸塩、硝酸塩、水酸化
物、および硝酸ナトリウムを用意した。(Example) As plate glass cullet powder, SiO 2 71% by weight%, Al 2 O 3 1.6
%, CaO 11%, MgO 2.1%, Na 2 O 13%, K 2 O 0.8% and a particle size adjusted to 200 mesh or less were prepared. Commercially available magnesium, calcium, strontium, barium carbonate, nitrate, hydroxide, and sodium nitrate were prepared as precipitation accelerators.
前記カレット粉と針状結晶析出促進剤を所定割合で乾式
混合、または水を7wt％添加混合して湿式混合し、乾式
混合により得られたものは20kg/cm2の圧力条件でプレス
し、また湿式混合によって得られたスラッジは鋳込成形
後乾燥して予備成形品とした。これを電気炉内で所定温
度まで400℃／時間の割合で昇温し所定時間保持し、次
いで徐冷することにより各種発泡試料を得た。さらに一
部の試料については熱処理後、炉から取出し予め当該温
度に予熱した鋼板に挟み、人手により上方からローラー
を転動して圧縮し、気泡を除去することにより緻密な試
料を得た。The cullet powder and the needle-shaped crystal precipitation accelerator are dry mixed at a predetermined ratio, or 7 wt% of water is added and mixed for wet mixing, and the product obtained by dry mixing is pressed under a pressure condition of 20 kg / cm 2. The sludge obtained by wet mixing was cast-molded and then dried to obtain a preform. Various foamed samples were obtained by raising the temperature to a predetermined temperature in an electric furnace at a rate of 400 ° C./hour, maintaining the temperature for a predetermined time, and then slowly cooling it. Further, some of the samples were taken out of the furnace after heat treatment, sandwiched between steel plates which had been preheated to the temperature in advance, and were manually rolled by a roller from above to be compressed to remove bubbles, thereby obtaining a dense sample.
これらの試料について以下の測定を行った。The following measurements were performed on these samples.
比重測定；比重ビンを用いた公知の測定手段による。Specific gravity measurement: By a known measuring means using a specific gravity bottle.
結晶の同定；主にＸ線回析および鏡下観察により、EPMA
分析を併用した。Crystal identification; EPMA mainly by X-ray diffraction and observation under a mirror
Combined analysis.
固相中の結晶量（重量百分体積率）の測定；公知のOhlb
erg-Stricklerが提唱した定量法によれば、ｘ線回析に
おける２θ＝20〜25°におけるガラスのバックグラウン
ド強度をIg、100％結晶のそれをIc、試料のそれをIsと
すれば、結晶料（wt％）＝Ig−Is/Ig−Icで与えられ
る。本法に則り検量線を作成し、定量した。また、鏡下
観測による定量法を補助的に採用した。Measurement of the amount of crystals (weight percentage volume ratio) in the solid phase; known Ohlb
According to the quantitative method proposed by erg-Strickler, if the background intensity of glass at 2θ = 20 to 25 ° in x-ray diffraction is Ig, that of 100% crystal is Ic, and that of the sample is Is, the crystal is Material (wt%) = Ig-Is / Ig-Ic. A calibration curve was prepared according to this method and quantified. In addition, a quantitative method based on observation under a mirror was adopted as an auxiliary.
熱衝撃試験（急冷試験）;50mm口×20mm厚の試料を電気
炉にセットして500℃に保持後、取出して直ちに10℃の
水中に投入、急冷し、目視において亀裂の生じていない
ものを良、小さな亀裂が生じたものを可、大きな亀裂を
生じ、または崩壊したものを不可の３ランクに区分し
た。Thermal shock test (quenching test); set a 50mm x 20mm thick sample in an electric furnace, hold at 500 ° C, take it out, immediately put it in water at 10 ° C, quench it, and check that there are no cracks visually. Good, those with small cracks were classified as good, and those with large cracks or collapsed were classified into three ranks.
さらに一部の試料については曲げ強度を測定した。Further, the bending strength of some of the samples was measured.
なお、ソーダ石灰ガラス粉に、リン酸塩、ホウ酸、鉛化
合物、硫酸塩、塩化物を夫々添加混合し、プレス成形し
たものを準備し、同様に熱処理し、測定して比較検討し
た。In addition, phosphate, boric acid, lead compound, sulfate, and chloride were added to and mixed with soda-lime glass powder, and press-molded was prepared, heat-treated in the same manner, measured, and comparatively examined.
試料作成条件および測定結果を第１表（実施例）、第２
表（比較例）に示す。Sample preparation conditions and measurement results are shown in Table 1 (Examples) and 2
The results are shown in the table (comparative example).
表から明らかな如く、本発明のものは耐熱衝撃性や機械
的強度に優れる。比較例１、２のリン酸塩を添加したも
のは主結晶としてシリカが析出する。比較例３、４のホ
ウ酸、鉛化合物を添加したものは結晶が析出せず、むし
ろガラス化領域を拡大するものと推察される。比較例５
ないし７の硫酸塩、塩化物は、分解せずに残留し、結晶
析出効果を示さない。これら比較例はいずれも耐熱性や
機械的強度に劣るものである。As is clear from the table, the present invention has excellent thermal shock resistance and mechanical strength. In those containing the phosphates of Comparative Examples 1 and 2, silica is precipitated as a main crystal. It is presumed that the crystals of Comparative Examples 3 and 4 to which boric acid and a lead compound were added did not precipitate crystals, but rather expanded the vitrification region. Comparative Example 5
The sulfates and chlorides of Nos. 7 to 7 remain without being decomposed and do not show a crystal precipitation effect. All of these comparative examples are inferior in heat resistance and mechanical strength.
（発明の効果） 本発明によればきわめて容易に結晶質泡ガラス、緻密結
晶質ガラス等の結晶質ガラスが製造でき、得られた結晶
質ガラスは、耐熱衝撃性、機械的強度や耐熱性、耐水性
にも優れ、耐熱高強度建材として有用であり、またその
製造もきわめて容易であって、結晶質泡ガラスや緻密結
晶質ガラスが自在に製造できるという効果を奏する。 (Effect of the invention) According to the present invention, crystalline glass such as crystalline foam glass and dense crystalline glass can be produced very easily, and the obtained crystalline glass has thermal shock resistance, mechanical strength and heat resistance, It has excellent water resistance, is useful as a heat-resistant and high-strength building material, is extremely easy to manufacture, and has an effect that crystalline foam glass or dense crystalline glass can be manufactured freely.
Claims (3)
スの製法において、ソーダ石灰系ガラス粉に対しアルカ
リ土類金属類の炭酸塩、硝酸塩、水酸化物、またはアル
カリ金属類の硝酸塩より選択される１種以上からなる針
状結晶析出促進剤を酸化物換算で10wt％添加した混合粉
体または混合スラッジを予備成形し、次いで該ソーダ石
灰シリカ系ガラスの軟化点ないし流動点間の適宜温度で
10分ないし60分加熱維持し、針状結晶を析出含有せしめ
るようにしたことを特徴とする結晶質ガラスの製造法。1. A method for producing crystalline glass containing 20 to 50 wt% of needle-shaped crystals, wherein an alkaline earth metal carbonate, nitrate, hydroxide or alkali metal nitrate is added to soda lime glass powder. A mixed powder or mixed sludge containing 10% by weight of an acicular crystal precipitation accelerating agent selected from the group consisting of at least one selected from the above is preformed, and then the softening point or pour point of the soda lime silica glass is between At appropriate temperature
A method for producing crystalline glass, characterized in that heating is maintained for 10 to 60 minutes so that acicular crystals are precipitated and contained.
ト、ディオプサイド、SrSiO3、Ba2Si3O8、BaSiO3または
Na2CaSi3O8の１種以上であることを特徴とする請求項１
記載の結晶質ガラスの製造法。2. The acicular crystals are wollastonite, devitrite, diopside, SrSiO 3 , Ba 2 Si 3 O 8 , BaSiO 3 or
2. One or more kinds of Na 2 CaSi 3 O 8 are included.
A method for producing the crystalline glass described above.
た後に圧密化せしめるようにしたことを特徴とする請求
項１または２記載の結晶質ガラスの製造法。3. The method for producing crystalline glass according to claim 1 or 2, wherein the glass is made to be consolidated while being heated or after being heated.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63300322A JPH0676230B2 (en) | 1988-11-28 | 1988-11-28 | Manufacturing method of crystalline glass |
| GB8919614A GB2224025B (en) | 1988-08-30 | 1989-08-30 | Glass-ceramics containing needle-like crystals and method of producing same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63300322A JPH0676230B2 (en) | 1988-11-28 | 1988-11-28 | Manufacturing method of crystalline glass |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02145456A JPH02145456A (en) | 1990-06-04 |
| JPH0676230B2 true JPH0676230B2 (en) | 1994-09-28 |
Family
ID=17883383
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63300322A Expired - Lifetime JPH0676230B2 (en) | 1988-08-30 | 1988-11-28 | Manufacturing method of crystalline glass |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0676230B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5418369A (en) * | 1993-03-12 | 1995-05-23 | At&T Corp. | System for continuously monitoring curing energy levels within a curing unit |
| JP4756254B2 (en) * | 2001-04-10 | 2011-08-24 | 昌利 佐藤 | Wollastonite low-temperature fired glass ceramics and method for producing the same |
| JP2010083721A (en) * | 2008-09-30 | 2010-04-15 | Reiseki:Kk | Method for storing granulate or powdery object to be stored |
| US9321695B2 (en) * | 2013-01-08 | 2016-04-26 | King Abdulaziz City for Science and Technology (KACST) | Method for manufacturing glass-ceramic composite |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5992944A (en) * | 1982-11-15 | 1984-05-29 | Ihara Chikuro Kogyo Kk | Foam glass |
| JPS6374936A (en) * | 1986-09-17 | 1988-04-05 | Kubota Ltd | Crystallized glass and production thereof |
-
1988
- 1988-11-28 JP JP63300322A patent/JPH0676230B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02145456A (en) | 1990-06-04 |
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