JPH05170479A - Glass composition - Google Patents
Glass compositionInfo
- Publication number
- JPH05170479A JPH05170479A JP35706891A JP35706891A JPH05170479A JP H05170479 A JPH05170479 A JP H05170479A JP 35706891 A JP35706891 A JP 35706891A JP 35706891 A JP35706891 A JP 35706891A JP H05170479 A JPH05170479 A JP H05170479A
- Authority
- JP
- Japan
- Prior art keywords
- glass
- glass composition
- present
- thermal expansion
- strength
- 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.)
- Pending
Links
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
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
- C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/12—Silica-free oxide glass compositions
- C03C3/14—Silica-free oxide glass compositions containing boron
- C03C3/145—Silica-free oxide glass compositions containing boron containing aluminium or beryllium
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、焼成すると３０〜３８
０℃における熱膨張係数が１５〜６０×１０-7／℃とな
るため、例えば、粉末状にした後、焼成することによっ
て各種の低膨張材料を接着することが可能なガラス組成
物に関するものである。BACKGROUND OF THE INVENTION The present invention is capable of burning 30-38 when fired.
Since the thermal expansion coefficient at 0 ° C. is 15 to 60 × 10 −7 / ° C., the present invention relates to a glass composition capable of adhering various low expansion materials by, for example, powdering and then firing. is there.
【０００２】[0002]
【従来の技術】従来より高温下で使用されるタービン
材、ガイド材、ロール材、熱電対保護管等の構造材料と
して、高強度で、耐熱性に優れた低膨張セラミックが使
用されており、例えば３０〜３８０℃において３０×１
０-7／℃の熱膨張係数を有するシリコンナイトライド、
４５×１０-7／℃の熱膨張係数を有するムライト、１６
×１０-7／℃の熱膨張係数を有するコージェライト等の
低膨張セラミックからなるものが実用化されている。2. Description of the Related Art Conventionally, low expansion ceramics having high strength and excellent heat resistance are used as structural materials such as turbine materials, guide materials, roll materials and thermocouple protection tubes which are used at high temperatures. For example, 30 × 1 at 30 to 380 ° C.
Silicon nitride having a coefficient of thermal expansion of 0 -7 / ° C,
Mullite having a coefficient of thermal expansion of 45 × 10 −7 / ° C., 16
Those made of low expansion ceramics such as cordierite having a thermal expansion coefficient of × 10 -7 / ° C have been put into practical use.
【０００３】ところでこのような低膨張セラミックから
上記したような各種の構造材料を作製するに際し、例え
ば複雑な形状の構造材料を作製するには、材料同士を接
合させる必要性が生じやすく、この場合、材料同士をネ
ジ止めによって接合したり、耐熱性に優れた無機接着剤
によって接着する方法が採られる。By the way, when various structural materials as described above are produced from such a low expansion ceramic, for example, in order to produce a structural material having a complicated shape, it is necessary to join the materials together. In this case, A method of joining materials by screwing or bonding with an inorganic adhesive having excellent heat resistance is used.
【０００４】[0004]
【発明が解決しようとする課題】しかしながらネジ止め
による接合の場合、セラミック自体が加工性に劣り、且
つ、熱収縮しやすい材料であるため、ネジ孔を正確に形
成したり、寸法精度の良いネジ孔を得ることが非常に困
難である。However, in the case of joining by screwing, since the ceramic itself is a material that is inferior in workability and easily heat-shrinks, a screw hole can be accurately formed or a screw having good dimensional accuracy. It is very difficult to get the holes.
【０００５】また無機接着剤としては、低膨張セラミッ
クとの間で熱歪が発生しないように、低膨張のセラミッ
ク粉末が使用されるが、これをビークルと混合してペー
スト状にした後、焼成すると、泡を多量に含む焼成体と
なるため、機械的強度や接着強度が低く、高い接着強度
が要求される用途には到底使用できない。As the inorganic adhesive, low expansion ceramic powder is used so as not to generate thermal strain with the low expansion ceramic. This powder is mixed with a vehicle to form a paste, which is then fired. Then, since it becomes a fired body containing a large amount of bubbles, it has low mechanical strength and adhesive strength, and cannot be used at all for applications requiring high adhesive strength.
【０００６】本発明の目的は、耐熱性に優れ、機械的強
度や接着強度が高く、しかも焼成すると３０〜３８０℃
における熱膨張係数が１５〜６０×１０-7／℃となるた
め、低膨張の材料同士を強固に接着することが可能なガ
ラス組成物に関するものである。The object of the present invention is excellent in heat resistance, high in mechanical strength and adhesive strength, and 30 to 380 ° C. when fired.
The present invention relates to a glass composition capable of firmly adhering low-expansion materials to each other, since the coefficient of thermal expansion in (5) is 15 to 60 × 10 −7 / ° C.
【０００７】[0007]
【課題を解決するための手段】本発明者は、上記目的を
達成すべく、種々の研究を重ねた結果、ＣａＯ−Ａｌ2
Ｏ3 −Ｂ2 Ｏ3 系ガラスが、非常に耐熱性に優れ、機械
的強度や接着強度が高く、しかもアルカリ金属酸化物を
含有しない場合、焼成した後に低膨張となることを見い
だし、本発明として提案するものである。The inventors of the present invention have conducted various studies to achieve the above object, and as a result, CaO--Al 2
It was found that the O 3 -B 2 O 3 based glass has very high heat resistance, high mechanical strength and adhesive strength, and when it does not contain an alkali metal oxide, it has a low expansion after firing, and the present invention Is proposed as.
【０００８】すなわち本発明のガラス組成物は、重量百
分率で、ＣａＯ １０〜６０％、Ａｌ2 Ｏ3 ２０〜３
４％、Ｂ2 Ｏ3 １５〜４０％、ＳｉＯ2 ０〜１０
％、ＺｒＯ2 ０〜１０％の組成を有し、本質的にアル
カリ金属酸化物を含有しないことを特徴とする。That is, the glass composition of the present invention has a weight percentage of 10 to 60% CaO and 20 to 3 Al 2 O 3 .
4%, B 2 O 3 15-40%, SiO 2 0-10
%, ZrO 2 0 to 10% and essentially free of alkali metal oxides.
【０００９】本発明のガラス組成物を接着剤として使用
する場合、まずガラス融液を急冷することによって、カ
レットを作製し、このカレットをボールミルで粉砕した
後、分級し、平均粒径が１〜５μｍの粉末を形成する。
次いでこの粉末をビークルと混合することによってペー
スト状にし、被接着材料の所定箇所に塗布した後、加熱
して焼結させる。When the glass composition of the present invention is used as an adhesive, a cullet is first produced by rapidly cooling the glass melt, and the cullet is crushed by a ball mill and then classified to have an average particle size of 1 to 1. A 5 μm powder is formed.
Next, this powder is mixed with a vehicle to form a paste, which is applied to predetermined portions of the material to be adhered and then heated and sintered.
【００１０】[0010]
【作用】本発明のガラス組成物は、結晶性ガラスであ
り、８００℃以上の温度で焼成することによって、Ｃａ
Ａｌ2 Ｂ2 Ｏ7 結晶が析出し、これによって低膨張で、
高強度の焼結体となる。The glass composition of the present invention is a crystalline glass, and when it is fired at a temperature of 800 ° C. or higher, Ca
Al 2 B 2 O 7 crystals are deposited, which results in low expansion and
It becomes a high-strength sintered body.
【００１１】本発明のガラス組成物の各構成成分を上記
のように限定した理由は、以下のとおりである。The reason why each component of the glass composition of the present invention is limited as described above is as follows.
【００１２】ＣａＯは、析出結晶であるＣａＡｌ2 Ｂ2
Ｏ7 結晶の構成成分であると共に、ガラスの溶融性を良
くするフラックス剤として作用する成分であり、その含
有量は、１０〜６０％である。１０％より少ないと、結
晶の析出量が少なくなると共に、フラックス剤としての
効果が不十分となる。一方、６０％より多いと、焼結体
の耐水性が悪くなり、接着強度が低下しやすくなるため
好ましくない。CaO is CaAl 2 B 2 which is a precipitated crystal.
It is a constituent component of the O 7 crystal and a component that acts as a flux agent that improves the meltability of glass, and its content is 10 to 60%. If it is less than 10%, the amount of crystals precipitated will be small and the effect as a fluxing agent will be insufficient. On the other hand, when it is more than 60%, the water resistance of the sintered body is deteriorated and the adhesive strength is apt to be lowered, which is not preferable.
【００１３】Ａｌ2 Ｏ3 も、ＣａＡｌ2 Ｂ2 Ｏ7 結晶の
構成成分であり、その含有量は、２０〜３４％である。
２０％より少ないと、結晶の析出量が少なくなり、一
方、３４％より多いと、ガラスの流動性が悪くなり、所
望の接着強度が得られ難い。Al 2 O 3 is also a constituent component of CaAl 2 B 2 O 7 crystals, and its content is 20 to 34%.
If it is less than 20%, the amount of crystals precipitated will be small, while if it is more than 34%, the fluidity of the glass will be poor and it will be difficult to obtain the desired adhesive strength.
【００１４】Ｂ2 Ｏ3 も、ＣａＡｌ2 Ｂ2 Ｏ7 結晶の構
成成分であると共に、ガラスの骨格を形成する成分であ
り、その含有量は、１５〜４０％である。１５％より少
ないと、結晶の析出量が少なくなると共に、ガラスの製
造が困難となる。一方、４０％より多いと、焼成体の耐
水性が悪くなる。B 2 O 3 is also a constituent of the CaAl 2 B 2 O 7 crystal and a constituent of the glass skeleton, and its content is 15-40%. If it is less than 15%, the amount of crystals deposited will be small, and it will be difficult to manufacture glass. On the other hand, when it is more than 40%, the water resistance of the fired product is deteriorated.
【００１５】ＳｉＯ2 は、ガラスの流動性を調整する成
分であるが、１０％より多いと、ガラスの軟化温度が高
くなり、接着時の作業温度が高くなるため好ましくな
い。SiO 2 is a component for adjusting the fluidity of glass, but if it is more than 10%, the softening temperature of glass becomes high and the working temperature at the time of bonding becomes high, which is not preferable.
【００１６】ＺｒＯ2 は、ガラスの流動性を調整すると
共に、耐水性を向上させる成分であるが、各々１０％よ
り多いと、ガラスの軟化温度が高くなりすぎるため好ま
しくない。ZrO 2 is a component that adjusts the fluidity of the glass and improves the water resistance, but if it exceeds 10%, the softening temperature of the glass becomes too high, which is not preferable.
【００１７】また本発明においては、上記成分以外にも
特性を損なわない限り、ＴｉＯ2 、Ｂｉ2 Ｏ3 、Ｚｎ
Ｏ、ＳｒＯ、ＢａＯ等の成分を１０％まで添加すること
が可能である。In the present invention, TiO 2 , Bi 2 O 3 and Zn are used as long as the characteristics other than the above components are not impaired.
It is possible to add components such as O, SrO and BaO up to 10%.
【００１８】しかしながらＮａ2 Ｏ、Ｋ2 Ｏ、Ｌｉ2 Ｏ
といったアルカリ金属酸化物を添加すると、焼成後の熱
膨張係数が高くなりすぎるため、含有しないほうが良
い。However, Na 2 O, K 2 O, Li 2 O
If such an alkali metal oxide is added, the coefficient of thermal expansion after firing becomes too high, so it is better not to include it.
【００１９】[0019]
【実施例】以下、本発明のガラス組成物を実施例に基づ
いて詳細に説明する。EXAMPLES Hereinafter, the glass composition of the present invention will be described in detail based on examples.
【００２０】表１は、本発明の実施例（試料Ｎｏ．１〜
６）及び比較例（試料Ｎｏ．７、８）を示すものであ
る。Table 1 shows examples of the present invention (Sample Nos. 1 to 1).
6) and Comparative Examples (Sample Nos. 7 and 8).
【００２１】[0021]
【表１】 [Table 1]
【００２２】表１の各試料は、以下のように調製した。Each sample in Table 1 was prepared as follows.
【００２３】まず表中のガラス組成になるように、炭酸
カルシウム、ホウ酸、酸化アルミニウム、二酸化ケイ
素、酸化ジルコニウム、炭酸ナトリウムの各原料を調合
し、これを白金ルツボに入れ、１４５０℃で２時間保持
して溶融した。次いでこの溶融ガラスを急冷して薄板状
に成形した後、アルミナボールミルで粉砕し、分級する
ことによって平均粒径が約３μｍの粉末を得、焼成した
場合の析出結晶や各種の特性を調べた。First, each raw material of calcium carbonate, boric acid, aluminum oxide, silicon dioxide, zirconium oxide, and sodium carbonate was prepared so as to have the glass composition shown in the table, which was placed in a platinum crucible and kept at 1450 ° C. for 2 hours. Hold and melt. Next, this molten glass was rapidly cooled to form a thin plate, then pulverized with an alumina ball mill and classified to obtain a powder having an average particle size of about 3 μm, and the precipitated crystals and various characteristics when fired were examined.
【００２４】表１から明らかなように、本発明の実施例
であるＮｏ．１〜６の各試料は、ＣａＡｌ2 Ｂ2 Ｏ7 結
晶を析出し、曲げ強度や接着強度が高く、耐熱性が良
く、熱膨張係数が２０〜５８×１０-7／℃であった。As is apparent from Table 1, No. 1 which is an embodiment of the present invention. In each of the samples 1 to 6, CaAl 2 B 2 O 7 crystals were precipitated, the bending strength and the adhesive strength were high, the heat resistance was good, and the thermal expansion coefficient was 20 to 58 × 10 −7 / ° C.
【００２５】一方、比較例であるＮｏ．７の試料は、Ａ
ｌ2 Ｏ3 を多量に含有し、流動性が悪いため、接着強度
が低かった。さらにＮｏ．８の試料は、Ｎａ2 Ｏを含有
するため、熱膨張係数が７０×１０-7／℃と高かった。On the other hand, No. Sample 7 is A
Since a large amount of l 2 O 3 was contained and the fluidity was poor, the adhesive strength was low. Furthermore, No. The sample of No. 8 contained Na 2 O and therefore had a high coefficient of thermal expansion of 70 × 10 −7 / ° C.
【００２６】表中の析出結晶は、上記粉末を８００〜９
００℃で１０〜６０分間焼成し、さらに粉砕した後、こ
の粉砕物を使用して粉末Ｘ線回折法で観察することによ
って調べた。The precipitated crystals in the table are the above powders 800 to 9
After calcination at 00 ° C. for 10 to 60 minutes and further crushing, the powder was examined by powder X-ray diffractometry using this powder.
【００２７】曲げ強度は、上記粉末を所定形状にプレス
成形し、８００〜９００℃で１０〜６０分間焼成してか
ら、５×５×５０ｍｍの大きさになるように研磨した
後、周知の３点荷重試験によって測定したものである。The bending strength is determined by press-molding the above powder into a predetermined shape, firing at 800 to 900 ° C. for 10 to 60 minutes, and then polishing to a size of 5 × 5 × 50 mm, and then the well-known 3 It is measured by a point load test.
【００２８】接着強度は、上記ガラス粉末を有機ビーク
ル（１％のニトロセルロースを含有する酢酸イソアミ
ル）と混合することによってペースト状にし、これを２
０×２０ｍｍの大きさのセラミック板の片面に塗布した
後、さらにその塗布面に同寸のセラミック板を重ね合わ
せた後、８００〜９００℃で１０〜６０分間焼成した。
次いで各セラミック板に対してずりの力を与え、各セラ
ミック板が剥離した時に与えた力を測定した。The adhesive strength was made into a paste by mixing the above glass powder with an organic vehicle (isoamyl acetate containing 1% nitrocellulose),
After coating on one surface of a ceramic plate having a size of 0 × 20 mm, a ceramic plate of the same size was further laminated on the coated surface, and then baked at 800 to 900 ° C. for 10 to 60 minutes.
Then, a shearing force was applied to each ceramic plate, and the force applied when each ceramic plate was peeled off was measured.
【００２９】また耐熱性は、曲げ強度試験に供したサン
プルの片端を、固定することが可能な治具に装着した状
態で電気炉中に静置し、１０００℃まで加熱した後の変
形の有無を目視で観察して変形がほとんど発生しなかっ
たものを良とした。The heat resistance is determined by the presence or absence of deformation after one end of the sample subjected to the bending strength test is placed in an electric furnace with it attached to a fixture that can be fixed and heated to 1000 ° C. When the sample was visually observed, it was regarded as good when there was almost no deformation.
【００３０】さらに熱膨張係数は、押し棒式熱膨張計
で、３０〜３８０℃の温度範囲における平均線膨張係数
を測定したものである。Further, the coefficient of thermal expansion is a value obtained by measuring an average coefficient of linear expansion in a temperature range of 30 to 380 ° C. with a push rod type thermal expansion meter.
【００３１】以上、本発明のガラス組成物を用いて、低
膨張セラミックを接着する場合についてのみ述べたが、
本発明は、これに限定されるものではなく、低膨張のボ
ロシリケートガラス等の他の材料を接着することも可能
であり、さらに接着剤以外にも各種の用途に使用するこ
とも可能である。The case where the low expansion ceramic is adhered using the glass composition of the present invention has been described above.
The present invention is not limited to this, and other materials such as low-expansion borosilicate glass can be adhered, and can be used for various applications other than the adhesive. ..
【００３２】[0032]
【発明の効果】以上のように本発明のガラス組成物は、
耐熱性に優れ、機械的強度や接着強度が高く、しかも焼
成すると低膨張となるため、例えば、このような特性が
要求される接着剤として好適である。As described above, the glass composition of the present invention is
It is excellent in heat resistance, has high mechanical strength and adhesive strength, and has low expansion when fired. Therefore, it is suitable as an adhesive that requires such characteristics, for example.
Claims (1)
Ａｌ2 Ｏ3 ２０〜３４％、Ｂ2 Ｏ3 １５〜４０％、
ＳｉＯ2 ０〜１０％、ＺｒＯ2 ０〜１０％の組成を
有し、本質的にアルカリ金属酸化物を含有しないことを
特徴とするガラス組成物。1. CaO 10 to 60% in weight percentage,
Al 2 O 3 20~34%, B 2 O 3 15~40%,
A glass composition having a composition of 0 to 10% SiO 2 and 0 to 10% ZrO 2 , and essentially not containing an alkali metal oxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP35706891A JPH05170479A (en) | 1991-12-24 | 1991-12-24 | Glass composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP35706891A JPH05170479A (en) | 1991-12-24 | 1991-12-24 | Glass composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH05170479A true JPH05170479A (en) | 1993-07-09 |
Family
ID=18452222
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP35706891A Pending JPH05170479A (en) | 1991-12-24 | 1991-12-24 | Glass composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH05170479A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1338584A1 (en) * | 2000-10-27 | 2003-08-27 | Yamatake Corporation | Jointing material and joining method |
| JP2009190967A (en) * | 2001-08-02 | 2009-08-27 | Three M Innovative Properties Co | METHOD FOR MAKING GLASS ARTICLE CONTAINING CaO-Al2O3-ZrO2 OR SrO-Al2O3-ZrO2 AND GLASS ARTICLE PRODUCED BY THE METHOD |
| JP2013512836A (en) * | 2009-12-02 | 2013-04-18 | アレヴァ・エヌセー | Method of assembling a two-part fluid tight assembly of silicon nitride |
| CN114380503A (en) * | 2022-02-24 | 2022-04-22 | 惠州亿纬锂能股份有限公司 | Lithium corrosion resistant sealing glass, sealing cover group and lithium battery |
-
1991
- 1991-12-24 JP JP35706891A patent/JPH05170479A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1338584A1 (en) * | 2000-10-27 | 2003-08-27 | Yamatake Corporation | Jointing material and joining method |
| EP1338584A4 (en) * | 2000-10-27 | 2006-12-06 | Yamatake Corp | Jointing material and joining method |
| US7198666B2 (en) | 2000-10-27 | 2007-04-03 | Yamatake Corporation | Jointing material comprising a mixture of boron oxide and aluminum oxide and method of jointing utilizing said jointing material |
| JP2009190967A (en) * | 2001-08-02 | 2009-08-27 | Three M Innovative Properties Co | METHOD FOR MAKING GLASS ARTICLE CONTAINING CaO-Al2O3-ZrO2 OR SrO-Al2O3-ZrO2 AND GLASS ARTICLE PRODUCED BY THE METHOD |
| JP2013512836A (en) * | 2009-12-02 | 2013-04-18 | アレヴァ・エヌセー | Method of assembling a two-part fluid tight assembly of silicon nitride |
| CN114380503A (en) * | 2022-02-24 | 2022-04-22 | 惠州亿纬锂能股份有限公司 | Lithium corrosion resistant sealing glass, sealing cover group and lithium battery |
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