JPH041048B2 - - Google Patents
Info
- Publication number
- JPH041048B2 JPH041048B2 JP58152677A JP15267783A JPH041048B2 JP H041048 B2 JPH041048 B2 JP H041048B2 JP 58152677 A JP58152677 A JP 58152677A JP 15267783 A JP15267783 A JP 15267783A JP H041048 B2 JPH041048 B2 JP H041048B2
- Authority
- JP
- Japan
- Prior art keywords
- selective absorption
- treatment
- stainless steel
- solar water
- water heater
- 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
- 229910001220 stainless steel Inorganic materials 0.000 claims description 11
- 239000010935 stainless steel Substances 0.000 claims description 10
- 238000000137 annealing Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 3
- 238000010521 absorption reaction Methods 0.000 description 23
- 229910000831 Steel Inorganic materials 0.000 description 11
- 239000010959 steel Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 8
- 239000012528 membrane Substances 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- JHWIEAWILPSRMU-UHFFFAOYSA-N 2-methyl-3-pyrimidin-4-ylpropanoic acid Chemical compound OC(=O)C(C)CC1=CC=NC=N1 JHWIEAWILPSRMU-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- KPVWDKBJLIDKEP-UHFFFAOYSA-L dihydroxy(dioxo)chromium;sulfuric acid Chemical compound OS(O)(=O)=O.O[Cr](O)(=O)=O KPVWDKBJLIDKEP-UHFFFAOYSA-L 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- MCUDGYVHPADJBD-UHFFFAOYSA-L hydroxy-(hydroxy(dioxo)chromio)oxy-dioxochromium sulfuric acid Chemical compound OS(O)(=O)=O.O[Cr](=O)(=O)O[Cr](O)(=O)=O MCUDGYVHPADJBD-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- JPJALAQPGMAKDF-UHFFFAOYSA-N selenium dioxide Chemical compound O=[Se]=O JPJALAQPGMAKDF-UHFFFAOYSA-N 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
Classifications
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F24—HEATING; RANGES; VENTILATING
- F24S—SOLAR HEAT COLLECTORS; SOLAR HEAT SYSTEMS
- F24S70/00—Details of absorbing elements
- F24S70/20—Details of absorbing elements characterised by absorbing coatings; characterised by surface treatment for increasing absorption
- F24S70/25—Coatings made of metallic material
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F24—HEATING; RANGES; VENTILATING
- F24S—SOLAR HEAT COLLECTORS; SOLAR HEAT SYSTEMS
- F24S70/00—Details of absorbing elements
- F24S70/20—Details of absorbing elements characterised by absorbing coatings; characterised by surface treatment for increasing absorption
- F24S70/225—Details of absorbing elements characterised by absorbing coatings; characterised by surface treatment for increasing absorption for spectrally selective absorption
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/40—Solar thermal energy, e.g. solar towers
Landscapes
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Thermal Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Combustion & Propulsion (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Heat Treatment Of Sheet Steel (AREA)
Description
【発明の詳細な説明】
本発明は、太陽熱選択吸収膜用ステンレス鋼板
およびその製造方法に関するものである。
ステンレス冷延鋼板の表面仕上げは、No.３〜No.
８バフ研磨仕上げの他に、還元性ガス（窒素＋水
素）雰囲気中で光輝焼鈍（以下、BAと称す）処
理したBA仕上げが利用される。
ところで、最近の製鋼技術の進歩により、極低
炭Mo添加フエライト・ステンレス鋼である
SUS444（18Cr−2Mo）BA仕上げ鋼板が生産され
るようになり、低廉なステンレス鋼が得られるよ
うになつた。このBA仕上げ鋼板の主要用途が太
陽熱温水器用集熱板であり、BA仕上げ鋼板表面
に、集熱効率を上げるために、太陽熱選択吸収膜
を形成させる化学処理がなされる。ところが、
BA処理条件の変動から、上記の選択吸収膜の形
成処理が均一かつ確実にできないケースが生じ、
著しい製品歩留りの低下を来している。
そこで、本発明者等は、BA仕上げ鋼板の表面
性状とBA処理条件について鋭意研究を重ねた結
果、BA処理を特定の条件下で行えば、確実に均
一な選択吸収膜の形成処理を行うことができる鋼
板が得られることを見出し、本発明に至つた。
本発明によるBA処理方法によれば、太陽熱集
熱板用ステンレス鋼板を得ることができ、製品の
歩留り向上による生産の効率化に大きく寄与す
る。
太陽熱温水器集熱板の選択処理膜形成処理は表
面処理の一種で、110℃以下の温度域において、
例えば、硫酸浴、クロム酸−硫酸浴、重クロム酸
−硫酸浴や、これらの酸性浴に酸化セレンやリン
酸を添加した酸性混合溶液中に浸漬することによ
り、ステンレス鋼表面に皮膜を析出形成させる方
法である。この処理工程で、ステンレス鋼板表面
に化学反応で暗青色の皮膜を形成する。従つて、
この皮膜形成が確実にできるか否かは、上記溶液
中におけるステンレス鋼板表面の化学反応の反応
速度に依存する。すなわち、これはBA仕上げ表
面皮膜の安定性に起因し、この皮膜の安定性が良
い程、選択吸収膜形成反応は進行し難くなる。
本発明者等は、表面皮膜の形態分析が可能であ
るＸ線光電子分光分析（ESCA）により、良好な
選択吸収膜のできる鋼板と良好な選択吸収膜ので
きない鋼板表面の分析を行い、表−１に示すよう
な結果を得た。その結果、良好な選択吸収膜ので
きる鋼板の場合、選択吸収膜形成処理反応にあず
かる鋼板表面の高々50Åまでの範囲で、Fe、Cr、
Mo等の金属元素が単体で、またニオブはNbOと
いう還元された状態で存在することが判明し、確
実に選択吸収膜処理を行うためには、BA処理に
て、鋼板表面に酸化物でなく還元された状態で存
在させることが必須条件であるとの知見を得た。
この知見に基づき種々の検討を重ねた結果、上
述のような還元された状態を有する表面をBA処
理で得さしむる条件を見出し、太陽熱温水器集熱
用ステンレス鋼板の製造方法を完成した。
本発明で行う光輝焼鈍は、次の条件を満足すれ
ば、確実に良好な太陽熱集熱用選択吸収膜の形成
処理を可能ならしめる。焼鈍雰囲気としては、ア
ンモニア分解ガス、水素などが用いられる。そし
て、その露点温度をｘ（℃）、焼鈍温度をｙ（℃）
とした時、
800≦ｙ≦1100
−70≦ｘ≦−30
10x＋1300≦ｙ
なる条件を満足する範囲内で光輝焼鈍を行えば良
い。選択吸収膜の形成処理は、（10〜50wt％）硫
酸＋（０〜30wt％）重クロム酸ナトリウム溶液
（80℃）中に最大30分間浸漬して行なつた。
以上のように、本発明において焼鈍条件を上記
の如く限定する理由は、添付図面に示す下記の実
施例の結果によるものであるが、その条件は、選
択吸収膜形成処理の良、不良との対応およびBA
処理後選択吸収膜形成処理までの間の耐発銹性と
いう観点から決定した。
雰囲気ガスとして水素を用いてその露点を変
え、またBA処理温度を変えた条件下で、BA処
理を行なつた。得られたBA処理鋼板について、
選択吸収膜形成処理の良・不良の判定および耐発
銹性試験を行なつた。その結果を添付図面にグラ
フとして示す。このグラフに示される斜線を付し
たＩの領域が、BA処理後選択吸収膜処理までの
間に発銹の恐れがなく、良好な選択吸収膜を形成
できる本発明の範囲である。領域は発銹により
良好な選択吸収膜ができない範囲であり、領域
は発銹はないが、良好な選択吸収膜ができない範
囲である。従つて、添付図面のグラフにおける領
域における条件により光輝焼鈍を施すことによ
り、鋼板表面が還元状態の金属元素濃化層を有す
るよう処理され、BA処理後選択吸収膜処理まで
の間に発銹もなく、良好な選択吸収膜を形成する
ことができ、製品の歩留り向上に多大な寄与をな
す。
なお、選択吸収膜の形成処理は、前述した多く
の他の酸性浴を用いても同様の結果が得られた。
添付図面に示す記号内の数字は後述する方法によ
り測定した電流密度の値であり、80ｍＡ／cm2以上
のものが良好な選択吸収膜が得られた。
選択吸収膜の適否の判定は、特願昭58−80664
号に開示されているように、10〜50wt％の硫酸
および０〜30wt％の重クロム酸ナトリウムを含
む水溶液を用い、15〜50℃の温度で、電位掃引速
度50ｍＶ／min以下の条件でアノード分極曲線を
測定し、その値が80ｍＡ／cm2を越えたものを適材
とした。
また、耐発銹性はJIS Ｚ 2371に規定されるよ
うに、35℃、５％食塩水中100時間の塩水噴霧試
験を行い、表面に発銹があるか否かを目視判定し
た。
【表】DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a stainless steel plate for a solar heat selective absorption membrane and a method for manufacturing the same. The surface finish of cold-rolled stainless steel sheets is No. 3 to No.
8 In addition to the buff polishing finish, a BA finish, which is bright annealed (hereinafter referred to as BA) in a reducing gas (nitrogen + hydrogen) atmosphere, is used. By the way, with recent advances in steelmaking technology, ultra-low carbon Mo-added ferritic stainless steel has become available.
SUS444 (18Cr-2Mo) BA-finished steel sheets began to be produced, making it possible to obtain inexpensive stainless steel. The main use of this BA-finished steel sheet is as a heat collection plate for solar water heaters, and the surface of the BA-finished steel sheet is chemically treated to form a solar heat selective absorption film in order to increase heat collection efficiency. However,
Due to variations in BA processing conditions, there may be cases where the selective absorption film formation process described above cannot be performed uniformly and reliably.
This results in a significant decrease in product yield. Therefore, as a result of extensive research into the surface properties of BA-finished steel sheets and BA treatment conditions, the present inventors have found that if BA treatment is performed under specific conditions, a uniform selective absorption film can be reliably formed. The present inventors have discovered that a steel plate can be obtained, which has led to the present invention. According to the BA treatment method of the present invention, a stainless steel plate for a solar heat collector plate can be obtained, which greatly contributes to production efficiency by improving product yield. Selective treatment of solar water heater heat collector plate Film formation treatment is a type of surface treatment, and in the temperature range of 110℃ or less,
For example, a film can be deposited on the surface of stainless steel by immersing it in a sulfuric acid bath, a chromic acid-sulfuric acid bath, a dichromic acid-sulfuric acid bath, or an acidic mixed solution in which selenium oxide and phosphoric acid are added to these acidic baths. This is the way to do it. In this treatment process, a dark blue film is formed on the surface of the stainless steel plate through a chemical reaction. Therefore,
Whether or not this film can be formed reliably depends on the reaction rate of the chemical reaction on the surface of the stainless steel sheet in the solution. That is, this is due to the stability of the BA finished surface film, and the better the stability of this film, the more difficult it is for the selective absorption film forming reaction to proceed. The present inventors used X-ray photoelectron spectroscopy (ESCA), which can analyze the morphology of surface films, to analyze the surfaces of steel sheets with good selective absorption films and steel sheets with no good selective absorption films. The results shown in 1 were obtained. As a result, in the case of a steel sheet that can form a good selective absorption film, Fe, Cr,
It has been discovered that metal elements such as Mo exist as a single substance, and niobium exists in a reduced state called NbO.In order to ensure selective absorption film treatment, BA treatment must be performed to prevent oxides from forming on the surface of the steel sheet. It was found that it is essential to exist in a reduced state. As a result of various studies based on this knowledge, we found the conditions under which a surface with the above-mentioned reduced state can be obtained by BA treatment, and completed a method for manufacturing stainless steel sheets for solar water heater heat collection. The bright annealing performed in the present invention can reliably form a good selective absorption film for collecting solar heat if the following conditions are satisfied. As the annealing atmosphere, ammonia decomposition gas, hydrogen, etc. are used. Then, the dew point temperature is x (℃) and the annealing temperature is y (℃).
Bright annealing may be performed within a range that satisfies the following conditions: 800≦y≦1100 −70≦x≦−30 10x+1300≦y. The selective absorption membrane formation treatment was performed by immersing it in a (10-50 wt%) sulfuric acid + (0-30 wt%) sodium dichromate solution (80°C) for a maximum of 30 minutes. As mentioned above, the reason why the annealing conditions are limited as described above in the present invention is due to the results of the following examples shown in the attached drawings, but the conditions are determined depending on whether the selective absorption film forming process is good or bad. Correspondence and BA
This was determined from the viewpoint of rust resistance after the treatment and before the selective absorption film formation treatment. BA treatment was carried out under conditions in which hydrogen was used as the atmospheric gas, its dew point was varied, and the BA treatment temperature was varied. Regarding the obtained BA treated steel plate,
Judgment as to whether the selective absorption film formation process was good or bad and a rust resistance test were conducted. The results are shown as graphs in the attached drawings. The shaded area I shown in this graph is the range of the present invention in which there is no risk of rusting between the BA treatment and the selective absorption membrane treatment and a good selective absorption membrane can be formed. The region is a range where a good selective absorption film cannot be formed due to rusting, and the region is a range where there is no rusting but a good selective absorption film cannot be formed. Therefore, by performing bright annealing under the conditions in the area shown in the graph of the attached drawing, the surface of the steel sheet is treated to have a metal element concentration layer in a reduced state, and rusting is also prevented between BA treatment and selective absorption film treatment. Therefore, it is possible to form a good selective absorption film, which greatly contributes to improving the yield of products. Note that similar results were obtained in the selective absorption membrane formation treatment using many of the other acid baths mentioned above.
The numbers in the symbols shown in the attached drawings are the values of current density measured by the method described below, and a selective absorption membrane with a good quality was obtained when the current density was 80 mA/cm 2 or more. The suitability of selective absorption membranes can be determined in Japanese Patent Application No. 58-80664.
As disclosed in the above issue, an anode was prepared using an aqueous solution containing 10 to 50 wt% sulfuric acid and 0 to 30 wt% sodium dichromate at a temperature of 15 to 50°C and a potential sweep rate of 50 mV/min or less. The polarization curve was measured, and those whose value exceeded 80 mA/cm 2 were considered suitable materials. Further, as specified in JIS Z 2371, the rust resistance was determined by performing a salt spray test in 5% saline at 35°C for 100 hours, and visually determining whether or not there was any rust on the surface. 【table】
添付図面は、雰囲気ガスの露点とBA処理温度
との関係を示すグラフである。
The attached drawing is a graph showing the relationship between the dew point of the atmospheric gas and the BA treatment temperature.
Claims (1)
に還元状態の金属元素濃化層を有することを特徴
とする太陽熱温水器用集熱板。 ２ 多くても深さ50Åまでのステンレス鋼板表面
に還元状態の金属元素濃化層を有する太陽熱温水
器用集熱板を製造するに際し、雰囲気ガスの露点
をｘ（℃）、光輝焼鈍温度をｙ（℃）とした時、次
の条件 800≦ｙ≦1100 −70≦ｘ≦−30 10x＋1300≦ｙ を満足する範囲で光輝焼鈍処理を行うことを特徴
とする太陽熱温水器用集熱板の製造方法。[Claims] 1. A heat collecting plate for a solar water heater, characterized in that it has a metal element concentrated layer in a reduced state on the surface of a stainless steel plate up to a depth of at most 50 Å. 2. When manufacturing a heat collector plate for a solar water heater that has a metal element concentrated layer in a reduced state on the surface of a stainless steel plate up to a depth of at most 50 Å, the dew point of the atmospheric gas is set to x (°C), and the bright annealing temperature is set to y ( ℃), a method for producing a heat collector plate for a solar water heater, characterized in that bright annealing is performed in a range that satisfies the following conditions: 800≦y≦1100 −70≦x≦−30 10x+1300≦y.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58152677A JPS6044772A (en) | 1983-08-22 | 1983-08-22 | Heat collecting plate for solar energy-powered hot water supplyer and its manufacture |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58152677A JPS6044772A (en) | 1983-08-22 | 1983-08-22 | Heat collecting plate for solar energy-powered hot water supplyer and its manufacture |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6044772A JPS6044772A (en) | 1985-03-09 |
| JPH041048B2 true JPH041048B2 (en) | 1992-01-09 |
Family
ID=15545692
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58152677A Granted JPS6044772A (en) | 1983-08-22 | 1983-08-22 | Heat collecting plate for solar energy-powered hot water supplyer and its manufacture |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6044772A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101607789B1 (en) * | 2011-11-22 | 2016-03-30 | 신닛테츠스미킨 카부시키카이샤 | Ferritic heat-resistant steel, and manufacturing method for same |
-
1983
- 1983-08-22 JP JP58152677A patent/JPS6044772A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6044772A (en) | 1985-03-09 |
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