JPH02145456A - Crystalline glass and production thereof - Google Patents
Crystalline glass and production thereofInfo
- Publication number
- JPH02145456A JPH02145456A JP30032288A JP30032288A JPH02145456A JP H02145456 A JPH02145456 A JP H02145456A JP 30032288 A JP30032288 A JP 30032288A JP 30032288 A JP30032288 A JP 30032288A JP H02145456 A JPH02145456 A JP H02145456A
- Authority
- JP
- Japan
- Prior art keywords
- glass
- needle
- crystals
- crystalline
- crystalline glass
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000011521 glass Substances 0.000 title claims abstract description 46
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 239000013078 crystal Substances 0.000 claims abstract description 60
- 239000000843 powder Substances 0.000 claims abstract description 16
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 10
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 8
- 239000010456 wollastonite Substances 0.000 claims abstract description 6
- 229910052882 wollastonite Inorganic materials 0.000 claims abstract description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 5
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 5
- 239000010802 sludge Substances 0.000 claims abstract description 5
- 239000011812 mixed powder Substances 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims abstract description 3
- 238000001556 precipitation Methods 0.000 claims description 33
- 238000010438 heat treatment Methods 0.000 claims description 15
- 239000005361 soda-lime glass Substances 0.000 claims description 12
- 150000002823 nitrates Chemical class 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- -1 debitrite Inorganic materials 0.000 claims description 5
- 150000004679 hydroxides Chemical class 0.000 claims description 5
- NWXHSRDXUJENGJ-UHFFFAOYSA-N calcium;magnesium;dioxido(oxo)silane Chemical compound [Mg+2].[Ca+2].[O-][Si]([O-])=O.[O-][Si]([O-])=O NWXHSRDXUJENGJ-UHFFFAOYSA-N 0.000 claims description 4
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 4
- 229910052637 diopside Inorganic materials 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- 230000035939 shock Effects 0.000 abstract description 8
- HUAUNKAZQWMVFY-UHFFFAOYSA-M sodium;oxocalcium;hydroxide Chemical compound [OH-].[Na+].[Ca]=O HUAUNKAZQWMVFY-UHFFFAOYSA-M 0.000 abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 abstract description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 abstract description 4
- 239000004566 building material Substances 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 abstract description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 abstract description 2
- 239000004317 sodium nitrate Substances 0.000 abstract description 2
- 235000010344 sodium nitrate Nutrition 0.000 abstract description 2
- 238000000151 deposition Methods 0.000 abstract 4
- 229910002651 NO3 Inorganic materials 0.000 abstract 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 abstract 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 21
- 230000000694 effects Effects 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 239000000377 silicon dioxide Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 239000006063 cullet Substances 0.000 description 6
- 239000011494 foam glass Substances 0.000 description 6
- 229910019142 PO4 Inorganic materials 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000002667 nucleating agent Substances 0.000 description 5
- 235000021317 phosphate Nutrition 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000005484 gravity Effects 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 150000001805 chlorine compounds Chemical class 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 238000004031 devitrification Methods 0.000 description 3
- 239000005357 flat glass Substances 0.000 description 3
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 3
- 229910004709 CaSi Inorganic materials 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000002159 abnormal effect Effects 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 239000004088 foaming agent Substances 0.000 description 2
- 150000002611 lead compounds Chemical class 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 238000004445 quantitative analysis Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 238000004017 vitrification Methods 0.000 description 2
- 239000004604 Blowing Agent Substances 0.000 description 1
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 229910001963 alkali metal nitrate Inorganic materials 0.000 description 1
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
- 229910052915 alkaline earth metal silicate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 150000001553 barium compounds Chemical class 0.000 description 1
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229940043430 calcium compound Drugs 0.000 description 1
- 150000001674 calcium compounds Chemical class 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000005356 container glass Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- AAOVKJBEBIDNHE-UHFFFAOYSA-N diazepam Chemical compound N=1CC(=O)N(C)C2=CC=C(Cl)C=C2C=1C1=CC=CC=C1 AAOVKJBEBIDNHE-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000010922 glass waste Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 150000002681 magnesium compounds Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000005392 opalescent glass Substances 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 229910000018 strontium carbonate Inorganic materials 0.000 description 1
- 150000003438 strontium compounds Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- CADICXFYUNYKGD-UHFFFAOYSA-N sulfanylidenemanganese Chemical compound [Mn]=S CADICXFYUNYKGD-UHFFFAOYSA-N 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229940072690 valium Drugs 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Landscapes
- Glass Compositions (AREA)
Abstract
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
ガラスに関し、さらに該結晶質ガラスの製法に関する。Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a crystalline glass in which acicular crystals are precipitated on a soda-lime glass, that is, a crystalline foam glass and a dense crystalline glass, and further relates to the crystalline glass. Concerning the manufacturing method.
（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 its Problems) Soda-lime glass is widely used for building and other window materials, containers, etc. because it is easily vitrified and can be manufactured 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
析出を避は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、旧来より賞月されて
いる。When manufacturing these materials, it is extremely important to avoid devitrification, that is, the precipitation of crystals, and to maintain transparency, and in this respect, the soda lime system is the best among the various component systems that are resistant to devitrification. It belongs to this category and has traditionally been awarded the award.
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６１−２
１９７４２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（、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, adding an alkaline earth metal carbonate such as calcium carbonate or magnesium carbonate to glass powder such as soda lime as a foaming agent and foaming by heating is known, for example, in JP-A-61-2
It is known as disclosed in No. 19742. However, in order to produce foam glass, it is not necessary to add a large amount of blowing agent (although it has been pointed out that adding a large amount may actually make the bubble diameter uneven or create cavities due to abnormal foaming. Not limited to the preceding example, there has been no attempt to employ the foaming agent as a needle-like 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 have been attempts to add a nucleating agent to soda-lime glass and forcibly crystallize it through heat treatment to impart decorative properties or improve mechanical strength, and to use the glass in 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 Patent Publication No. 42-2271, a fluorine content or further titanium oxide or zirconium oxide was added to soda lime-based raw materials, in Japanese Patent Publication No. 45-3554, heavy metal sulfides were added to soda lime-based raw materials, and in Japanese Patent Publication No. 49-69730. Similarly, it is disclosed that iron sulfide or manganese sulfide is added, each is melted and vitrified, and then crystallized by heat treatment.
これらの方法ではウオ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, silica crystals such as cristobalite and tridymite are preferentially precipitated in addition to needle-shaped crystals such as wollastonite. However, silica crystals are undesirable because they undergo abnormal volume changes due to transition in the low-temperature heating range, which can cause distortion or collapse of 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, uniform dispersion of the nucleating agent requires advanced technology from raw material preparation to melt preparation. Generally, the nucleating agent used is one with a high specific gravity and an extremely fine powder, so careful attention must be paid to its segregation, and appropriate techniques are required.
さらに−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 forming glass and then heat-treating and crystallizing it again has disadvantages such as poor production efficiency and deformation during 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 are also disclosed examples in which crystals are precipitated without a nucleating agent.
特公昭３６−１６７２９号にはソーダ石灰系ガラスの微
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。Japanese Patent Publication No. 36-16729 discloses an opalescent glass in which fine powder of soda-lime glass is integrated with phosphates such as sodium and potassium as a binder, and the glass is devitrified and opalescent in the devitrification temperature range.
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。However, addition of phosphate preferentially precipitates silica crystals as described above, and thus does not improve mechanical strength or thermal shock resistance.
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 solves the above problems and produces a crystalline glass with excellent mechanical strength and thermal shock resistance, that is, a dense crystalline glass or It is an object of the present invention to provide crystalline foam glasses and also 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６３−２１６１４
３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, the present applicant has previously filed patent application No. 63-21614.
In No. 3, we proposed a crystalline glass with excellent thermal shock resistance and mechanical strength that uses soda-lime glass powder and carbonate or hydroxide of alkali metals, which are accelerators for the precipitation of needle crystals, as precursor raw materials. As a result of further investigation, the present inventors have discovered a crystalline glass with improved water resistance and heat resistance that employs a new acicular crystal precipitation promoter, thereby achieving the present invention.
（問題点を解決するための手段）
本発明はソーダ石灰系ガラス粉と針状結晶析出促進剤を
前駆原料とした熱処理成形体であって、針状結晶を２０
−ｔ％以上かつ５０ｗｔ％以下含有した結晶質ガラスに
おいて、前記針状結晶析出促進剤が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種以上であり、具体的には前記
針状結晶がウオラストナイト、デビトライト、ディオプ
サイド、５ｒＳｉ０３、ＢａｚＳｉ３０ｇ、Ｂａ５ｉｃ
、またはＮａ、ＣａＳｉ 、０．の１種以上よりなるも
の、およびその製造法に関し、ソーダ石灰系ガラス粉に
対し針状結晶析出促進剤を酸化物換算で１ないし１０ｓ
ｖｔ％添加した混合粉体ないし混合スラッジを予備成形
し、次いで該ソーダ石灰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６〇分加熱維持し、針状結
晶を析出せしめるようにしたこと、さらに前記加熱維持
に際し、または加熱維持した後に圧密化せしめることか
らなる。(Means for Solving the Problems) The present invention is a heat-treated molded article using soda-lime-based glass powder and a needle-like crystal precipitation accelerator as precursor raw materials.
- In the crystalline glass containing t% or more and 50wt% or less, the acicular crystal precipitation promoter is one type selected from carbonates, nitrates, hydroxides of alkaline earth metals, or nitrates of alkali metals. Specifically, the needle-like crystals include wollastonite, debitrite, diopside, 5rSi03, BazSi30g, Ba5ic.
, or Na, CaSi, 0. Regarding products consisting of one or more of
The mixed powder or mixed sludge added with vt% is preformed, and then heated and maintained for 10 to 60 minutes at an appropriate temperature between the softening point and pour point of the soda lime glass to precipitate needle-like crystals. and further comprises compacting during or after maintaining the heating.
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メツシユ（１
００μｍφ）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, soda lime glass waste (referred to as glass cullet), which is often used for sheet glass, container glass, etc., is used as a starting material, and 150 meshes (1
00 μmφ) or less. In order to react favorably with the acicular crystal precipitation accelerator described later, it is desirable that the specific surface area is large and therefore the particles are fine, and in particular, the particle size is preferably equal to or less 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。針状結晶とはウオラストナ
イト、デビトライト、ディオプサイド、ＳｒＳｉＯ，、
ＢａｚＳｉ、、Ｏｓ、 ＢａＳｉＯ３、Ｎａ。A needle crystal precipitation promoter (hereinafter simply referred to as a precipitation promoter) is used as the other starting material. Acicular crystals include wollastonite, debitrite, diopside, SrSiO, etc.
BazSi, , Os, BaSiO3, Na.
Ｃａ５ｉ３０ｓ等の針状に発達する結晶をいう。Refers to crystals that develop into needle shapes such as Ca5i30s.
これら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。As a component that promotes the selective precipitation of these needle-shaped crystals, one or more types of alkaline earth metal carbonates, nitrates, hydroxides, and alkali metal nitrates are appropriately selected.
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メツシュ（１００μｍφ）以下のもの
を用いる。These are melted by heat treatment and rapidly precipitate needle-like crystals by reaction with the glass powder, and like the glass cullet powder, those having a diameter of 150 meshes (100 μmφ) or less are used.
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、１ｌｈｔ％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。A precipitation accelerator is added to the glass cullet powder in an amount of 1 wt % to 10 wt % in terms of oxide, mixed wet or dry, and then press-molded into a desired shape or cast as a sludge. When the amount added is less than 1 wt%, the action of precipitating needle-like crystals is small, and when it exceeds 1 lht%, the region of crystal precipitated components changes, and crystals other than needle-like crystals tend to precipitate.
なお、本出願人が先に出願した特開昭６３−２１６１４
３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
、Ｎａ、ＣａＳｉ、０．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, Japanese Patent Application Laid-Open No. 63-21614, which the present applicant previously applied for,
In No. 3, when an alkali metal carbonate or hydroxide is used as a precipitation accelerator, low melting point debitrite, Na, CaSi, 0. A large amount of crystals containing a large amount of alkali metals may be precipitated or a glass matrix may be formed, but in either case, the heat resistance of the crystalline glass is poor and the water resistance is also deteriorated. When the alkaline earth metal compound of the present invention is used, needle-like crystals made of alkaline earth metal silicate with a high melting point are easily precipitated, and the glass matrix also contains a relatively large amount of alkaline earth metal, resulting in heat resistance and water resistance. It becomes a crystalline glass with excellent properties.
本発明において、析出促進剤のより好ましい添加範囲は
５ｗｔχ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, a more preferable addition range of the precipitation accelerator is 5 wt% to 10 wt%. In addition, preforming is necessary to maintain the shape and to bring the cullet powder into close contact with the precipitation accelerator.
次いで原ガラスの軟化点（粘度において１０７・６５ボ
イズ、通例の板ガラスにおいて７２０℃）以上、流動点
（同様に１０’ボイズ、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。Next, the temperature is raised to an appropriate temperature within the range of the softening point of the raw glass (viscosity: 107.65 voids, 720°C for regular plate glass) and below the pour point (also 10' voids, 900°C) for 10 to 60 minutes. Hold. Note that below the glass softening point, the reaction with the precipitation accelerator is insufficient, and above the pour point, the temperature approaches the liquidus temperature, that is, the vitrification temperature, and the tendency for crystal precipitation to weaken. Also, if the time is less than 10 minutes, the precipitation of needle-like crystals will be insufficient, and if the time exceeds 60 minutes, depending on the precipitation accelerator, the crystal phase and the glass phase may react again to form a new glass phase, or the needle-like crystals may not be sufficiently precipitated. Precipitation reaches its end, and crystals such as cristobalite, which have an adverse effect on heat resistance, tend to precipitate.
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 this temperature range, the softened glass reacts with the decomposed and melted precipitation accelerator, and some of the decomposed gas components are captured in the reaction viscous liquid to form a foam glass, while the grain boundaries of the glass cullet powder and the reaction Crystals begin to precipitate into the glass phase. In addition, a more preferable range of heat treatment temperature and time 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。Precipitation accelerators provide melt components and viscosity suitable for the precipitation of the needle-like crystals, and like so-called nucleating agents, they exist as foreign substances that are difficult to melt and diffuse, and are used to form crystals based on them. 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
物等はその作用を殆ど示さない。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。Of the alkaline earth metals, magnesium and calcium have the greatest effect on precipitating needle-like crystals, while strotium,
Valium is slightly inferior to this. Furthermore, even in the same alkaline earth metal system, the effects of carbonates, nitrates, and hydroxides are significant. However, strontium carbonate and barium carbonate, which have extremely high decomposition temperatures, are inferior in their effectiveness. Note that sulfates, chlorides, etc. have almost no effect. Further, phosphates are not preferred because silica crystals, which tend to cause adverse effects on heat resistance and mechanical strength, preferentially precipitate.
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
いては解明していないが、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。It is not clear why the precipitation tendency differs depending on the alkaline earth metal or depending on the type of compound even in the same alkaline earth metal system, but it may be due to factors such as the diffusion rate of the alkaline earth metal ion and the dissociation temperature of the compound. It is presumed that they are doing so.
ソーダ石灰系ガラスにおいてはその成分領域からウオラ
ストナイト、デビトライト、ＮａｚＣａＳｉ３ｏｌｌ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Ｓｒ
ＳｉＯ＋が、バリウム化合物の場合はＢａ２Ｓｉ３０Ｂ
、Ｂａ５ｉｎｓが析出し易い。In soda-lime glass, silica crystals such as wollastonite, debitrite, and NazCaSi3oll needle crystals, as well as cristobalite and tridymite, precipitate due to its component range, but in systems in which a precipitation accelerator is added, the precipitation of silica crystals is suppressed. Ru. Although it depends on the amount of precipitation accelerator added and the heat treatment conditions, when a calcium compound is added, the above-mentioned acicular crystals are added, when a magnesium compound is added, diopside is added, and when a strontium compound is added, Sr is added.
If SiO+ is a barium compound, Ba2Si30B
, Ba5ins are likely to precipitate.
本発明においては前記針状結晶をガラス中に２０〜５０
ｗｔ％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。２０ｗ ｔ％未満ではそれらの効果が小さ
い。５０ｉｙ ｔ％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２３〜４５ｗ ｔ％の範囲である。In the present invention, 20 to 50 acicular crystals are added to the glass.
Mechanical strength and heat resistance are significantly improved by including wt%. If the amount is less than 20wt%, their effects are small. If it is attempted to precipitate more than 50iyt%, silica crystals will also be generated, which is natural due to the compositional range, and this will impair 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 crystalline foam glass in which countless bubbles remain, and by passing through an annealing process, the product becomes a product with even bubbles.
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, if compression means, such as passing between a pair of rolls and squeezing between the rolls, are used during heat treatment or in a thermally softened state after heat treatment, bubbles can be appropriately released and crystals with controlled bulk specific gravity can be obtained. The result is fine foam glass, or dense crystalline glass with most of the bubbles escaping. A 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５ｉＯｚ７１％、Ａ
１ｚ０３１．６％、Ｃａ０１１％、ＭｇＯ２，１％、Ｎ
ａ２Ｏ１３％、Ｋ２Ｏ０，８％の組成を有する粒度２０
０メソシユ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) 5iOz71% by weight as plate glass cullet powder, A
1z031.6%, Ca011%, MgO2,1%, N
Particle size 20 with a composition of 13% a2O, 0.8% K2O
A sample adjusted to less than 0 mesohydr was prepared. Commercially available carbonates, nitrates, hydroxides, and sodium nitrate of magnesium, calcium, strontium, and barium were prepared as precipitation accelerators.
前記カレン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／ａｆｔ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 current powder and the needle-like crystal precipitation accelerator are dry mixed in a predetermined ratio, or wet mixed by adding 7 wt % of water, and the product obtained by dry mixing is pressed under a pressure condition of 20 kg/aft, and wet mixed. The sludge obtained by mixing was cast and dried to obtain a preformed product. This was heated to a predetermined temperature in an electric furnace at a rate of 400° C./hour, held for a predetermined time, and then gradually cooled to obtain various foamed samples. Furthermore, some of the samples were taken out of the furnace after heat treatment, sandwiched between steel plates preheated to the relevant temperature, and manually compressed by rolling a roller from above to remove air bubbles to obtain dense samples.
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 known measuring means using a specific gravity bottle.
結晶の同定；主にＸ線回折および鏡下観察により、ＥＰ
ＭＡ分析を併用した。Identification of crystals; mainly by X-ray diffraction and observation under a microscope, EP
MA analysis was also used.
固相中の結晶量（重量百分体積率）の測定；公知のＯｈ
ｌｂｅｒｇ−３ｔｒｉｃｋｌｅｒが提唱した定量法によ
れば、Ｘ線回折における２θ−２０〜２５°におけるガ
ラスのバックグラウンド強度をＩｇ、 １００χ結晶の
それをＩ ｃ−、試料のそれをＩｓ とすれば、結晶量
（ｗｔχ）＝Ｉｇ−４ｓ／Ｉｇ−１ｃ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 Oh
According to the quantitative method proposed by Robert Trickler, if the background intensity of glass at 2θ-20 to 25° in X-ray diffraction is Ig, that of a 100χ crystal is Ic-, and that of the sample is Is, then The amount (wtχ) is given by = Ig-4s/Ig-1c. A calibration curve was created and quantified according to this method. In addition, a quantitative method based on observation under a mirror was used as an auxiliary method.
熱衝撃試験（急冷試験） ； ５０ｍｍ口Ｘ２０ｍｍ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): A sample of 50 mm opening x 20 mm thickness was placed in an electric furnace and held at 500°C, then taken out and immediately placed in water at 10°C to be rapidly cooled. , items with small cracks are acceptable, items with large cracks or collapse are unacceptable.
Classified into ranks.
さらに一部の試料については曲げ強度を測定した。Furthermore, 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, phosphates, boric acid, lead compounds, sulfates, and chlorides were added to soda-lime glass powder, and press-molded products were prepared, heat-treated in the same way, and measured and compared.
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 (Example) and Table 2.
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 products of the present invention have excellent thermal shock resistance and mechanical strength. In Comparative Example 1.2 to which phosphate was added, silica precipitated as the main crystal. It is presumed that in Comparative Examples 3.4 to which boric acid and lead compounds were added, no crystals were precipitated, but rather the vitrification region was expanded. Comparative example 5
The sulfates and chlorides of 7 to 7 remain without being decomposed and do not exhibit crystal precipitation effects. All of these comparative examples are inferior in heat resistance and mechanical strength.
（発明の効果）
本発明における安価で入手容易なソーダー石灰系ガラス
屑と特定の針状結晶析出促進剤を前駆原料とした熱処理
成形結晶質ガラスは、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。(Effects of the Invention) The heat-treated and formed crystalline glass made from cheap and easily available soda-lime-based glass waste and a specific acicular crystal precipitation accelerator as precursor raw materials in the present invention has excellent thermal shock resistance, mechanical strength, heat resistance, It has excellent water resistance and is useful as a heat-resistant, high-strength building material.
Moreover, the production thereof is extremely easy, and it has the effect that crystalline foam glass and dense crystalline glass can be produced freely.
Claims (1)
原料とした熱処理成形体であって、針状結晶を２０ｖｏ
ｌ％以上、５０ｖｏｌ％以下含有した結晶質ガラスにお
いて、前記針状結晶析出促進剤が、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種以上であることを特徴とする
結晶質ガラス。 ２、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、ＳｒＳｉＯ＿３、Ｂａ＿２Ｓｉ＿３Ｏ＿６
、ＢａＳｉＯ＿３またはＮａ＿２ＣａＳｉ＿３Ｏ＿８の
１種以上よりなることを特徴とする請求項１記載の結晶
質ガラス。 ３、ソーダ石灰系ガラス粉に対し針状結晶析出促進剤を
酸化物換算で１ないし１０ｗｔ％添加した混合粉体ない
し混合スラッジを予備成形し、次いで該ソーダ石灰系ガ
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。 ４、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を特徴とする請求項３記載
の結晶質ガラスの製造法。[Scope of Claims] 1. A heat-treated molded article using soda-lime glass powder and a needle-like crystal precipitation accelerator as precursor raw materials, wherein the needle-like crystals are 20vo
In the crystalline glass containing 1% or more and 50vol% or less, the acicular crystal precipitation promoter is one selected from carbonates, nitrates, hydroxides of alkaline earth metals, or nitrates of alkali metals. A crystalline glass characterized by the above. 2. Acicular crystals are wollastonite, debitrite, diopside, SrSiO_3, Ba_2Si_3O_6
, BaSiO_3, or Na_2CaSi_3O_8. 3. Preform a mixed powder or mixed sludge in which 1 to 10 wt% of an acicular crystal precipitation accelerator is added in terms of oxide to soda lime glass powder, and then form a mixture between the softening point and pour point of the soda lime glass. A method for producing crystalline glass, characterized in that heating is maintained at an appropriate temperature for 10 to 60 minutes to precipitate needle-like crystals. 4. The method for producing crystalline glass according to claim 3, wherein the crystalline glass is compacted while maintaining heating or after maintaining heating.
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 true JPH02145456A (en) | 1990-06-04 |
| JPH0676230B2 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) |
Cited By (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 |
| JP2002308646A (en) * | 2001-04-10 | 2002-10-23 | Masatoshi Sato | Wollastonite-based glass ceramic fired at low temperature and method of producing the same |
| JP2010083721A (en) * | 2008-09-30 | 2010-04-15 | Reiseki:Kk | Method for storing granulate or powdery object to be stored |
| EP2752394A1 (en) * | 2013-01-08 | 2014-07-09 | King Abdulaziz City for Science & Technology (KACST) | Method for manufacturing glass-ceramic composite |
Citations (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
Patent Citations (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 |
Cited By (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 |
| JP2002308646A (en) * | 2001-04-10 | 2002-10-23 | Masatoshi Sato | Wollastonite-based glass ceramic fired at low temperature and method of producing the same |
| JP2010083721A (en) * | 2008-09-30 | 2010-04-15 | Reiseki:Kk | Method for storing granulate or powdery object to be stored |
| EP2752394A1 (en) * | 2013-01-08 | 2014-07-09 | King Abdulaziz City for Science & Technology (KACST) | Method for manufacturing glass-ceramic composite |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0676230B2 (en) | 1994-09-28 |
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