JPS63284266A - High-temperature oxidation inhibitor for steel material - Google Patents
High-temperature oxidation inhibitor for steel materialInfo
- Publication number
- JPS63284266A JPS63284266A JP11716587A JP11716587A JPS63284266A JP S63284266 A JPS63284266 A JP S63284266A JP 11716587 A JP11716587 A JP 11716587A JP 11716587 A JP11716587 A JP 11716587A JP S63284266 A JPS63284266 A JP S63284266A
- Authority
- JP
- Japan
- Prior art keywords
- alumina
- weight
- specified
- ceramic
- paint
- 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
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 36
- 239000010959 steel Substances 0.000 title claims abstract description 36
- 230000003647 oxidation Effects 0.000 title claims abstract description 9
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 9
- 239000000463 material Substances 0.000 title claims description 30
- 239000003112 inhibitor Substances 0.000 title 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000003973 paint Substances 0.000 claims abstract description 38
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 25
- 239000000843 powder Substances 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000000919 ceramic Substances 0.000 claims abstract description 17
- 239000000835 fiber Substances 0.000 claims abstract description 17
- 238000005245 sintering Methods 0.000 claims abstract description 16
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002245 particle Substances 0.000 claims abstract description 13
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910010271 silicon carbide Inorganic materials 0.000 claims abstract description 10
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 10
- 229910052581 Si3N4 Inorganic materials 0.000 claims abstract description 8
- 239000011230 binding agent Substances 0.000 claims abstract description 8
- 230000007935 neutral effect Effects 0.000 claims abstract description 8
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims abstract description 8
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 claims abstract description 7
- 229910052845 zircon Inorganic materials 0.000 claims abstract description 7
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052802 copper Inorganic materials 0.000 claims abstract description 6
- 239000010445 mica Substances 0.000 claims abstract description 6
- 229910052618 mica group Inorganic materials 0.000 claims abstract description 6
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 5
- 229920001577 copolymer Polymers 0.000 claims abstract description 5
- 239000013078 crystal Substances 0.000 claims abstract description 5
- 229910052742 iron Inorganic materials 0.000 claims abstract description 5
- 239000007787 solid Substances 0.000 claims abstract description 4
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 3
- 229920000642 polymer Polymers 0.000 claims abstract description 3
- 239000011248 coating agent Substances 0.000 claims description 23
- 238000000576 coating method Methods 0.000 claims description 23
- 230000003078 antioxidant effect Effects 0.000 claims description 16
- 239000003963 antioxidant agent Substances 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000004615 ingredient Substances 0.000 claims description 9
- 239000008119 colloidal silica Substances 0.000 claims description 8
- 239000010419 fine particle Substances 0.000 claims description 4
- 230000002401 inhibitory effect Effects 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 238000002425 crystallisation Methods 0.000 claims description 2
- 230000008025 crystallization Effects 0.000 claims description 2
- 239000000839 emulsion Substances 0.000 claims description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims 3
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims 2
- 229920001519 homopolymer Polymers 0.000 claims 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims 1
- 239000005977 Ethylene Substances 0.000 claims 1
- 229920001038 ethylene copolymer Polymers 0.000 claims 1
- 229920000915 polyvinyl chloride Polymers 0.000 claims 1
- 239000004800 polyvinyl chloride Substances 0.000 claims 1
- 229920001897 terpolymer Polymers 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 abstract description 8
- 239000002184 metal Substances 0.000 abstract description 8
- 238000002156 mixing Methods 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 description 17
- 239000010949 copper Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 230000001590 oxidative effect Effects 0.000 description 8
- 239000007789 gas Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 239000011819 refractory material Substances 0.000 description 2
- 239000011882 ultra-fine particle Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、鋼材、特に鋼片スラブの表面に塗布してその
高温酸化の防止を図り、また加熱炉中の高温酸化雰囲気
でのスケール発生を防止せしめ、そして圧延前に容易に
剥離でき、特に連続式加熱炉の入口付近において鋼材と
加熱空気との温度差により生ずる結露小滴による塗膜の
損傷を防止する鋼材用高温酸化防止塗料に関する。[Detailed Description of the Invention] [Field of Industrial Application] The present invention is applied to the surface of steel materials, especially steel billet slabs, to prevent high-temperature oxidation, and also to prevent scale formation in a high-temperature oxidizing atmosphere in a heating furnace. The present invention relates to a high-temperature oxidation-inhibiting coating for steel materials, which can be easily peeled off before rolling, and which prevents damage to the coating film due to small droplets of condensation caused by the temperature difference between the steel material and the heated air, especially near the entrance of a continuous heating furnace. .
［従来の技術］
周知の如く、鋼片スラブは加熱炉又は均熱炉にて１０５
０〜１２００℃の温度で加熱され、圧延されて製品とな
る。この鋼片スラブが普通鋼レベルの鋼材の場合には、
加熱炉におけるスケールの発生は少なく、デスケーリン
グも比較的容易である。しかし、この鋼片スラブが高級
鋼レベルの品質の場合には、在炉時間、温度の影響で酸
化スケールが多く発生し、デスケーリングも困難で、歩
留低下による生産性、省資源並びに製品仕上げの観点か
ら問題となっている。[Prior Art] As is well known, steel billet slabs are heated in a heating furnace or a soaking furnace at 105°C.
It is heated at a temperature of 0 to 1200°C and rolled into a product. If this billet slab is made of steel at the level of ordinary steel,
There is little scale generation in the heating furnace, and descaling is relatively easy. However, if the billet slab is of high-grade steel quality, a large amount of oxidized scale will occur due to the time and temperature in the furnace, and descaling will be difficult. It is a problem from this point of view.
従来、高温のもとでの鋼片スラブの酸化及びスケール発
生を防止する為に多くの高温酸化防止塗料が研究、開発
されている。多くの塗料は、シリカ系耐火物、マグシア
系耐火物、低融点の金属又は無機塩を含有するものであ
るが、Ｃｕ、Ｎｉ、Ｃ「等の含有スラブの鋼種や連続式
またはバッチ式加熱炉という操業方法の差異により、酸
化防止及びスケール発生防止並びに剥離性が不充分であ
る等の欠点がある。それ故に現在では、高級鋼スラブに
薄鉄板製保護カバーで鋼材表面をおおって加熱炉に送入
し、鋼材表面が酸化雰囲気にできるだけ曝されないよう
にして、スラブスケールの発生を防止している。しかし
、この薄鉄板保護カバーは鋼材への取付に多大な労力を
必要とすると共に、間接加熱になるため加熱炉燃料の原
単位の悪化要因とも成っている。Conventionally, many high-temperature oxidation-inhibiting paints have been researched and developed in order to prevent oxidation and scale formation of steel billet slabs under high temperatures. Many paints contain silica-based refractories, magcia-based refractories, low-melting point metals, or inorganic salts, but they do not require the use of slab steels containing Cu, Ni, C, etc., or continuous or batch heating furnaces. Due to the difference in operating methods, there are drawbacks such as insufficient oxidation prevention, scale generation prevention, and peelability.Therefore, at present, high-grade steel slabs are covered with thin iron plate protective covers to cover the surface of the steel material and heat the furnace. The steel surface is exposed to an oxidizing atmosphere as much as possible to prevent the occurrence of slab scale. However, this thin steel plate protective cover requires a great deal of labor to attach to the steel material, and requires indirect Because it causes heating, it is also a factor in deteriorating the unit consumption of heating furnace fuel.
高温酸化防止塗料は、酸化防止及びスケール発生防止と
ともに、容易に剥離すること並びにスケールが発生した
場合でもそのスケールが塗料と共に圧延前に高圧水によ
って容易に剥離すること、要するにデスケーリングが容
易であることが要求される。もしスケール及び塗料が圧
延時に残存したならば、製品の表面にキズが生じてしま
う。High-temperature antioxidant paint not only prevents oxidation and scale generation, but also peels off easily, and even if scale occurs, the scale can be easily peeled off together with the paint using high-pressure water before rolling, in other words, it is easy to descale. This is required. If scale and paint remain during rolling, scratches will occur on the surface of the product.
そこで本発明者等は、これらの要求を満足する高温酸化
防止塗料を特願昭５９−１０６５２６号、同５９−１０
６５２７号及び同５９−１８３８３８号の出願によって
提案した。これらの出願の中で、特に良い効果を示した
特願昭５９−１８３８３８号出願の高温酸化防止塗料は
以下の組成のものである：
ａ） セラミック基材としての炭化珪素、窒化珪素、安
定化ジルコン、雲母の群の内の少なくとも１種；２０〜
５０重量％、
ｂ） セラミック助材としての以下の３種のアルミナ；
２５〜５０重量％
アルミナ（１）：α晶が大きく且つ焼結収縮率の小さい
扁平状微粒アルミナ、
アルミナ（２）＝α化率が高く、焼成収縮が安定してい
る平均粒度１００μ以下の扁平粒状アルミナ及び
アルミナ（３）：水分含有量が少なく、中ソーダーグレ
ードの易焼結性超微粒アルミナ、Ｃ） バインダーとし
ての中性リン酸アルミニウム、コロイダルシリカ、アル
ミナゾルの群の内の少なくとも１ｆ５１；ｌｏ〜４０重
量％、ｄ） Ｆ ｅ、Ｃｕ、Ｎ を及びＣｒ粉の群の
内の少なくとも１種； ５〜１０重量％
ｅ） セラミック焼結促進剤としての炭酸ナトリウム；
５〜３０重量％、及び
ｆ） 耐水性の塗膜を形成する重合体及び／または共重
合体の水性エマルジョンまたは水溶液；２．５〜１５重
量％（固形分）
（但し、ａ）〜ｆ）成分の合計は １００重量％である
。）
この塗料を鋼材上に塗布するに当って、追加的に約１０
〜１５重量％（組成物全体量に対して）の水を該当組成
物に混入した場合に塗装作業性が向上することが判って
いる。Therefore, the present inventors have developed a high-temperature oxidation-preventing paint that satisfies these requirements in Japanese Patent Application No. 59-106526 and No. 59-10.
The invention was proposed by application No. 6527 and No. 59-183838. Among these applications, the high-temperature antioxidant paint of Japanese Patent Application No. 183838/1983 which showed particularly good effects has the following composition: a) Silicon carbide, silicon nitride, and stabilization as the ceramic base material. At least one species from the group of zircon and mica; 20~
50% by weight, b) the following three types of alumina as ceramic auxiliary materials;
25-50% by weight Alumina (1): flat fine grain alumina with large α crystals and low sintering shrinkage rate, alumina (2) = flat fine grained alumina with high α crystallization rate and stable sintering shrinkage with an average particle size of 100μ or less Granular alumina and alumina (3): low moisture content, medium soda grade, easily sinterable ultrafine alumina, C) at least 1f51 of the group of neutral aluminum phosphate, colloidal silica, alumina sol as a binder; lo ~40% by weight, d) at least one member from the group of Fe, Cu, N and Cr powder; 5-10% by weight e) sodium carbonate as ceramic sintering accelerator;
5 to 30% by weight, and f) an aqueous emulsion or aqueous solution of a polymer and/or copolymer that forms a water-resistant coating; 2.5 to 15% by weight (solid content) (However, a) to f) The sum of the components is 100% by weight. ) When applying this paint on the steel material, add approximately 10%
It has been found that coating workability is improved when up to 15% by weight (based on the total weight of the composition) of water is mixed into the composition.
［発明が解決しようとする問題点］
しかし、鋼材は加熱炉に操入される前に金属製のロール
上を移送されるので、この塗料を鋼材に塗布した場合に
は、塗布された塗料の一部が金属製のロールによる物理
的な衝撃等はより剥離し、加熱炉内でこの剥離した部分
にスケールを生ぜしめるという問題点があった。このス
ケールの発生を回避させる為に加熱炉に入る手前でこの
塗料を乾燥させることも考えられるが、もしそうしたと
しても、生産性が低下し、経済性が悪化するという問題
点がある。[Problems to be solved by the invention] However, since the steel material is transferred on metal rolls before being put into the heating furnace, when this paint is applied to the steel material, the applied paint is There was a problem in that physical impact caused by a partially metal roll caused further peeling, and scale was generated in the peeled part in the heating furnace. In order to avoid the formation of this scale, it is possible to dry the paint before entering the heating furnace, but even if this is done, there is a problem that productivity will decrease and economic efficiency will deteriorate.
［問題点を解決するための手段］
この発明に係る高温酸化防止塗料は、特願昭５９−１８
３８３８号出願に係る高温酸化防止塗料に更に３〜１５
重量％のチタン酸カリウ、ム繊維（ｇ）成分〕を混合さ
せることにより上記問題点を解決したものである。[Means for solving the problems] The high-temperature antioxidant paint according to the present invention is disclosed in Japanese Patent Application No. 59-18
3 to 15 in addition to the high temperature antioxidant paint related to application No. 3838.
The above-mentioned problems were solved by mixing % by weight of potassium titanate and mu fiber (g) component.
すなわち、本発明者等は特願昭５９−１８３８３８号出
願に係る高温酸化防止塗料にチタン酸カリウム繊維を混
合させると、この繊維が骨材として作用して塗膜量係合
強度が高まり、高温酸化ガスの浸透が防止されるととも
に物理的な衝撃に対して強度が高まることを見出した。That is, the present inventors have discovered that when potassium titanate fibers are mixed into the high-temperature antioxidant paint applied in Japanese Patent Application No. 59-183838, the fibers act as aggregates and increase the coating film engagement strength, resulting in high-temperature It has been found that the penetration of oxidizing gas is prevented and the strength against physical impact is increased.
ここで、ｇ）成分であるチタン酸カリウム繊維の混入量
を３〜１５重量％の範囲としたのは、チタン酸カリウム
繊維が３重量％未満では骨材としての効果が少なく、１
５重量％を越えるとこの繊維が塗膜の表面に突出してし
まい、均一な組成の塗膜が得られなくなるが、３〜１５
重量％の範囲ではかかる不都合を生ずることなく塗膜の
強度を高めることができるからである。Here, the amount of potassium titanate fiber mixed in as component g) was set in the range of 3 to 15% by weight because if the potassium titanate fiber is less than 3% by weight, it has little effect as an aggregate.
If it exceeds 5% by weight, these fibers will protrude onto the surface of the coating film, making it impossible to obtain a coating film with a uniform composition, but if the content exceeds 3 to 15% by weight,
This is because within the weight percent range, the strength of the coating film can be increased without causing such disadvantages.
また、ｇ）成分として用いられるこのチタン酸カリウム
繊維としては、組成； Ｋ、Ｔｉ４０．及び／又はに、
Ｔｉ、０□５、直径：１０〜３０μ、長さ；１００〜５
００μのトンネル状の結晶構造を有し、接触面積の大き
な板状繊維が好ましい。In addition, the potassium titanate fiber used as component g) has a composition: K, Ti40. and/or to,
Ti, 0□5, diameter: 10~30μ, length: 100~5
A plate-like fiber having a tunnel-like crystal structure of 00 μm and a large contact area is preferable.
基材としてのセラミックス（ａ）成分）は耐熱性の高い
もの（例えば炭化珪素は２２００℃）がよく、その使用
量は、成分ａ）、 ｂ）、 ｃ）、 ｄ）及びｅ） （
以下、全成分と略す）の合計の２０〜５０重量％の範囲
にある必要がある。ａ）成分が２０重量％未満では塗膜
がち密に形成されず、酸化雰囲気ガスの浸透量が多くな
り、所望の酸化防止効果が得られず、５０重量％を越え
ると熱伝導性が低下し、加熱エネルギーの消費が増して
エネルギーロスが多くなる。The ceramic (component a) used as the base material is preferably one with high heat resistance (for example, silicon carbide at 2200°C), and the amount used is as follows: component a), b), c), d), and e) (
It needs to be in the range of 20 to 50% by weight of the total of all components (hereinafter abbreviated as "all components"). If the component (a) is less than 20% by weight, the coating film will not be formed densely and the amount of oxidizing atmosphere gas permeated will increase, making it impossible to obtain the desired antioxidant effect, and if it exceeds 50% by weight, the thermal conductivity will decrease. , heating energy consumption increases and energy loss increases.
セラミック助材としてのアルミナ（ｂ）成分）は、α化
率の高い扁平状粒子〔アルミナ（１）及び（２）〕と易
焼結性の超微粒子〔アルミナ（３）〕との組合せ物であ
る。Alumina (component (b)) as a ceramic auxiliary material is a combination of flat particles with a high gelatinization rate [alumina (1) and (2)] and easily sinterable ultrafine particles [alumina (3)]. be.
アルミナ（１）は、α晶が大きく、焼結収縮率が小さく
、殊に ５％以下（１６００℃、３時間）であり、そし
て扁平状の隠ぺい力に優れた、殊に１〜ｌＯμの微粒子
である。Alumina (1) has a large α crystal, a small sintering shrinkage rate of 5% or less (1600°C, 3 hours), and has excellent flat hiding power, especially fine particles of 1 to 1Oμ. It is.
アルミナ（２）は、焼成収縮が安定しており、殊に収縮
率が１０％以下（１８００℃、３時間）であり、α化率
の高い、平均粒度１００μ以下、殊に２０μ以上、殊に
３０〜６０μの、隠ぺい力に優れた扁平状の粒子である
。Alumina (2) has stable firing shrinkage, especially shrinkage rate of 10% or less (1800°C, 3 hours), high gelatinization rate, average particle size of 100μ or less, especially 20μ or more, especially They are flat particles with a diameter of 30 to 60μ and excellent hiding power.
アルミナ（３）は、水分含有量が少なく、殊にＮａ２Ｏ
を０．２〜０．３重量％含有する中ソーダーグレード、
平均粒度１μ以下の易焼結性超微粒子である。Alumina (3) has a low water content, especially Na2O
Medium soda grade containing 0.2-0.3% by weight of
Easily sinterable ultrafine particles with an average particle size of 1μ or less.
セラミック助材としてのアルミナ（ｂ）成分〕は、膜厚
１００μ以下の場合、２５重量％以下では充分な隠ぺい
力あるち密な塗膜を得ることができず、５０重量％以上
では、塗膜の剥離性が不良になる。Alumina (b) component as a ceramic auxiliary material] cannot obtain a dense coating film with sufficient hiding power when the film thickness is 100μ or less, if it is less than 25% by weight, and if it is more than 50% by weight, the coating film becomes Peelability becomes poor.
アルミナ（１）、 （２）及び（３）は、相互に（１，
５〜３）：（０，５〜２）：（１〜３）の重量比で用い
た時に有利な結果が得られることが判っている。Alumina (1), (2) and (3) are mutually (1,
It has been found that advantageous results are obtained when a weight ratio of 5-3):(0,5-2):(1-3) is used.
バインダーとして使用される中性リン酸アルミニウム、
コロイダルシリカ、アルミナゾルの群の内の少なくとも
１種（Ｃ）成分〕は、前記ａ）成分であるセラミック基
材の結合を安定化せしめるとともに、鋼材との密着性を
高めるために使用するのであり、その使用量は全成分の
１０〜４０重量％の範囲にある必要がある。このバイン
ダーは、１０重量％以下では混合練成物が固く鋼材面へ
の密着力が得られず、４０重量％以上ではバインダーと
しての効果が増加しない。Neutral aluminum phosphate, used as a binder
At least one component (C) from the group consisting of colloidal silica and alumina sol] is used to stabilize the bonding of the ceramic base material, which is component a), and to improve the adhesion to the steel material. The amount used should be in the range of 10 to 40% by weight of the total ingredients. If the binder is less than 10% by weight, the mixed mixture will be hard and will not be able to adhere to the surface of the steel material, and if it is more than 40% by weight, the effect as a binder will not increase.
Ｆ ｅ、Ｃｕ、Ｎ ｌ及びＣｒ粉の群の内の少なくとも
１種からなる金属粉（ｄ）成分〕は加熱炉中に於ける酸
化雰囲気（一般的に排ガス中の０２ ：１〜２％）が鋼
材表面に接触することを避け、或は最小限にくいとめる
ために還元雰囲気を保持するものである。金属粉が５重
量％未満では鋼材表面部が酸化雰囲気となり、１０重量
％を越えるとこの金属粉が高温において鋼材と反応或は
溶着し、鋼材表面、所謂製品表面の性質を変化せしめ、
悪影響をもたらす。Metal powder (component (d)) consisting of at least one of the group consisting of Fe, Cu, Nl, and Cr powder] is added in an oxidizing atmosphere in a heating furnace (generally 02:1 to 2% in exhaust gas). A reducing atmosphere is maintained in order to avoid or minimize contact with the steel surface. If the metal powder is less than 5% by weight, the surface of the steel material becomes an oxidizing atmosphere, and if it exceeds 10% by weight, the metal powder reacts with or welds to the steel material at high temperatures, changing the properties of the steel surface, the so-called product surface.
bring about negative effects.
セラミック焼結促進材（ｅ）成分）は、３００〜８００
℃においてセラミック基材並びにバインダーの焼結を促
進せしめるもので、塗料の混合練成物を固くし、鋼材表
面への密着強度を高め、塗膜をち密にする役目を果す。Ceramic sintering accelerator (e) component) is 300 to 800
It accelerates the sintering of the ceramic base material and binder at ℃, and plays the role of hardening the paint mixture, increasing the adhesion strength to the steel surface, and making the paint film denser.
適正な焼結速度を保持するには５重量％が下限である。5% by weight is the lower limit to maintain proper sintering rates.
５重量％未満であると焼結状態が悪く（弱く）、混合練
成物内の塗膜量強度が低下し、酸化雰囲気の侵食域とな
って鋼材表面が悪化し、３０重量％を越えると塗膜がち
密に形成されず、初期の目的から逸脱してしまう。If it is less than 5% by weight, the sintering condition will be poor (weak), the coating strength in the mixed mixture will decrease, and the surface of the steel material will deteriorate due to an oxidizing atmosphere erosion zone, and if it exceeds 30% by weight, The coating film is not formed densely and deviates from the initial purpose.
ｆ）成分の使用量は、固形分含有量として２．５〜１５
重量％（塗料全体を基準とする）、殊に２．５〜１３重
量％であるのが好ましい。２．５重量％より少ないと実
効が得られず、１５重量％を越えると、連続式加熱炉中
においてこの成分の燃焼によってガスが発生し、これが
塗膜のフクレ、剥離現象を惹き起し得る。f) The amount of component used is 2.5 to 15% as solid content.
Preference is given to % by weight (based on the total paint), in particular from 2.5 to 13% by weight. If it is less than 2.5% by weight, it will not be effective, and if it exceeds 15% by weight, gas will be generated by combustion of this component in a continuous heating furnace, which may cause blistering and peeling of the paint film. .
本発明の塗料の場合、塗装作業性を向上させる為に、ｆ
）成分に含まれる水分に加えて水を適当量混入してもよ
い。塗料中に含まれる水分は、ｆ）成分に含まれる量も
含めて約１０〜１５重量％（塗料全体に対して）である
のが好ましい。In the case of the paint of the present invention, in order to improve painting workability, f
) In addition to the water contained in the ingredients, an appropriate amount of water may be mixed. The amount of water contained in the paint, including the amount contained in component f), is preferably about 10 to 15% by weight (based on the entire paint).
［実施例］ 以下、実施例によって本発明を更に詳細に説明する。。[Example] Hereinafter, the present invention will be explained in more detail with reference to Examples. .
東ＪＬＬ二１
炭化珪素 １０重量％窒化珪素
７ 〃安定化酸化ジルコン
７ 〃アルミナ（１）
２０ ））” （３）
５ ／／中性リン酸アルミニウム １２〃Ｆ
ｅ粉 ３〃
銅 粉 ３
〃炭酸ナトリウム ５ 〃チタン
酸カリウム繊維 １５））水
適当量の他に、平均粒度５μで収縮、率（
１６００℃、３時間）５％以下の扁平状の高α晶アルミ
ナ（これはアルミナ（１） に相当し、以下、アルミナ
１と略す）２０重量％、平均粒度４５μ、収縮率１０％
以下（１８００℃、３時間）のα化率１００％の扁平状
アルミナ（これはアルミナ（２）に相当し、以下、アル
ミナ２と略す） ５重量％及び０．２５重量％のＮａ２
Ｏ含有量の平均粒度０．４μで且つ粒度分布０．１〜１
゜５μの中ソーダーグレードのアルミナ（これはアルミ
ナ（３）に相当し以下、アルミナ３と略す） ５重量％
並びに適当量の水を含有する混合物を製造する。East JLL 21 Silicon carbide 10% by weight silicon nitride
7 Stabilized zircon oxide
7 Alumina (1)
20))” (3)
5 // Neutral aluminum phosphate 12〃F
e powder 3 Copper powder 3
〃Sodium carbonate 5 〃Potassium titanate fiber 15)) Water
In addition to the appropriate amount, the shrinkage rate (
1600℃, 3 hours) 20% by weight of flat high α-crystalline alumina (this corresponds to alumina (1), hereinafter abbreviated as alumina 1) of 5% or less, average particle size 45μ, shrinkage rate 10%
Flat alumina with a gelatinization rate of 100% (this corresponds to alumina (2), hereinafter abbreviated as alumina 2): 5% by weight and 0.25% by weight of Na2
Average particle size of O content is 0.4μ and particle size distribution is 0.1-1
゜5μ medium soda grade alumina (this corresponds to alumina (3) and is hereinafter abbreviated as alumina 3) 5% by weight
and prepare a mixture containing the appropriate amount of water.
この塗料を、無加熱状態の厚板用鋼材の超高張力鋼、高
張力鋼及び普通鋼のそれぞれに５０μ及び１００μの塗
膜厚さで塗布し、２４時間自然乾燥した後、耐水性試験
として表面に５秒当り １ｏｏｃｃ／ｍ２の割合で水道
水を４時間噴霧して損傷状況を見、その鋼材を第１表（
後記）に示す在炉時間及び炉温度のもとで加熱して圧延
する。This paint was applied to ultra-high tensile strength steel, high tensile strength steel, and ordinary steel, respectively, in an unheated state to a film thickness of 50μ and 100μ, and after air drying for 24 hours, a water resistance test was performed. Spray tap water on the surface at a rate of 1oocc/m2 per 5 seconds for 4 hours, check the damage, and compare the steel materials to Table 1 (
It is heated and rolled under the furnace time and furnace temperature shown in (described later).
スケールの発生状況及び酸化防止塗料の耐水性及び剥離
性について測定結果を第１表に示す。Table 1 shows the measurement results regarding scale generation and the water resistance and removability of the antioxidant paint.
実施例−２ 以下の成分を用いる他は、実施例−１を繰り返す。Example-2 Example-1 is repeated except that the following ingredients are used.
炭化珪素 ５重量％窒化珪素
１０〃
雲母 ５ 〃アルミナ１
１５ 〃〃 ２ ５
〃
）） ３ ＩＱ ｌ）中性
リン酸アルミニウム １０／／コロイダルシリカ
６ 〃Ｆｅ粉 ２ 〃
Ｃｕ粉 ５ 〃
Ｎｉ粉 ２ 〃
炭酸ナトリウム ５ 〃チタン酸カリウ
ム繊維 ＩＱ ＩＩ水
適当量試験結果を第１表に示す。Silicon carbide 5% by weight silicon nitride
10 Mica 5 Alumina 1
15 〃〃 2 5
〃 )) 3 IQ l) Neutral aluminum phosphate 10//Colloidal silica
6 Fe powder 2 Cu powder 5 Ni powder 2 Sodium carbonate 5 Potassium titanate fiber IQ II water
The appropriate amount test results are shown in Table 1.
１直１ニュ 以下の成分を用いる他は、実施例−１を繰り返す。1 shift 1 new Example-1 is repeated except that the following ingredients are used.
窒化珪素 ５重量％安定化酸化ジ
ルコン 五８〃
雲母 ３ 〃アルミナ１
４ 〃
〃 ３ ８ 〃
コロイダルシリカ １５〃
Ｆｅ粉 ２ 〃
Ｃ「粉 ５ 〃
炭酸ナトリウム ８ 〃チタン酸カリウ
ム繊維 ６ 〃水
適当量試験結果を第１表に示す。Silicon nitride 5% by weight stabilized zircon oxide 58 Mica 3 Alumina 1
4 〃 〃 3 8 〃 Colloidal silica 15〃 Fe powder 2 〃 C powder 5 〃 Sodium carbonate 8 〃 Potassium titanate fiber 6 〃 Water
The appropriate amount test results are shown in Table 1.
及五班二五 以下の成分を用いる他は、実施例−１を繰り返す。Group 25 Example-1 is repeated except that the following ingredients are used.
炭化珪素 １８重量％安定化酸化ジ
ルコン ５ 〃
アルミナ１ １０ 〃コロイダルシリ
カ ３ 〃アルミナゾル
１０〃
Ｃｕ粉 ３〃
Ｎｉ粉 ４〃
炭酸ナトリウム １７〃チタン酸カリウ
ム繊維 ８ 〃水
適当量
試験結果を第１表に示す。Silicon carbide 18% by weight stabilized zircon oxide 5 Alumina 1 10 Colloidal silica 3 Alumina sol
10 Cu powder 3 Ni powder 4 Sodium carbonate 17 Potassium titanate fiber 8 Water
The appropriate amount test results are shown in Table 1.
夫産里二ｊ 以下の成分を用いる他は、実施例−１を繰り返す。Rinji Husband Example-1 is repeated except that the following ingredients are used.
炭化珪素 １５重量％窒化珪素
３ 〃雲母
５ 〃
アルミナ１ ５ 〃
〃 ２ ５ 〃
コロイダルシリカ ｌＱ ／／アルミナゾ
ル ２ 〃Ｆｅ粉 ｌ
〃
Ｃｕ粉 ２ 〃
Ｎｉ粉 ４〃
炭酸ナトリウム ７ 〃チタン酸カリウ
ム繊維 １２〃
水 適当量
試験結果を第１表に示す。Silicon carbide 15% by weight silicon nitride
3 Mica
5 〃 Alumina 1 5 〃 〃 2 5 〃 Colloidal silica lQ // Alumina sol 2 〃Fe powder l
Cu powder 2 Ni powder 4 Sodium carbonate 7 Potassium titanate fiber 12 Water Appropriate amount test results are shown in Table 1.
比較例−１ 以下の成分を用いる他は、実施例−１を繰り返す。Comparative example-1 Example-1 is repeated except that the following ingredients are used.
炭化珪素 ２５重量％窒化珪素
５ 〃アルミナ１
１０ 〃Ｊ） ２ １０
））中性リン酸アルミニウム １９〃
Ｃｕ粉 ５ 〃
Ｎｉ粉 ２〃
炭酸ナトリウム ７ 〃水
適当量
試験結果を第１表に示す。Silicon carbide 25% by weight silicon nitride
5 Alumina 1
10 〃J) 2 10
)) Neutral aluminum phosphate 19 Cu powder 5 Ni powder 2 Sodium carbonate 7 Water
The appropriate amount test results are shown in Table 1.
比較例−２ 以下の成分を用いる他は、実施例−１を繰り返す。Comparative example-2 Example-1 is repeated except that the following ingredients are used.
炭化珪素 １５重量％安定化酸化ジ
ルコン ２０〃
アルミナ１ １５ 〃〃 ２
５ 〃
コロイダルシリカ ３ 〃アルミナゾル
１０〃
Ｆｅ粉 ３〃
Ｃｕ粉 ３〃
炭酸ナトリウム ３ 〃水
適当量
試験結果を第１表に示す。Silicon carbide 15% by weight Stabilized zircon oxide 20 Alumina 1 15 2
5 Colloidal silica 3 Alumina sol
10〃 Fe powder 3〃 Cu powder 3〃 Sodium carbonate 3〃 Water
The appropriate amount test results are shown in Table 1.
第１表から判る様に本発明の高温酸化防止塗料は優れた
耐衝撃性を有しており、そしてスケール発生度及び剥離
性に関する優れた性買はかかる優れた耐衝撃性により金
属ローラー搬送中に塗膜の剥離が生じないことが１つの
理由となっている。As can be seen from Table 1, the high-temperature antioxidant coating of the present invention has excellent impact resistance, and its excellent performance in terms of scale generation and peelability is due to this excellent impact resistance during conveyance by metal rollers. One reason is that the coating film does not peel off.
ｇ）成分を除いた成分が本発明の塗料と同じである比較
例−１及び−２（特願昭５９−１８３８３８号）の塗料
は耐衝撃性に難点があり、連続式加熱炉、バッチ炉共に
操入前に一部剥離しスケールの発生が認められる。The paints of Comparative Examples-1 and -2 (Japanese Patent Application No. 183838-1983), which have the same components as the paints of the present invention except for g), have poor impact resistance and cannot be used in continuous heating furnaces or batch furnaces. In both cases, some peeling and scale formation were observed before operation.
本発明の塗料は、上述の如くセラミックを基材とした塗
膜量強度、鋼材表面への密着強度を高めるとともに、中
性で且つ薄い塗膜で熱伝導率が低下しないことから省資
源・作業性・省エネルギー・環境雰囲気改善等多くの成
果を達成する他に、連続式加熱炉の入口付近における結
露小滴による塗膜の損傷の防止も達成してい多。As mentioned above, the paint of the present invention uses ceramic as a base material to increase the strength of the coating film and the adhesion strength to the surface of steel materials, and because it is neutral and has a thin coating that does not reduce thermal conductivity, it saves resources and labor. In addition to achieving many results such as efficiency, energy savings, and improved environmental atmosphere, we have also achieved many successes in preventing damage to paint films caused by small droplets of condensation near the entrance of continuous heating furnaces.
本発明の塗料は、５０μ程度の薄い塗膜でも、充分な酸
化防止効果を示し、スケールの発生を防止及び抑制する
。特殊・高級鋼材（Ｃｕ、村ｉ、Ｃｒ入り）についても
、これらの効果を示す。しかしながら、２００μを越え
ると加熱は伝達が悪化し、炉操業のヒートパターンを変
更し、加熱時間延長もやむなしの悪影響を生むことにな
り好ましくない。The coating material of the present invention exhibits a sufficient antioxidant effect even in a thin coating film of about 50 μm, and prevents and suppresses the occurrence of scale. These effects are also shown for special/high-grade steel materials (Cu, Cr, and Cr-containing). However, if it exceeds 200μ, the heating transmission will deteriorate, the heat pattern of the furnace operation will change, and the extension of the heating time will have an unavoidable adverse effect, which is not preferable.
［発明の効果コ
本発明の塗料は、従来の高温酸化防止塗料にチタン酸カ
リウムｉｌ＋維を混合させているので、この繊維が塗膜
の骨材として作用して塗膜量係合強度が高まり、高温酸
化ガスの浸透が防止されるとともに物理的な衝撃に対し
て強度が高まり、鋼材の熱膨張に追従して塗膜の剥離が
防止されるという効果がある。[Effects of the invention] Since the paint of the present invention mixes potassium titanate il + fibers with the conventional high-temperature antioxidant paint, these fibers act as aggregates for the paint film, increasing the coating strength. This has the effect of preventing penetration of high-temperature oxidizing gases, increasing strength against physical impact, and preventing peeling of the coating film by following the thermal expansion of the steel material.
Claims (5)
、安定化ジルコン、雲母の群の内の少なくとも１種；２
０〜５０重量％、 ｂ）セラミック助材としての以下の３種のアルミナ；２
５〜５０重量％、 アルミナ（１）：α晶が大きく且つ焼結収縮率が小さい
扁平微粒アルミナ、 アルミナ（２）：α化率が高く、焼成収縮が安定してい
る平均粒度１００μ以下の扁平粒状アルミナ、 アルミナ（３）：水分含有量が少なく中ソーダーグレー
ドの易焼結性超微粒アルミナ、 ｃ）バインダーとしての中性リン酸アルミニウム、コロ
イダルシリカ、アルミナゾルの群の内の少なくとも１種
；１０〜４０重量％、ｄ）Ｆｅ、Ｃｕ、ＮｉおよびＣｒ
粉の群の内の少なくとも１種；５〜１０重量％、 ｅ）セラミック焼結促進剤としての炭酸ナトリウム；５
〜３０重量％ ｆ）耐水性の塗膜を形成する重合体および／または共重
合体の水性エマルジョンまたは水溶液；２．５〜１５重
量％（固形分）、及びｇ）骨材として作用し、塗膜間結
合強度を高めるチタン酸カリウム繊維；５〜１５重量％
より組成され、但しａ）〜ｇ）成分の合計が１００重量
％である鋼材用高温酸化防止塗料。(1) a) At least one member from the group consisting of silicon carbide, silicon nitride, stabilized zircon, and mica as a ceramic base material; 2
0 to 50% by weight, b) The following three types of alumina as ceramic auxiliary materials; 2
5 to 50% by weight, Alumina (1): flat fine grain alumina with large α crystals and low sintering shrinkage rate, Alumina (2): flat fine grained alumina with a high α crystallization rate and stable sintering shrinkage rate, with an average particle size of 100μ or less Granular alumina, alumina (3): medium soda grade, easily sinterable ultrafine alumina with low water content, c) at least one member from the group of neutral aluminum phosphate, colloidal silica, and alumina sol as a binder; 10 ~40% by weight, d) Fe, Cu, Ni and Cr
at least one of the group of powders; 5-10% by weight; e) sodium carbonate as ceramic sintering accelerator; 5
~30% by weight f) an aqueous emulsion or aqueous solution of a polymer and/or copolymer that forms a water-resistant coating; 2.5 to 15% by weight (solids); and g) acts as an aggregate and Potassium titanate fiber that increases intermembrane bonding strength; 5-15% by weight
A high-temperature oxidation-inhibiting coating for steel materials, wherein the total of components a) to g) is 100% by weight.
焼結収縮率；５％以下（１６００℃、３時間）の扁平微
粒子、 前記アルミナ（２）が、焼成収縮率；１０％以下（１８
００℃、３時間）、平均粒度；２０μ以上、特に３０〜
６０μの扁平微粒子、 前記アルミナ（３）が、Ｎａ＿２Ｏ含有量；０．２〜０
．３重量％、平均粒度；１μ以下の微粒子であることを
特徴とする特許請求の範囲第１項に記載の高温酸化防止
塗料。(2) the alumina (1) has an average particle size of 1 to 10 μ;
Flat fine particles with a sintering shrinkage rate of 5% or less (1600°C, 3 hours), the alumina (2) has a sintering shrinkage rate of 10% or less (18
00°C, 3 hours), average particle size: 20μ or more, especially 30~
60 μ flat fine particles, the alumina (3) has a Na_2O content of 0.2 to 0
．． The high-temperature antioxidant paint according to claim 1, wherein the high-temperature antioxidant paint contains fine particles of 3% by weight and an average particle size of 1 μm or less.
成分〕を（１．５〜３）：（０．５〜２）：（１〜３）
の重量比で含有することを特徴とする特許請求の範囲第
１項または第２項に記載の高温酸化防止塗料。(3) Alumina (1), (2) and (3) [b)
Ingredients] (1.5-3): (0.5-2): (1-3)
The high-temperature antioxidant paint according to claim 1 or 2, wherein the high-temperature antioxidant paint is contained in a weight ratio of .
ビニルの共重合体、塩化ビニルの単一重合体または塩化
ビニルの共重合体であることを特徴とする特許請求の範
囲第１項〜３項のいずれか１項に記載の高温酸化防止塗
料。(4) Claim 1, wherein the component f) is a vinyl acetate homopolymer, a vinyl acetate copolymer, a vinyl chloride homopolymer, or a vinyl chloride copolymer. The high-temperature antioxidant paint according to any one of items 1 to 3.
エチレン−共重合体または酢酸ビニル／エチレン塩化ビ
ニル−三元共重合体であることを特徴とする特許請求の
範囲第１項〜４項のいずれか１項に記載の高温酸化防止
塗料。(5) Component f) is polyvinyl chloride, vinyl acetate/
The high-temperature antioxidant paint according to any one of claims 1 to 4, which is an ethylene copolymer or a vinyl acetate/ethylene vinyl chloride terpolymer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62117165A JPH0662888B2 (en) | 1987-05-15 | 1987-05-15 | High temperature antioxidant paint for steel |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62117165A JPH0662888B2 (en) | 1987-05-15 | 1987-05-15 | High temperature antioxidant paint for steel |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63284266A true JPS63284266A (en) | 1988-11-21 |
| JPH0662888B2 JPH0662888B2 (en) | 1994-08-17 |
Family
ID=14705060
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62117165A Expired - Lifetime JPH0662888B2 (en) | 1987-05-15 | 1987-05-15 | High temperature antioxidant paint for steel |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0662888B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03243716A (en) * | 1990-02-22 | 1991-10-30 | Nippon Stainless Steel Co Ltd | Surface antioxidant for high-ni-fe alloy |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102005045666A1 (en) * | 2005-09-14 | 2007-03-15 | Itn Nanovation Gmbh | Layer or coating and composition for its production |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57102967A (en) * | 1980-12-18 | 1982-06-26 | Otsuka Chem Co Ltd | Heat-insulating coat composition |
| JPS58198573A (en) * | 1982-05-13 | 1983-11-18 | Otsuka Chem Co Ltd | Wear resistant coating material |
| JPS6038452A (en) * | 1983-08-10 | 1985-02-28 | Otsuka Chem Co Ltd | Vinylidene fluoride resin composition |
| JPS6164813A (en) * | 1984-09-04 | 1986-04-03 | Sumitomo Metal Ind Ltd | High-temperature oxidation preventive paint for steel material |
| JPS61176669A (en) * | 1985-01-30 | 1986-08-08 | Dainichi Seika Kogyo Kk | Paint composition |
-
1987
- 1987-05-15 JP JP62117165A patent/JPH0662888B2/en not_active Expired - Lifetime
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57102967A (en) * | 1980-12-18 | 1982-06-26 | Otsuka Chem Co Ltd | Heat-insulating coat composition |
| JPS58198573A (en) * | 1982-05-13 | 1983-11-18 | Otsuka Chem Co Ltd | Wear resistant coating material |
| JPS6038452A (en) * | 1983-08-10 | 1985-02-28 | Otsuka Chem Co Ltd | Vinylidene fluoride resin composition |
| JPS6164813A (en) * | 1984-09-04 | 1986-04-03 | Sumitomo Metal Ind Ltd | High-temperature oxidation preventive paint for steel material |
| JPS61176669A (en) * | 1985-01-30 | 1986-08-08 | Dainichi Seika Kogyo Kk | Paint composition |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03243716A (en) * | 1990-02-22 | 1991-10-30 | Nippon Stainless Steel Co Ltd | Surface antioxidant for high-ni-fe alloy |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0662888B2 (en) | 1994-08-17 |
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