JPH01122936A - Glass for coating metallic surface - Google Patents
Glass for coating metallic surfaceInfo
- Publication number
- JPH01122936A JPH01122936A JP27997287A JP27997287A JPH01122936A JP H01122936 A JPH01122936 A JP H01122936A JP 27997287 A JP27997287 A JP 27997287A JP 27997287 A JP27997287 A JP 27997287A JP H01122936 A JPH01122936 A JP H01122936A
- Authority
- JP
- Japan
- Prior art keywords
- glass
- thermal expansion
- coefficient
- na2o
- zro2
- 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 33
- 238000000576 coating method Methods 0.000 title claims abstract description 17
- 239000011248 coating agent Substances 0.000 title claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 9
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 abstract description 8
- 230000007797 corrosion Effects 0.000 abstract description 7
- 238000005260 corrosion Methods 0.000 abstract description 7
- 230000009477 glass transition Effects 0.000 abstract description 7
- 239000003513 alkali Substances 0.000 abstract description 6
- 239000002253 acid Substances 0.000 abstract description 5
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 abstract description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 3
- 239000005354 aluminosilicate glass Substances 0.000 abstract description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 2
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 239000000843 powder Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 101100348017 Drosophila melanogaster Nazo gene Proteins 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
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 2
- 239000002585 base Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005336 cracking Methods 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
- 238000005259 measurement Methods 0.000 description 1
- 238000003303 reheating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 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)
Abstract
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
ティ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 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ィングす
ることは一般に行われている。BACKGROUND ART Conventionally, when metal equipment used in the chemical industry, pharmaceutical industry, food industry, etc. is required to have corrosion resistance, it has been common practice to coat the surface of the metal equipment used with corrosion-resistant glass.
そのコーティングはガラス粉末をスプレー等によって金
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.
一般にコーティ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１ｒｍ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ィ
ングを行うことが必要である。Generally, in order for a coated glass to withstand severe corrosive conditions for a long period of time, the thickness of the glass layer must be approximately 1 rm, and for this purpose it is necessary to perform multiple coatings.
この場合、金属表面に既にコーティ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ックが生
ずる。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.
このクラックを防ぐためには、室温からガラス転移温度
までの熱膨張係数α、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−α、
（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 cracking, the difference between the coefficient of thermal expansion α from room temperature to the glass transition temperature and the coefficient of thermal expansion α2 from the glass transition temperature to the glass yielding temperature, that is, α2−α,
(hereinafter referred to as Δα) is required to be small, and α1 is required to be close to the value of the thermal expansion coefficient of the metal base.
従来のコーティング用ガラスはΔαがΔα〉１３０ Ｘ
ｌ０−’ （’Ｃ−’）程度であり、クラックが生じ易
い欠点があった。Conventional coating glass has a Δα of Δα〉130
It was about 10-'('C-'), and had the disadvantage that cracks were likely to occur.
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の値をより小さくし、複数コーティングに際し
てもクランクが生じ難い金属表面へのコーティング用ガ
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 reduces the value of Δα and is less likely to cause cranking 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Ｙ
２Ｏ，含有アルミノ珪酸塩ガラス（ＹｚＯｓ−ＡｌｚＯ
ｓ Ｓｔｏｗ）を開発した。（八、 Ｍｄ１ｓｈｉａ
＋ａ。SUMMARY OF THE INVENTION The present inventors first developed Y, which has a high modulus of elasticity, high hardness, and high corrosion resistance.
2O, containing aluminosilicate glass (YzOs-AlzO
s Stow). (8, Md1shia
+a.
Ｙ、 Ｔａｎ＋ｕｒａ、 Ｔ、 ５ａｋａｉｎｏ、 Ｊ
、 Ａｍｅｒｉｃａｎ ＣｅｒａｍｉｃＳｏｃｉｅｔｙ
、 ６１． Ｐ２４７（１９７８）このガラスにＮａ
、０を添加するとΔαがΔα〉１００ Ｘｌ０−’ （
’Ｃ−’）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ィング用
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。Y, Tan+ura, T, 5akaino, J
, American Ceramic Society
, 61. P247 (1978) Na in this glass
, 0 is added, Δα becomes Δα〉100 Xl0−' (
'C-') or less, and it has been found that adding ZrO2 can provide a coating glass with improved alkali resistance and acid resistance. The present invention was completed based on this knowledge.
本発明の要旨は、
モル％で、Ｓｔｏｗ ５９〜７１％、Ｎａｔｏ １６〜
２８％、ｙｚｏ＊ ４．３３〜６．５％、Ａｌｔｏｚ
６．５〜８．６６％、ＺｒＯ。The gist of the invention is: In mol%, Stow 59-71%, Nato 16-71%
28%, yzo* 4.33-6.5%, Altoz
6.5-8.66% ZrO.
１〜３．５％の組成からなる金属表面へのコーティング
用ガラスにある。Glass for coating on metal surfaces having a composition of 1 to 3.5%.
このガラスにおいて、Ｓｉｎｇが５９モル％（以下％は
モル％を示す）より少ないとΔαが１００ Ｘｌ０−’
（”Ｃ−’ ）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 Sing is less than 59 mol% (hereinafter % indicates mol%), Δα is 100 Xl0-'
("C-'") or more, and if it exceeds 71%, it becomes difficult to vitrify and high quality glass cannot be obtained.
ＮａｇＯ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
値が大きくなってしまう。If NagO is less than 16%, the vitrification temperature will be too high and high quality glass cannot be obtained, and if it exceeds 28%, the value of Δα will become large.
Ｙ、Ｏ！ｌ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。Y, O! If l is less than 4.33%, Δα becomes large, and even if it exceeds 6.5%, Δα becomes large.
ＡｌｚＯｓ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 AlzOs is less than 6.5% and exceeds 8 or 66%, Δα becomes large.
Ｚｒ０１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、コーティン
グするために必要な温度が高くなる。When Zr01 is less than 1%, Δα is small, but alkali resistance is not sufficient. If it exceeds 3.5%, the temperature required for coating becomes high.
本発明のコーティング用ガラスを製造するには、原料と
してＮａ２Ｏ成分にはＮａ、ＣＯ，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°Ｃ以下
で溶融することによって得られる。In order to manufacture the coating glass of the present invention, Na and CO are used as raw materials for the Na2O component, and oxides are used for the other components, and these raw material powders are thoroughly mixed in a predetermined ratio, and then placed in an alumina crucible. It can be obtained by melting at 1550°C or less.
実施例１゜
モル％で、５ｉｆｔ ６２．７６％、ＮａＪ ２１．３
８％、Ｙ２Ｏ３５，３６％、Ａｌｔｏｓ ７．５０％、
Ｚｒ０ｚ ３．０％のガラスを、Ｎａ、Ｏの原料として
はＮａ１ＣＯ，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°Ｃで３時間溶融した。このガラスを
３φ（ｍｎ＋）の丸棒に成形し、徐冷して熱膨張測定用
試料とした。熱膨張特性は差動トランス型装置を用い、
５（”Ｃ／分）の昇温速度で測定した。Example 1 mol %, 5ift 62.76%, NaJ 21.3
8%, Y2O35,36%, Altos 7.50%,
Using 3.0% Zr0z glass, using Na1CO as raw materials for Na and O, and using oxides as raw materials for other components, the raw material powder mixture was placed in an alumina crucible and heated at 1550°C in an electric furnace. The mixture was melted for 3 hours. This glass was formed into a round bar of 3φ (mn+) and slowly cooled to provide a sample for thermal expansion measurement. Thermal expansion characteristics are determined using a differential transformer type device.
Measurements were made at a heating rate of 5"C/min.
このガラスの密度は、２．７８ｇ／ｃｍ″、室温からガ
ラス転移温度までの熱膨張係数α１は８７Ｘ１０−’（
’Ｃ”）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５２Ｘ１０−
’じＣ−’）であった。The density of this glass is 2.78 g/cm'', and the coefficient of thermal expansion α1 from room temperature to glass transition temperature is 87X10-' (
'C''), and the value of Δα, which is the difference between this value and the coefficient of thermal expansion α2 from the glass transition temperature to the yield temperature, is 52X10-
'JC-').
実施例２゜
モル％で、５ｉＯｚ ６９％、Ｎａｚｏ １５％、Ａｌ
ｚＯｓ７．８％、ＹｚＯ＊ ５．２％、Ｚｒ０ｚ ３％
の組成のガーｙスを実施例１と同じ方法で作った。この
ガラスの密度は２．７４ｇ／Ｃｍ’ 、室温からガラス
転移温度までの熱膨張係数α、は７４Ｘ１０−’ （’
Ｃ−’） 、Δαは９０×１０−’ （”Ｃ−’）であ
った。２０重量％ＨＣＩ水溶液（８０”Ｃ）とＩ Ｎ
−ＮａＯＨ水溶液（８０”Ｃ）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 Mol%: 5iOz 69%, Nazo 15%, Al
zOs7.8%, YzO* 5.2%, Zr0z 3%
A girdle having a composition of was prepared in the same manner as in Example 1. The density of this glass is 2.74 g/Cm', and the coefficient of thermal expansion α from room temperature to glass transition temperature is 74X10-'('
C-'), Δα was 90 × 10-'("C-'). 20% by weight HCI aqueous solution (80"C) and I N
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２．４ ｇ／ｍ”・ｄａｙであった。As a result, the acid resistance was 0.35 g/m2·day, and the alkali resistance was 2.4 g/m''·day.
実施例３゜
モル％で、５ｉＯｚ ６９％、Ｎａｚｏ １６．６４％
、Ａｌ２０３８．４７％、ＹｚＯｓ ４．３９％、Ｚｒ
（ｈ １．５％の組成のガラスを実施例１と同じ方法で
ガラスを作った。このガラスの密度は２．６６ｇ／ｃｎ
＋３、α、は７８Ｘ１０−’（”Ｃ−’）、Δαは９９
Ｘ１０−７（”Ｃ−’）であった。Example 3 Mol%: 5iOz 69%, Nazo 16.64%
, Al2038.47%, YzOs 4.39%, Zr
(h) A glass with a composition of 1.5% was made in the same manner as in Example 1. The density of this glass was 2.66 g/cn.
+3, α is 78X10-'("C-'), Δα is 99
It was X10-7 ("C-').
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°Ｃで溶融することを３回繰り返してガラスコー
ティングを行ったがクランクは生じなかった。This glass powder is sprayed onto a stainless steel plate,
Glass coating was performed by repeating melting at 890°C three times, but no cranking 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
ＮａｇＯを添加することによりΔαの値が１００×１Ｏ
−７（”Ｃ−’）以下と小さくなり、ガラスコーティン
グを繰り返してもクランクの発生がなくなり、またＺｒ
Ｏ□の添加により耐酸、耐アルカリの腐食性を高め得、
コーティ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 100×1O by adding NagO to Y2O3-containing aluminosilicate glass.
-7 ("C-') or less, no cranking occurs even after repeated glass coating, and Zr
Addition of O□ can improve acid and alkali corrosion resistance,
This is an excellent coating glass.
Claims (1)
２８％、Ｙ＿２Ｏ＿３４．３３〜６．５％、Ａｌ＿２Ｏ
＿３６．５〜８．６６％、ＺｒＯ＿２１〜３．５％の組
成からなる金属表面へのコーティング用ガラス。In mol%, SiO_259~71%, Na_2O16~
28%, Y_2O_34.33-6.5%, Al_2O
A glass for coating metal surfaces with a composition of _36.5 to 8.66% and ZrO_21 to 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 true JPH01122936A (en) | 1989-05-16 |
| JPH0433746B2 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) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011502032A (en) * | 2007-10-02 | 2011-01-20 | ソルヴェイ（ソシエテ アノニム） | Use of silicon-containing compositions to improve the corrosion resistance of containers |
| EP2855383A2 (en) * | 2012-05-31 | 2015-04-08 | Corning Incorporated | Ion exchangeable transition metal-containing glasses |
| US9073779B2 (en) | 2008-02-26 | 2015-07-07 | Corning Incorporated | Fining agents for silicate glasses |
| CN112876080A (en) * | 2021-02-04 | 2021-06-01 | 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
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011502032A (en) * | 2007-10-02 | 2011-01-20 | ソルヴェイ（ソシエテ アノニム） | Use of silicon-containing compositions to improve the corrosion resistance of containers |
| US9073779B2 (en) | 2008-02-26 | 2015-07-07 | Corning Incorporated | Fining agents for silicate glasses |
| US10040715B2 (en) | 2008-02-26 | 2018-08-07 | Corning Incorporated | Silicate glasses having low seed concentration |
| US10626042B2 (en) | 2008-02-26 | 2020-04-21 | Corning Incorporated | Fining agents for silicate glasses |
| EP2855383A2 (en) * | 2012-05-31 | 2015-04-08 | Corning Incorporated | Ion exchangeable transition metal-containing glasses |
| EP2855383B1 (en) * | 2012-05-31 | 2021-06-16 | Corning Incorporated | Ion exchangeable transition metal-containing glasses |
| CN112876080A (en) * | 2021-02-04 | 2021-06-01 | 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 |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0433746B2 (en) | 1992-06-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5153070A (en) | Coated refractory article and method | |
| US3184320A (en) | Ceramic protective coating composition | |
| US3368712A (en) | Semicrystalline glass and method of applying the same to metallic bases | |
| US5198393A (en) | Rare earth-containing frits having a high glass transition temperature and their use for the production of enamels having improved heat resistance | |
| US3458344A (en) | Semicrystallized ground coats and enameled articles manufactured therefrom | |
| JPH01122936A (en) | Glass for coating metallic surface | |
| US3285773A (en) | Vitreous enamels for hot water tanks | |
| US2829062A (en) | Refractory vitreous ceramic coating materials | |
| US2911312A (en) | Non-toxic aluminum enamel frits | |
| EP0202750B1 (en) | Glazes for glass-ceramic articles | |
| CA2492744C (en) | Water-resistant porcelain enamel coatings and method of manufacturing same | |
| US3061449A (en) | Vitreous enamel frit | |
| US5264287A (en) | Rare earth-containing frits having a high glass transition temperature and their use for the production of enamels having improved heat resistance | |
| JPH01297471A (en) | Heat-resistant inorganic composition | |
| JPH0440300B2 (en) | ||
| EP1230183B1 (en) | Water-resistant porcelain enamel coatings and method of manufacturing same | |
| JPH07126035A (en) | Low-melting glass | |
| KR950012487B1 (en) | Method for making an enamelled aluminum | |
| US3014816A (en) | Acid-resistant enamel for stainless steel | |
| JPH01145347A (en) | Aluminum enamel article having high brightness | |
| JPS58117261A (en) | Corrosion-resistant paint for high-temperature melting metal | |
| JPH04214044A (en) | Frit composition | |
| Koenigstein et al. | The Effects of Silica on the Properties of Vitreous Enamels. | |
| Kurushivna et al. | The thermal shock endurance of a plasma sprayed ZrO2 coating on steel | |
| JPS5838506B2 (en) | Anti-adhesive thermal spray material for high temperature gas furnaces |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |