JP2506981B2 - Hydrogen embrittlement prevention paint - Google Patents
Hydrogen embrittlement prevention paintInfo
- Publication number
- JP2506981B2 JP2506981B2 JP63214011A JP21401188A JP2506981B2 JP 2506981 B2 JP2506981 B2 JP 2506981B2 JP 63214011 A JP63214011 A JP 63214011A JP 21401188 A JP21401188 A JP 21401188A JP 2506981 B2 JP2506981 B2 JP 2506981B2
- Authority
- JP
- Japan
- Prior art keywords
- whiskers
- hydrogen embrittlement
- zinc oxide
- needle
- zinc
- 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 - Lifetime
Links
Landscapes
- Crystals, And After-Treatments Of Crystals (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Paints Or Removers (AREA)
Description
【発明の詳細な説明】 産業上の利用分野 本発明は水素脆性防止塗料に関する。さらに詳しく
は、天然ガス輸送用鋼管やガス貯蔵鋼材など硫化水素を
含む流体と接触する鋼材に塗布し、硫化水素の塗膜表面
から鋼表面への浸透・拡散を遮断する水素脆性防止塗料
に関する。TECHNICAL FIELD The present invention relates to a hydrogen embrittlement prevention coating. More specifically, the present invention relates to a hydrogen embrittlement prevention coating which is applied to a steel material such as a natural gas transportation steel pipe or a gas storage steel material that comes into contact with a fluid containing hydrogen sulfide to block permeation / diffusion of hydrogen sulfide from the coating surface to the steel surface.
従来の技術 この用途の鋼材は一般に、弱酸性下で硫化水素と反応
して、ブリスター(ふくれ)発生や水素脆性を示すた
め、従来よりこれを防止するために、硫化水素と相互作
用する金属粉や金属酸化物を含む熱硬化性塗料が塗布さ
れてきた。Conventional technology Steel materials for this purpose generally react with hydrogen sulfide under weak acidity and show blister generation and hydrogen embrittlement. To prevent this, metal powder that interacts with hydrogen sulfide has been conventionally used. Thermosetting paints containing metal oxides have been applied.
すなわち、金属酸化物としては、鉛丹、一酸化鉛、亜
鉛華、亜酸化銅、酸化第二銅、などの他、酸化カルシウ
ム、酸化バリウム、酸化マグネシウム、酸化ストロンチ
ウム、などのアルカリ土類系などが使用されてきた。ま
た、金属では、亜鉛、銅などが使用されてきた。また、
熱硬化性樹脂としては、アミン硬化エポキシ樹脂、メラ
ミン樹脂硬化エポキシ樹脂などが用いられてきた。That is, as the metal oxide, in addition to lead oxide, lead monoxide, zinc oxide, cuprous oxide, cupric oxide, etc., alkaline earth metals such as calcium oxide, barium oxide, magnesium oxide, strontium oxide, etc. Has been used. As the metal, zinc, copper, etc. have been used. Also,
As the thermosetting resin, amine-cured epoxy resin, melamine resin-cured epoxy resin and the like have been used.
発明が解決しようとする課題 しかるに、硫化水素の浸透・拡散を完全に遮断するた
めには、塗膜にピンホールが無く、耐クラック性が高
く、耐衝撃性の高い、ある程度の厚膜の塗膜が必要であ
ったが、現実には、十分な特性を確保するために、例え
ば亜鉛華の場合は、大きさ0.1〜1μm程度の細かい針
状や粒状亜鉛華を高密度に充填しなければならなかっ
た。そのため塗膜は、もろくなり、耐衝撃性や耐クラッ
ク性の高い塗膜を得ることが難かしく、初期状態で十分
な特性が確保できても、長期間使用時に結果的にクラッ
クが入り水素脆性防止塗料の役目を果さなくなるのが一
般的であった。However, in order to completely block the permeation / diffusion of hydrogen sulfide, there is no pinhole in the coating film, the crack resistance is high, and the impact resistance is high. Although a film was required, in order to ensure sufficient characteristics, in the case of zinc white, for example, fine needle-like or granular zinc white having a size of about 0.1 to 1 μm must be packed at a high density. did not become. Therefore, the coating becomes brittle, and it is difficult to obtain a coating with high impact resistance and crack resistance, and even if sufficient properties can be secured in the initial state, as a result, cracks will occur after long-term use and hydrogen embrittlement It was common to lose the role of anti-paint.
課題を解決するための手段 本発明は、上記課題に対して鋭意研究の結果、以下の
手段により、高反応性のフィラーを低密度で均一に膜厚
塗膜中に均一に分布させ、耐衝撃性、耐クラック性それ
に水素脆性防止効果の優れた塗料を提供するものであ
る。Means for Solving the Problems The present invention has been made as a result of earnest research on the above problems, and by the following means, a highly reactive filler is uniformly distributed in a thin film coating film at a low density to obtain an impact resistance The present invention provides a coating having excellent properties, crack resistance, and hydrogen brittleness prevention effect.
すなわち、本発明は、酸化亜鉛ウィスカーが組成物に
配合されており、かつ前記酸化亜鉛ウィスカーは核部と
この核部から異なる複数軸方向に伸びた針状結晶部から
なり、前記針状結晶部の基部の径が0.7〜14μmであ
り、前記針状結晶部の基部から先端までの長さが3〜20
0μmであることを特長とする。That is, the present invention is that the zinc oxide whiskers are blended in the composition, and the zinc oxide whiskers are composed of a core portion and needle-like crystal portions extending in different axial directions from the core portion, and the needle-like crystal portion. Has a diameter of 0.7 to 14 μm, and a length from the base to the tip of the needle-shaped crystal part is 3 to 20.
The feature is that it is 0 μm.
本発明に用いる酸化亜鉛ウィスカーは、表面に酸化皮
膜を有する金属亜鉛粉末を酸素を含む雰囲気下で加熱処
理して生成させることができる。得られた酸化亜鉛ウィ
スカーは、みかけの嵩比重0.02〜0.1を有し、70wt%以
上の高収率で極めて量産的である。第1図はその電子顕
微鏡写真を示す。これによると上記の形態的、寸法的特
長が明確に認められる。(以下、テトラポット構造と表
記する。) ところで、酸化亜鉛ウィスカーの針状結晶部が3軸あ
るいは、2軸、さらには1軸のものが混入する場合があ
るが、これは4軸のものの一部が折損したものと考えら
れる。また板状晶のものが混入する場合もある。これら
のウィスカーのX線回折図をとると、すべて酸化亜鉛の
ピークを示し、一方、電子線回折分布の結果も、転移、
格子欠陥の少ない単結晶性を示した。また、不純物の含
有量も少なく、原子吸光分析の結果、酸化亜鉛が99.98
%であった。The zinc oxide whiskers used in the present invention can be produced by heat-treating metallic zinc powder having an oxide film on its surface in an atmosphere containing oxygen. The obtained zinc oxide whiskers have an apparent bulk specific gravity of 0.02 to 0.1, and are highly mass-producible with a high yield of 70 wt% or more. FIG. 1 shows the electron micrograph. According to this, the above-mentioned morphological and dimensional features are clearly recognized. (Hereinafter, it will be referred to as a tetrapot structure.) By the way, the needle-shaped crystal part of the zinc oxide whiskers may be mixed with triaxial, biaxial, or even uniaxial ones. It is thought that the part was broken. In addition, plate crystals may be mixed in. The X-ray diffractograms of these whiskers all show the peaks of zinc oxide, while the electron diffraction distribution results also show the transition,
It showed single crystallinity with few lattice defects. In addition, the content of impurities is low, and as a result of atomic absorption spectrometry, zinc oxide is 99.98.
%Met.
水素脆性防止塗料の特性の面から、大き過ぎる(長さ
200μmより大で径が14μmより大)ウィスカーが大き
な割合を占める系では、テトラポット構造が処理工程で
壊れる確率が高くなり、塗膜の耐衝撃性が低下し、ま
た、硫化水素と反応すべき面積が低下するので好ましく
ない。一方、小さ過ぎる(長さが3μmより小さく、径
が0.7μmより小)ウィスカーが大きな割合を占める系
では、低密度(低コンテント)配合時には、元来、酸化
亜鉛の比重が大きい(5.7)ため沈降分離し、均一分散
が難かしくなり水素脆性防止性が悪くなるとともに、耐
衝撃性および耐クラック性が低下し、好ましくない。In view of the characteristics of hydrogen embrittlement prevention paint, it is too large (length
In a system with a large proportion of whiskers (larger than 200 μm and diameter larger than 14 μm), the probability that the tetrapot structure will be destroyed in the treatment process will decrease the impact resistance of the coating film, and it should react with hydrogen sulfide. The area is reduced, which is not preferable. On the other hand, in a system in which whiskers are too small (length is smaller than 3 μm and diameter is smaller than 0.7 μm) and a large proportion of whiskers are contained, when the low density (low content) is blended, the specific gravity of zinc oxide is originally large (5.7). Sedimentation and separation make it difficult to uniformly disperse, the hydrogen embrittlement prevention property deteriorates, and the impact resistance and crack resistance decrease, which is not preferable.
マトリックスには、従来より用いられている樹脂がす
べて適用でき、特に、アミン硬化エポキシ樹脂、メラミ
ン樹脂硬化エポキシ樹脂等のエポキシ樹脂類をはじめと
する熱硬化性樹脂が適用できる。For the matrix, all conventionally used resins can be applied, and in particular, thermosetting resins including epoxy resins such as amine-cured epoxy resin and melamine resin-cured epoxy resin can be used.
マトリックスに対する酸化亜鉛ウィスカーの配合割合
は特に限定されるものではないが、配合量が少な過ぎる
場合は水素脆性防止性の目的が達せられず、必要以上に
多量であると塗料の粘度が上がり過ぎ使用に耐えなくな
るので良くない。そのため、水素脆性防止性の適用目的
に応じて好ましい配合割合がある。即ち、ウィスカーの
大きさと、樹脂の種類や使用目的にもよるが、一般に0.
5vol%〜20vol%が使用され、特に3〜15vol%で極めて
優れた特性が得られる。The blending ratio of zinc oxide whiskers to the matrix is not particularly limited, but if the blending amount is too small, the purpose of preventing hydrogen embrittlement cannot be achieved, and if it is unnecessarily large, the viscosity of the coating will increase and it will be used. It's not good because I can't stand it. Therefore, there is a preferable blending ratio depending on the purpose of applying the hydrogen embrittlement preventing property. That is, it generally depends on the size of the whiskers, the type of resin, and the purpose of use, but is generally 0.
5 vol% to 20 vol% is used, and particularly 3 to 15 vol% gives extremely excellent characteristics.
さらに、酸化亜鉛ウィスカーと他のフィラー、例え
ば、ガラス繊維、ガラスフレーク、ガラスチョップ、タ
ルク、マイカ、アルミナ、シリカ、SiCウィスカー、チ
タン酸カリウムウィスカー等と併用することも可能であ
る。Furthermore, it is also possible to use zinc oxide whiskers in combination with other fillers such as glass fibers, glass flakes, glass chops, talc, mica, alumina, silica, SiC whiskers, potassium titanate whiskers and the like.
作 用 本発明の酸化亜鉛ウィスカーはテトラポット構造であ
るため、各ウィスカーが積み重なると骨格の安定した嵩
密度の極めて小さい疎な空間を実現することができる。
この構造を利用することにより低配合(低密度)であり
ながら均一に分散した厚膜塗膜を容易に得ることができ
る。Work Since the zinc oxide whiskers of the present invention have a tetrapot structure, stacking the whiskers makes it possible to realize a sparse space in which the skeleton is stable and the bulk density is extremely small.
By utilizing this structure, it is possible to easily obtain a thick coating film having a low composition (low density) and uniformly dispersed.
またこの塗膜は低配合であるため樹脂分が多いこと
と、それに、テトラポット状酸化亜鉛ウィスカー自体の
衝撃吸収作用により耐衝撃性が高くなる。Further, since this coating film has a low content, it has a large amount of resin, and in addition, the tetrapod-shaped zinc oxide whiskers themselves have high impact resistance due to the impact absorbing action.
さらに、この塗膜は、ウィスカーによる塗膜の補強効
果により耐クラック性が向上する。Furthermore, the coating film has improved crack resistance due to the reinforcing effect of the coating film by whiskers.
次に、このテトラポット状酸化亜鉛ウィスカーは、各
脚が結晶学的なC軸方向に伸びた純粋な単結晶であり、
C軸に平行な面に亜鉛面が存在し、この面は硫化水素に
極めて活性である。テトラポット状酸化亜鉛ウィスカー
はこの活性な亜鉛面の割合が極めて大きいため水素脆性
防止効果が特に大きくなる。Next, this tetrapot zinc oxide whisker is a pure single crystal in which each leg extends in the crystallographic C-axis direction,
There is a zinc surface on a plane parallel to the C-axis, and this surface is extremely active for hydrogen sulfide. Since the tetrapot-like zinc oxide whiskers have an extremely large proportion of this active zinc surface, the effect of preventing hydrogen embrittlement becomes particularly large.
実施例 以下に本発明を実施例により具体的に説明するが、本
発明はこれらの実施例のみに限定されるものではない。Examples The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
実施例1 大きめのテトラポット状酸化亜鉛ウィスカー(針状結
晶部の基部から先端までの長さ:100〜200μm;基部の径:
5〜14μm)を用意し、メラミン樹脂硬化エポキシ樹脂
に5vol%配合して十分混合した後、鋼板上に塗布(厚
さ:500μm)した後、硬化し、評価試験を実施した。Example 1 Large tetrapod-shaped zinc oxide whiskers (length from the base to the tip of the needle-shaped crystal part: 100 to 200 μm; diameter of the base part:
5 to 14 μm) was prepared, and 5 vol% was mixed with a melamine resin-cured epoxy resin and sufficiently mixed, and then applied on a steel plate (thickness: 500 μm), cured, and an evaluation test was performed.
評価項目は、初期の耐衝撃性試験とヒートサイクル
(−20℃/4Hr+50℃/4Hr)後の、塗膜に生ずるクラック
観察と水素脆性試験によるブリスター(ふくれ)の発生
状態観察であった。その結果を第1表に示した。The evaluation items were the initial impact resistance test and the observation of cracks occurring in the coating film after the heat cycle (-20 ° C / 4Hr + 50 ° C / 4Hr) and the blister (blister) generation state by the hydrogen embrittlement test. The results are shown in Table 1.
その後、塗膜中のウィスカーの状態をSEM観察したと
ころ、あるテトラポット状ウィスカーは折損して、1軸
や2軸や3軸の針状結晶に変化していたが、完全なテト
ラポット状ウィスカーも観察された。After that, when the state of the whiskers in the coating film was observed by SEM, one tetrapot-shaped whisker was broken and changed into a uniaxial, biaxial, or triaxial needle-shaped crystal. Was also observed.
実施例2〜3 大きさの中位と小さめのテトラポット状ウィスカーを
用いて実施例1と全く同じ試験を実施し、その結果を第
1表に示した。Examples 2 to 3 Exactly the same test as in Example 1 was carried out using medium-sized and small-sized tetrapot-shaped whiskers, and the results are shown in Table 1.
比較例1〜2 極めて大きなウィスカーと極めて小さなウィスカーを
用いて実施例1と全く同じ試験を実施し、その結果を第
1表に示した。Comparative Examples 1-2 Using the extremely large whiskers and the extremely small whiskers, the same tests as in Example 1 were carried out, and the results are shown in Table 1.
比較例1の塗膜中のテトラポット状ウィスカーの大部
分は折損して、1軸の針状ウィスカーに変化していた。Most of the tetrapot-shaped whiskers in the coating film of Comparative Example 1 were broken and changed into uniaxial needle-shaped whiskers.
比較例3〜6 形状が粒状と針状の市販の亜鉛華を用いて実施例1と
全く同じ試験を実施し、その結果を第1表に示した。Comparative Examples 3 to 6 The same test as in Example 1 was carried out using commercially available zinc white having a granular or acicular shape, and the results are shown in Table 1.
発明の効果 水素脆性防止塗料が必要な天然ガス輸送用鋼管やガス
貯蔵などの需要が増加している昨今、合わせてその腐食
に対する安全対策が叫ばれている。本発明はその要求に
呼応して発明された高性能な塗料であるため、その産業
性は甚だ大なるものがある。 EFFECTS OF THE INVENTION In recent years, the demand for steel pipes for natural gas transportation and gas storage, which require hydrogen embrittlement prevention paints, is increasing. Since the present invention is a high-performance paint invented in response to the demand, its industriality is extremely great.
第1図は酸化亜鉛ウィスカーの結晶の構造を示す電子顕
微鏡写真である。FIG. 1 is an electron micrograph showing the structure of zinc oxide whisker crystals.
フロントページの続き (72)発明者 浜辺 猛 大阪府門真市大字門真1006番地 松下電 器産業株式会社内 (72)発明者 北野 基 大阪府門真市大字門真1006番地 松下電 器産業株式会社内Front page continued (72) Inventor Takeshi Hamabe 1006 Kadoma, Kadoma City, Osaka Prefecture Matsushita Electric Industrial Co., Ltd. (72) Moto Ki Kitano, 1006 Kadoma, Kadoma City, Osaka Prefecture Matsushita Electric Industrial
Claims (2)
おり、かつ前記酸化亜鉛ウィスカーは核部とこの核部か
ら異なる複数軸方向に伸びた針状結晶部からなり、前記
針状結晶部の基部の径が0.7〜14μmであり、前記針状
結晶部の基部から先端までの長さが3〜200μmである
ことを特長とする水素脆性防止塗料。1. A zinc oxide whisker is compounded in a composition, and the zinc oxide whisker comprises a core portion and needle-shaped crystal portions extending in different axial directions from the core portion. A hydrogen embrittlement prevention coating characterized in that the base has a diameter of 0.7 to 14 µm, and the needle-like crystal portion has a length from the base to the tip of 3 to 200 µm.
囲第1項記載の水素脆性防止塗料。2. The hydrogen embrittlement preventive coating composition according to claim 1, wherein the number of axes in the plural axis directions is 4.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP63214011A JP2506981B2 (en) | 1988-08-29 | 1988-08-29 | Hydrogen embrittlement prevention paint |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP63214011A JP2506981B2 (en) | 1988-08-29 | 1988-08-29 | Hydrogen embrittlement prevention paint |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH0260967A JPH0260967A (en) | 1990-03-01 |
JP2506981B2 true JP2506981B2 (en) | 1996-06-12 |
Family
ID=16648791
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP63214011A Expired - Lifetime JP2506981B2 (en) | 1988-08-29 | 1988-08-29 | Hydrogen embrittlement prevention paint |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP2506981B2 (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105189671A (en) * | 2013-04-10 | 2015-12-23 | 威士伯采购公司 | Sour gas resistant coating |
-
1988
- 1988-08-29 JP JP63214011A patent/JP2506981B2/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
JPH0260967A (en) | 1990-03-01 |
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