JPH02305975A - High corrosion resistant steel plated by zn-mg-fe alloy - Google Patents
High corrosion resistant steel plated by zn-mg-fe alloyInfo
- Publication number
- JPH02305975A JPH02305975A JP12599589A JP12599589A JPH02305975A JP H02305975 A JPH02305975 A JP H02305975A JP 12599589 A JP12599589 A JP 12599589A JP 12599589 A JP12599589 A JP 12599589A JP H02305975 A JPH02305975 A JP H02305975A
- Authority
- JP
- Japan
- Prior art keywords
- steel
- plated
- alloy
- layer
- corrosion resistance
- 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.)
- Pending
Links
- 229910000640 Fe alloy Inorganic materials 0.000 title description 2
- 239000010935 stainless steel Substances 0.000 title description 2
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 32
- 239000010959 steel Substances 0.000 claims abstract description 32
- 238000007747 plating Methods 0.000 claims abstract description 30
- 230000007797 corrosion Effects 0.000 claims abstract description 16
- 238000005260 corrosion Methods 0.000 claims abstract description 16
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 14
- 239000000956 alloy Substances 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 229910019089 Mg-Fe Inorganic materials 0.000 claims abstract description 4
- 239000000463 material Substances 0.000 claims description 9
- 239000012535 impurity Substances 0.000 claims description 2
- 229910009369 Zn Mg Inorganic materials 0.000 abstract description 8
- 229910007573 Zn-Mg Inorganic materials 0.000 abstract description 8
- 238000000034 method Methods 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 5
- 238000010438 heat treatment Methods 0.000 abstract description 5
- 229910052742 iron Inorganic materials 0.000 abstract description 3
- 238000001771 vacuum deposition Methods 0.000 abstract description 3
- 230000002411 adverse Effects 0.000 abstract description 2
- 239000003513 alkali Substances 0.000 abstract description 2
- 230000001070 adhesive effect Effects 0.000 abstract 1
- 239000011261 inert gas Substances 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 229910000861 Mg alloy Inorganic materials 0.000 description 5
- 239000003973 paint Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000002585 base Substances 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- 229910001335 Galvanized steel Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241000221535 Pucciniales Species 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000010960 cold rolled steel Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 239000008397 galvanized steel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Landscapes
- Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)
- Physical Vapour Deposition (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は塩水散布環境下の様な高腐食性条件下において
も優れた耐食性を発揮するＺｎ−Ｍｇ−Ｆｅ合金めっき
鋼材に関するものである。尚本発明の鋼材は板、線、棒
、パイプ等の如何を問わないが、以下板材を代表例に取
上げて説明する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a Zn-Mg-Fe alloy plated steel material that exhibits excellent corrosion resistance even under highly corrosive conditions such as a salt water spray environment. Although the steel material of the present invention may be a plate, wire, rod, pipe, etc., the following description will be made using a plate material as a representative example.
［従来の技術］
耐食性鋼板としては色々なめつｈｍ板が知られており、
中でもＺｎめっき鋼板はもっとも汎用的な鋼板として大
量に生産され、自動車、家庭用電気機器、建築材料の分
野で賞月されている。[Prior art] Various slick hm plates are known as corrosion-resistant steel plates.
Among them, Zn-plated steel sheets are the most widely used steel sheets and are produced in large quantities, and are prized in the fields of automobiles, household electrical equipment, and building materials.
しかしながらＺｎめっき鋼板は如何なる腐食環境にも耐
え得るという訳ではなく、例えば寒冷地で行なわれてい
る路盤凍結防止用の塩水散布条件の下では自動車用外板
として使用されているＺｎめっき鋼板がかなり早く発錆
することが分かってきた。However, Zn-plated steel sheets cannot withstand any kind of corrosive environment; for example, under the conditions of salt water spraying to prevent roadbeds from freezing in cold regions, Zn-plated steel sheets used as outer panels of automobiles are subject to considerable damage. I've learned that it rusts quickly.
そこでＺｎめっきを改良することが研究され、例えば溶
融Ｚｎめっき後に加熱処理を施してＺｎめっき層と素地
鉄を合金化させるという合金化溶融亜鉛めっき鋼板が開
発された。このめっき鋼板は耐食性、塗膜密着性、スポ
ット溶接性等の緒特性が優れている′為、従来の単純Ｚ
ｎめっき鋼板にとって代って主流材料となっているが、
耐食性において未だ問題が残されている。特に前記寒冷
条件下で行なわれている塩水散布環境での耐食性につい
ては、例えば自動車外板における穴あき防止期間１０年
、外観錆防止期間５年、更には構造部材における耐食性
２年という各条件を満足することが必要になっており、
より一層の耐食性改善がなされなければならない。Therefore, research has been conducted to improve Zn plating, and for example, an alloyed hot-dip galvanized steel sheet has been developed in which a heat treatment is performed after hot-dip Zn plating to alloy the Zn-plated layer and the base iron. This plated steel sheet has excellent properties such as corrosion resistance, paint film adhesion, and spot weldability, so it
Although it has become the mainstream material replacing n-plated steel sheet,
There are still problems with corrosion resistance. In particular, regarding corrosion resistance in the salt water spray environment that is carried out under the above-mentioned cold conditions, for example, the conditions of 10 years of preventing punctures on automobile exterior panels, 5 years of preventing external rust, and 2 years of corrosion resistance of structural members are considered. It has become necessary to be satisfied,
Further improvements in corrosion resistance must be made.
本発明は上記事情に着目してなされたものであって、塗
膜密着性、スポット溶接性等を満たす上に上述の如き厳
格な高耐食性要求にも答え得る様なＺｎ系めっき鋼材の
提供を目的とするものである。The present invention has been made in view of the above circumstances, and aims to provide a Zn-based plated steel material that satisfies paint film adhesion, spot weldability, etc. and also meets the above-mentioned strict requirements for high corrosion resistance. This is the purpose.
［課題を解決する為の手段］
上記課題を解決することのできた本発明のＺｎ系めっき
鋼材とは、鋼基材上に、
Ｆｅ： ６〜１５重量％
Ｍ ｇ ７０．４〜１５重量％
Ｚｎ及び不可避不純物：残部
からなるめっき層を形成したものである。[Means for Solving the Problems] The Zn-based plated steel material of the present invention that can solve the above problems has the following properties: Fe: 6 to 15% by weight M g 70.4 to 15% by weight Zn and unavoidable impurities: A plating layer consisting of the remainder is formed.
［作用］
本発明のめっき鋼板は従来のＺｎ−Ｆｅ系合金化溶融Ｚ
ｎめっき鋼板に更にＭｇが合金化されており、腐食の初
期にこのＭｇがＭｇトとなって溶出し、めっき表面に緻
密な保護皮膜を形成する。[Function] The plated steel sheet of the present invention is different from conventional Zn-Fe alloyed Z
The n-plated steel sheet is further alloyed with Mg, and at the beginning of corrosion, this Mg is eluted as Mg and forms a dense protective film on the plated surface.
そしてこの保護皮膜がその後の腐食反応を極力遅延させ
るものと考えられる。It is believed that this protective film delays the subsequent corrosion reaction as much as possible.
本発明のめっき組成を前記の如く定めた理由を説明する
。The reason why the plating composition of the present invention was determined as described above will be explained.
ＦｅはＺｎ系めっき層に塩水耐食性を与える重大な元素
であり、６％（重量％の意味、以下同じ）未満では上記
効果が発揮されない。一方１５％を超えると鋼板の加工
時にめっき層の割れや剥離が生じ易くなり、めっき鋼板
としての加工性が低下する。Fe is an important element that provides salt water corrosion resistance to the Zn-based plating layer, and if it is less than 6% (meaning % by weight, the same applies hereinafter), the above effect will not be exhibited. On the other hand, if it exceeds 15%, cracking or peeling of the plating layer tends to occur during processing of the steel sheet, and the workability of the plated steel sheet decreases.
Ｍｇは上述の如く緻密な保護皮膜を形成する為の重要な
元素であり、０．４％未満では上記作用が発揮されない
０Ｍｇの含有量を増大すればそれに見合った耐食性向上
効果が得られるが、１５％あたりでその効果が飽和し、
それ以上は車にコスト上昇の不利益が出るので１５％を
上限とした。As mentioned above, Mg is an important element for forming a dense protective film, and if it is less than 0.4%, the above effect will not be exhibited.If the content of 0Mg is increased, a corresponding improvement in corrosion resistance can be obtained. The effect saturates around 15%,
Anything higher than that would put the car at a disadvantage due to increased costs, so we set the upper limit at 15%.
本発明は上記組成のめつき層を有することがポイントで
あり、この様なめっき層を形成する手段そのものは本発
明の限定要件とはならない。しかしＺｎ−Ｍｇ混合浴に
よる溶融めっき法ではＭｇが非常に高活性であるため酸
化消耗が激しく、浴組成のコントロールが困難になると
いう問題があり、ま、た水溶液からの電気めつ合法では
Ｍｇのイオン化傾向が水素よりも高いため次に述べる様
な方法を採用することが推奨される。The key point of the present invention is to have a plating layer having the above composition, and the means for forming such a plating layer itself is not a limiting requirement of the present invention. However, in the hot-dip plating method using a Zn-Mg mixed bath, there is a problem that Mg is very highly active, resulting in severe oxidation consumption and making it difficult to control the bath composition. Since the ionization tendency of hydrogen is higher than that of hydrogen, it is recommended to use the method described below.
（１）鋼板表面を予め清浄にしておき、その表面に真空
蒸着法を適用してＺｎ−Ｍｇ合金めつきを施す。次に加
熱処理を施して鋼基材とＺｎ−Ｍｇ合金めっき層の間で
拡散による合金化反応を行わせ、希望組成のＺｎ−Ｆｅ
−Ｍｇ合金層を形成する。実験例の幾つかを説明すると
、Ｚ ｎ −１１，５Ｍｇ合金めつきを形成してから加
熱すればＺｎ−１０ＭＺｎ−１Ｏ合金めつ籾が生成し、
またＺ ｎ −１０，８Ｍ ｇ合金めつきを形成してか
ら加熱すればＺｎ−１０Ｍｇ−１３Ｆａ合金めつきが生
成した。(1) The surface of the steel plate is cleaned in advance, and a Zn-Mg alloy plating is applied to the surface by applying a vacuum evaporation method. Next, heat treatment is performed to cause an alloying reaction by diffusion between the steel base material and the Zn-Mg alloy plating layer, and Zn-Fe of the desired composition is formed.
- Forming a Mg alloy layer. To explain some experimental examples, if Zn-11,5Mg alloy plating is formed and then heated, Zn-10MZn-1O alloy paddy is produced,
Further, if a Zn-10,8Mg alloy plating was formed and then heated, a Zn-10Mg-13Fa alloy plating was formed.
（２）鋼板表面を予め清浄にしておき、その表面にＺｎ
、Ｆｅ、Ｍｇの３金属を同時的に、真空蒸着めっきする
。この方法であればめっき室の真空度におけるＺｎ、Ｆ
ｅ、Ｍｇの各蒸気圧を念頭におき、各金属の加熱温度を
制御して一気に所定組成のＺｎ−Ｆｅ−Ｍｇ合金めワき
層を形成する。(2) Clean the surface of the steel plate in advance, and apply Zn on the surface.
, Fe, and Mg are simultaneously vacuum evaporated and plated. With this method, Zn, F at the vacuum level of the plating chamber
By keeping in mind the vapor pressures of e and Mg, the heating temperature of each metal is controlled to form a Zn-Fe-Mg alloy plating layer of a predetermined composition at once.
（３） まず（１）の方法に従ってＺｎ−Ｍｇめつき層
を形成し、その上へ真空蒸着めっき或は電気めっき等の
方法を適用してＺｎ−Ｆｅ合金めつき層またはＦｅめつ
き層を上層として形成する。次いで加熱を加えることに
よってこれら各めっき層間で相互に拡散を行なわせ全体
として所定組成のＺｎ−Ｆｅ−Ｍｇ合金めっき層とする
。(3) First, a Zn-Mg plating layer is formed according to method (1), and a Zn-Fe alloy plating layer or Fe plating layer is applied thereon by vacuum evaporation plating or electroplating. Form as an upper layer. Next, heating is applied to cause mutual diffusion between these plating layers, resulting in a Zn--Fe--Mg alloy plating layer having a predetermined composition as a whole.
（４）従来法で得られた合金化溶融Ｚｎめつき鋼板を母
材とし、その上へ真空蒸着法によってＺｎ−Ｍｇ合金め
っきを形成する。次いでこれを加熱処理して所定の組成
Ｚｎ−Ｆｅ−Ｍｇ合金めっき層を生成する。′
［実施例］
厚さ０．８ｍｍの冷延鋼板を電解アルカリ脱脂して清浄
化した０次いで鋼板を２５０℃に予熱し、１０−’Ｔｏ
ｒｒの真空蒸発室に搬入し、前記（１）の方法でＺｎ−
Ｍｇ合金蒸着めっきを施した。蒸着量は４０ ｇ／ｃａ
’とし、次いでＡｒガス雰囲気中３５０℃×３０分の加
熱処理を行ない、第１表に示す組成のＺｎ−Ｆｅ−Ｍｇ
合金めっき層を形成した。(4) An alloyed hot-dip Zn-plated steel sheet obtained by a conventional method is used as a base material, and a Zn-Mg alloy plating is formed thereon by a vacuum evaporation method. Next, this is heat-treated to produce a Zn-Fe-Mg alloy plating layer having a predetermined composition. ' [Example] A cold-rolled steel plate with a thickness of 0.8 mm was cleaned by electrolytic alkali degreasing.Then, the steel plate was preheated to 250°C and heated to 10-'To
Zn-
Mg alloy vapor deposition plating was applied. Deposition amount is 40 g/ca
' and then heat-treated at 350°C for 30 minutes in an Ar gas atmosphere to produce Zn-Fe-Mg having the composition shown in Table 1.
An alloy plating layer was formed.
各供試めっき鋼板を夫々下記の方法で評価した。結果は
第１表に一括して示す。Each sample plated steel sheet was evaluated by the following method. The results are summarized in Table 1.
（イ）耐食性
めっき鋼板表面を化成処理した後、２０μｍ厚さで電着
塗装を施し、更に３５μＩ厚さの中塗り、最後に３５μ
ｍ厚さの上塗りを施した。これをクロスカットし、２０
００時間の塩水噴霧試験を行ない、鋼素地の孔あぎ深さ
で判定した。(a) After chemically treating the surface of the corrosion-resistant plated steel sheet, apply electrodeposition coating to a thickness of 20μm, then apply an intermediate coat to a thickness of 35μI, and finally apply a 35μI thick coating.
A top coat of m thickness was applied. Cross cut this, 20
A salt spray test was conducted for 00 hours, and judgment was made based on the drilling depth of the steel substrate.
Ｏ：優秀
Δ：良好
×：不良
（０）塗膜密着性
上記と全く同様にして上塗りまでを施した。クロスカッ
トを形成し温水中に浸漬して塗膜の健全な基盤目の数で
評価した。O: Excellent Δ: Good ×: Poor (0) Paint film adhesion A top coat was applied in exactly the same manner as above. A cross cut was formed and the film was immersed in warm water to evaluate the number of healthy base lines of the paint film.
０８９５％以上
Δ：９５〜８０％
×：８０％以下
（八）スポット溶接性
めっき鋼板を用いて連続スポット溶接を施し、溶接作業
性が不良になるまでの連続打点可能回数で評価した。0895% or more Δ: 95 to 80% ×: 80% or less (8) Spot weldability Continuous spot welding was performed using a plated steel plate, and evaluation was made based on the number of consecutive points possible until welding workability became poor.
○ ： ５０００点超
○〜△： ５０００点未溝〜３０００点以上△ ： ３
０００点未満〜２０００点以上ｘ ：２０００点未満
第 １ 表
第１表に見られる通り１本発明のめっき組成条件を満足
するものは全３項目とも満足な成績を残したが、１つで
も満足しないものは評価項目の全てで合格点を得るには
至らなかワた。○: Over 5,000 points ○~△: 5,000 points missing ~ 3,000 points or more △: 3
Less than 000 points - 2000 points or more Those who do not do so will not be able to obtain passing scores on all evaluation items.
本発明は上記の様に構成されているので、塗膜密着性や
スポット溶接性に悪影響を与えることなく、耐食性を大
幅に向上させることができた。Since the present invention is configured as described above, corrosion resistance can be significantly improved without adversely affecting paint film adhesion or spot weldability.
Claims (1)
る高耐食性Ｚｎ−Ｍｇ−Ｆｅ合金めっき鋼材。[Scope of Claims] A plating layer having the following composition: Fe: 6 to 15% by weight, Mg: 0.4 to 15% by weight, Zn and unavoidable impurities: the balance is formed on a steel base material. Highly corrosion resistant Zn-Mg-Fe alloy plated steel.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12599589A JPH02305975A (en) | 1989-05-18 | 1989-05-18 | High corrosion resistant steel plated by zn-mg-fe alloy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12599589A JPH02305975A (en) | 1989-05-18 | 1989-05-18 | High corrosion resistant steel plated by zn-mg-fe alloy |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02305975A true JPH02305975A (en) | 1990-12-19 |
Family
ID=14924116
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12599589A Pending JPH02305975A (en) | 1989-05-18 | 1989-05-18 | High corrosion resistant steel plated by zn-mg-fe alloy |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02305975A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19527515C1 (en) * | 1995-07-27 | 1996-11-28 | Fraunhofer Ges Forschung | Corrosion-resistant steel sheet prodn., e.g. for the automobile industry |
| CN111334748A (en) * | 2020-04-07 | 2020-06-26 | 天津联优新材料科技有限公司 | Protective layer of steel product, preparation method of protective layer and steel product |
-
1989
- 1989-05-18 JP JP12599589A patent/JPH02305975A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19527515C1 (en) * | 1995-07-27 | 1996-11-28 | Fraunhofer Ges Forschung | Corrosion-resistant steel sheet prodn., e.g. for the automobile industry |
| CN111334748A (en) * | 2020-04-07 | 2020-06-26 | 天津联优新材料科技有限公司 | Protective layer of steel product, preparation method of protective layer and steel product |
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