JPH0433746B2 - - Google Patents
Info
- Publication number
- JPH0433746B2 JPH0433746B2 JP27997287A JP27997287A JPH0433746B2 JP H0433746 B2 JPH0433746 B2 JP H0433746B2 JP 27997287 A JP27997287 A JP 27997287A JP 27997287 A JP27997287 A JP 27997287A JP H0433746 B2 JPH0433746 B2 JP H0433746B2
- Authority
- JP
- Japan
- Prior art keywords
- glass
- coating
- thermal expansion
- temperature
- mol
- 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.)
- Expired
Links
- 239000011521 glass Substances 0.000 claims description 31
- 238000000576 coating method Methods 0.000 claims description 14
- 239000011248 coating agent Substances 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 229910052593 corundum Inorganic materials 0.000 claims description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 5
- 239000003513 alkali Substances 0.000 description 5
- 230000009477 glass transition Effects 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000005354 aluminosilicate glass Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000002585 base Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007572 expansion measurement Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000003303 reheating Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000004017 vitrification Methods 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
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Glass Compositions (AREA)
Description
【発明の詳細な説明】
産業上の利用分野
本発明は金属製機器類を耐食性にする金属表面
へのコーテイング用ガラスに関するものである。DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a glass for coating metal surfaces to make metal equipment corrosion resistant.
従来技術
従来、化学工業、医薬品工業、食品工業等にお
いて使用する金属製機器類の耐食性が要求される
場合、それに用いる金属製機器の表面に耐食性ガ
ラスをコーテイングすることは一般に行われてい
る。Prior Art Conventionally, when corrosion resistance is required for metal equipment used in the chemical industry, pharmaceutical industry, food industry, etc., it has been common practice to coat the surface of the metal equipment used with corrosion-resistant glass.
そのコーテイングはガラス粉末をスプレー等に
よつて金属表面へ塗付し、そのガラス粉末を高温
軟化流動化させた後、冷却する方法が一般に行わ
れている。 The coating is generally performed by applying glass powder to the metal surface by spraying or the like, softening and fluidizing the glass powder at a high temperature, and then cooling it.
一般にコーテイングガラスが長期間の苛酷な腐
食条件に耐えるようにするにはガラス層の厚さは
約１mm程度にすることが必要であり、そのために
は複数回のコーテイングを行うことが必要であ
る。この場合、金属表面に既にコーテイングされ
たガラス層は、再加熱時に引張り応力を受ける。
この引張り応力の値がガラス自体の抗張力を超え
る温度ではクラツクが生ずる。 Generally, in order for coated glass to withstand severe corrosive conditions for a long period of time, the thickness of the glass layer must be approximately 1 mm, and for this purpose it is necessary to perform coating multiple times. In this case, the glass layer already coated on the metal surface is subjected to tensile stress during reheating.
Cracks occur at temperatures where the value of this tensile stress exceeds the tensile strength of the glass itself.
このクラツクを防ぐためには、室温からガラス
転移温度までの熱膨張係数α1とガラス転移温度か
らガラス屈伏温度までの熱膨張係数α2の差、すな
わち、α2−α1（以下Δαと記載する）が小さく、し
かもα1が金属素地の熱膨張係数の値に近いことが
必要となる。 In order to prevent this crack, the difference between the thermal expansion coefficient α 1 from room temperature to the glass transition temperature and the thermal expansion coefficient α 2 from the glass transition temperature to the glass yielding temperature, that is, α 2 − α 1 (hereinafter referred to as Δα), must be calculated. ) is small, and α 1 needs to be close to the value of the thermal expansion coefficient of the metal base.
従来のコーテイング用ガラスはΔαがΔα＞130
×10-7（℃-1）程度であり、クラツクが生じ易い
欠点があつた。 For conventional coating glass, Δα is Δα>130
×10 -7 (°C -1 ), which had the disadvantage of being prone to cracks.
発明の目的
本発明は前記欠点を改善せんとするものであ
り、その目的はΔαの値より小さくし、複数コー
テイングに際してもクラツクが生じ難い金属表面
へのコーテイング用ガラスを提供しようとするに
ある。OBJECTS OF THE INVENTION The present invention aims to improve the above-mentioned drawbacks, and its purpose is to provide a glass for coating metal surfaces that has a value smaller than Δα and is less likely to cause cracks even when multiple coatings are applied.
発明の要旨
本発明者らはさきに高弾性率、高硬度で耐食性
も高いY2O3含有アルミノ珪酸塩ガラス（Y2O3−
Al2O3−SiO2）を開発した。（A.Makishima，Y.
Tamura，T.Sakaino，J.American Ceramic
Society.61，P247（1978）
このガラスにNa2Ｏを添加するとΔαがΔα＞
100×10-7（℃-1）以下と小さくなり、また、ZrO2
を添加すると耐アルカリ性及び耐酸性が向上した
コーテイング用ガラスが得られることを知見し得
た。この知見に基づいて本発明を完成した。Summary of the Invention The present inventors first developed Y 2 O 3 -containing aluminosilicate glass (Y 2 O 3 −
Developed Al 2 O 3 −SiO 2 ). (A.Makishima, Y.
Tamura, T. Sakaino, J. American Ceramic
Society.61, P247 (1978) When Na 2 O is added to this glass, Δα becomes Δα＞
It is smaller than 100×10 -7 (℃ -1 ), and ZrO 2
It has been found that a coating glass with improved alkali resistance and acid resistance can be obtained by adding . The present invention was completed based on this knowledge.
本発明の要旨は、
モル％で、SiO259〜71％、Na2O16〜28％、Y2
O34.33〜6.5％、Al2O36.5〜8.66％、ZrO2１〜3.5
％の組成からなる金属表面へのコーテイング用ガ
ラスにある。 The gist of the invention is: In mol%, SiO 2 59-71%, Na 2 O 16-28%, Y 2
O 3 4.33-6.5%, Al 2 O 3 6.5-8.66%, ZrO 2 1-3.5
% composition of glass for coating metal surfaces.
このガラスにおいて、SiO2が59モル％（以下
％はモル％を示す）より少ないとΔαが100×10-7
（℃-1）以上と大きくなり、71％を超えるとガラ
ス化し難くなり良質のガラスが得られない。 In this glass, if SiO 2 is less than 59 mol% (hereinafter % indicates mol%), Δα is 100×10 -7
(℃ -1 ) or more, and if it exceeds 71%, it becomes difficult to vitrify and high quality glass cannot be obtained.
Na2Ｏが16％より少ないとガラス化の温度が高
くなり良質のガラスが得られなく、28％を超える
とΔαの値が大きくなつてしまう。 If the Na 2 O content is less than 16%, the vitrification temperature will be high and high quality glass cannot be obtained, and if it exceeds 28%, the value of Δα will become large.
Y2O3が4.33％より少ないとΔαが大きくなり、
6.5％を超えてもΔαが大きくなる。 When Y 2 O 3 is less than 4.33%, Δα increases,
Even if it exceeds 6.5%, Δα becomes large.
Al2O3が6.5％より少なく、また8.66％を超えて
もΔαが大きくなる。 Even if Al 2 O 3 is less than 6.5% and exceeds 8.66%, Δα becomes large.
ZrO2が１％より少ない場合はΔαは小さいが耐
アルカリ性が十分でない。3.5％を超えると、コ
ーテイングするために必要な温度が高くなる。 When ZrO 2 is less than 1%, Δα is small, but alkali resistance is not sufficient. If it exceeds 3.5%, the temperature required for coating increases.
本発明のコーテイング用ガラスを製造するに
は、原料としてNa2Ｏ成分にはNa2CO3を使用し、
それ以外の成分は酸化物を原料とし、これら原料
粉末を所定比に充分混合し、アルミナルツボに入
れ、1550℃以下で溶融することによつて得られ
る。 In order to manufacture the coating glass of the present invention, Na 2 CO 3 is used as the Na 2 O component as a raw material,
The other components are obtained by using oxides as raw materials and thoroughly mixing these raw material powders in a predetermined ratio, placing them in an alumina crucible, and melting them at 1550° C. or lower.
実施例 １
モル％で、SiO262.76％、Na2O21.38％、Y2O3
5.36％、Al2O37.50％、ZrO23.0％のガラスを、
Na2Ｏの原料としてはNa2CO3を使用し、他の成
分は酸化物を原料として使用し、原料粉末混合物
をアルミナルツボに入れ、電気炉中で1550℃で３
時間溶融した。このガラスを3φ（mm）の丸棒に成
形し、徐冷して熱膨張測定用試料とした。熱膨張
特性は作動トランス型装置を用い、５（℃／分）
の昇温速度で測定した。Example 1 In mol%, SiO2 62.76 %, Na2O21.38 %, Y2O3
5.36%, Al2O3 7.50% , ZrO2 3.0% glass,
Na 2 CO 3 is used as the raw material for Na 2 O, and oxides are used as the raw materials for the other components.
melted for an hour. This glass was formed into a round bar of 3φ (mm) and slowly cooled to prepare a sample for thermal expansion measurement. Thermal expansion characteristics were measured at 5 (°C/min) using a working transformer type device.
Measured at a heating rate of .
このガラスの密度は、2.78g／cm3、室温からガ
ラス転移温度までの熱膨張係数α1は87×10-7（℃-
１）で、この値とガラス転移温度から屈伏温度ま
での熱膨張係数α2との差であるΔαの値は52×
10-7（℃-1）であつた。 The density of this glass is 2.78g/cm 3 , and the coefficient of thermal expansion α 1 from room temperature to glass transition temperature is 87×10 -7 (℃ -
1 ), the value of Δα, which is the difference between this value and the coefficient of thermal expansion α 2 from the glass transition temperature to the yield temperature, is 52 ×
The temperature was 10 -7 (℃ -1 ).
実施例 ２
モル％で、SiO269％、Na2O15％、Al2O37.8
％、、Y2O35.2％、ZrO2３％の組成のガラスを実
施例１と同じ方法で作つた。このガラスの密度は
2.74g／cm3、室温からガラス転移温度までの熱膨
張係数α1は74×10-7（℃-1）Δαは90×10-7（℃-1）
であつた。20重量％HCI水溶液（80℃）と1N−
NaOH水溶液（80℃）を使用し、試料の重量変
化を測定することにより耐酸性と耐アルカリ性を
評価した。Example 2 In mol%, SiO 2 69%, Na 2 O 15%, Al 2 O 3 7.8
A glass having a composition of 5.2% Y 2 O 3 and 3% ZrO 2 was prepared in the same manner as in Example 1. The density of this glass is
2.74g/cm 3 , The coefficient of thermal expansion from room temperature to glass transition temperature α 1 is 74×10 -7 (℃ -1 ) Δα is 90×10 -7 (℃ -1 )
It was hot. 20 wt% HCI aqueous solution (80℃) and 1N−
Acid resistance and alkali resistance were evaluated by measuring the weight change of the sample using NaOH aqueous solution (80°C).
その結果、耐酸性は0.35g／m2・dayで、耐アル
カリ性は2.4g／m2・dayであつた。 As a result, the acid resistance was 0.35 g/m 2 ·day, and the alkali resistance was 2.4 g/m 2 ·day.
実施例 ３
モル％で、SiO269％、Na2O16.64％、Al2O3
8.47％、Y2O34.39％、ZrO21.5％の組成のガラス
を実施例１と同じ方法でガラスを作つた。このガ
ラスの密度は2.66g／cm3、α1は78×10-7（℃-1）、
Δαは99×10-7（℃-1）であつた。Example 3 In mol%, SiO 2 69%, Na 2 O 16.64%, Al 2 O 3
A glass having a composition of 8.47%, Y 2 O 3 4.39%, and ZrO 2 1.5% was prepared in the same manner as in Example 1. The density of this glass is 2.66g/cm 3 , α 1 is 78×10 -7 (℃ -1 ),
Δα was 99×10 −7 (°C −1 ).
このガラス粉末をステンレス板にスプレーで付
着させ、890℃で溶融することを３回繰り返して
ガラスコーテイングを行つたがクラツクは生じな
かつた。 Glass coating was performed by spraying this glass powder onto a stainless steel plate and melting it at 890°C three times, but no cracks occurred.
発明の効果
本発明のガラスはY2O3含有アルミノ珪酸塩ガ
ラスにNa2Ｏを添加することによりΔαの値が100
×10-7（℃-1）以下と小さくなり、ガラスコーテ
イングを繰り返してもクラツクの発生がなくな
り、またZrO2の添加により耐酸、耐アルカリの
腐触性を高め得、コーテイング用ガラスとして優
れたものとなし得たものである。Effects of the Invention The glass of the present invention has a Δα value of 100 by adding Na 2 O to Y 2 O 3- containing aluminosilicate glass.
×10 -7 (℃ -1 ) or less, no cracks occur even after repeated glass coatings, and the addition of ZrO 2 improves acid and alkali corrosion resistance, making it an excellent coating glass. It is something that could be realized.
Claims (1)
Y2O34.33〜6.5％、Al2O36.5〜8.66％、ZrO2１〜
3.5％の組成からなる金属表面へのコーテイング
用ガラス。1 mol%, SiO 2 59-71%, Na 2 O 16-28%,
Y2O3 4.33 ~6.5%, Al2O3 6.5 ~8.66%, ZrO2 1 ~
Glass for coating metal surfaces with a composition of 3.5%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27997287A JPH01122936A (en) | 1987-11-05 | 1987-11-05 | Glass for coating metallic surface |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27997287A JPH01122936A (en) | 1987-11-05 | 1987-11-05 | Glass for coating metallic surface |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01122936A JPH01122936A (en) | 1989-05-16 |
| JPH0433746B2 true JPH0433746B2 (en) | 1992-06-03 |
Family
ID=17618506
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27997287A Granted JPH01122936A (en) | 1987-11-05 | 1987-11-05 | Glass for coating metallic surface |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01122936A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20100089835A (en) * | 2007-10-02 | 2010-08-12 | 솔베이(소시에떼아노님) | Use of compositions containing silicon for improving the corrosion resistance of vessels |
| JP5583606B2 (en) | 2008-02-26 | 2014-09-03 | コーニング インコーポレイテッド | Refining agent for silicate glass |
| CN104768889B (en) * | 2012-05-31 | 2020-05-15 | 康宁股份有限公司 | Ion-exchangeable transition metal-containing glasses |
| CN112876080B (en) * | 2021-02-04 | 2022-02-15 | 中国科学院合肥物质科学研究院 | Glass ceramic coating for lead-based reactor pump impeller and preparation method thereof |
-
1987
- 1987-11-05 JP JP27997287A patent/JPH01122936A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01122936A (en) | 1989-05-16 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |