TW201910537A - High-strength lubricating galvanized steel sheet and method of manufacturing the same wherein the steel sheet is provided with a uniform appearance and an excellent corrosion resistance - Google Patents
High-strength lubricating galvanized steel sheet and method of manufacturing the same wherein the steel sheet is provided with a uniform appearance and an excellent corrosion resistance Download PDFInfo
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本發明係關於一種鋼板及其製造方法，且更特定言之，係關於一種高強度潤滑鍍鋅鋼板及其製造方法。The present invention relates to a steel sheet and a method of manufacturing the same, and more particularly to a high strength lubricating galvanized steel sheet and a method of manufacturing the same.
鍍鋅鋼板具有良好的耐腐蝕性、易成型及塗漆等優點，廣泛應用於家電、電子產品、機械及建築等產業。尤其是針對家電或傢俱製品的功能滑軌部件而言，更加要求底材本身的機械強度、外觀表面品質及產品特殊功能特性，例如耐腐蝕性、潤滑性及耐磨耗性等。Galvanized steel sheets have good corrosion resistance, easy forming and painting, and are widely used in home appliances, electronic products, machinery and construction industries. In particular, for functional rail components of home appliances or furniture products, the mechanical strength, appearance surface quality and special functional properties of the substrate itself, such as corrosion resistance, lubricity and wear resistance, are more required.
功能滑軌產品普遍使用含0.17~0.21%碳含量的高強度鋼種，而上述鋼種之碳含量接近包晶點，鋼胚凝固體積變化大，易產生微裂，造成鋼帶表面隨機分佈連點成線狀的缺陷，該等缺陷會導致膜層在塗覆過程中不均勻，進而影響產品外觀及功能性。The functional rail products generally use high-strength steel with 0.17~0.21% carbon content, and the carbon content of the above steel species is close to the peritectic point. The solidification volume of the steel embryo changes greatly, and it is easy to produce micro-cracks, resulting in random distribution of the surface of the steel strip. Linear defects that cause the film to be uneven during the coating process, which in turn affects the appearance and functionality of the product.
此外，習知使用之水性金屬表面處理劑因環保無鉻化趨勢，目前皆朝向使用水性無三價鉻及六價鉻組成之金屬表面處理劑，惟，經上述處理劑表面處理後之金屬材料（例如：鋼板）應用在家電及辦公傢俱功能滑軌部件（例如：冰箱拉門、桌櫃抽屜、推拉門板滑軌材料等）時，因不具備潤滑特性，容易造成使用者在操作滑軌拉門時之不順暢，而在滑軌料上塗覆潤滑油則不符現今高品質產品之需求。另外，使用一般含有機樹脂之耐指紋水性塗料於金屬材料上，雖可降低動摩擦係數及提升潤滑性，卻仍無法承受使用者長期抽拉之動作，以致仍會發生接觸面磨耗及潤滑性劣化之結果。In addition, the water-based metal surface treatment agent used in the prior art is oriented toward the use of a metal surface treatment agent composed of water-free trivalent chromium and hexavalent chromium because of the environmentally-friendly non-chromium tendency. However, the metal material after surface treatment by the above treatment agent is used. (for example: steel plate) used in home appliance and office furniture function rail components (such as: refrigerator door, table cabinet drawer, sliding door panel rail material, etc.), because it does not have lubrication characteristics, it is easy for the user to operate the slide rail The door is not smooth, and the application of lubricating oil to the rail material does not meet the needs of today's high quality products. In addition, the use of fingerprint-resistant water-based paints generally containing organic resin on metal materials, although reducing the dynamic friction coefficient and improving lubricity, but still can not withstand the user's long-term pulling action, so that contact surface wear and lubrication degradation will still occur The result.
因此，有必要提供一創新且具進步性之高強度潤滑鍍鋅鋼板及其製造方法，以解決上述問題。Therefore, it is necessary to provide an innovative and progressive high-strength lubricating galvanized steel sheet and a method of manufacturing the same to solve the above problems.
在一實施例中，一種高強度潤滑鍍鋅鋼板包括一鋼底材、一鋅鍍層及一無鉻塗覆層。該鋼底材具有一表面。該鋅鍍層設置於該鋼底材之表面。該無鉻塗覆層設置於該鋅鍍層上。In one embodiment, a high strength lubricated galvanized steel sheet includes a steel substrate, a zinc coating, and a chromium-free coating. The steel substrate has a surface. The zinc coating is disposed on the surface of the steel substrate. The chromium-free coating layer is disposed on the zinc plating layer.
在一實施例中，一種高強度潤滑鍍鋅鋼板之製造方法包括以下步驟：提供一鋼底材，該鋼底材具有一表面；形成一鋅鍍層於該鋼底材之表面；及形成一無鉻塗覆層於該鋅鍍層上，以製得高強度潤滑鍍鋅鋼板。In one embodiment, a method of manufacturing a high-strength lubricating galvanized steel sheet includes the steps of: providing a steel substrate having a surface; forming a zinc coating on a surface of the steel substrate; and forming a A chromium coating is applied to the zinc coating to produce a high strength lubricated galvanized steel sheet.
參閱圖1，其係顯示本發明高強度潤滑鍍鋅鋼板之結構示意圖。本發明之高強度潤滑鍍鋅鋼板10包括一鋼底材11、一鋅鍍層12及一無鉻塗覆層13。Referring to Figure 1, there is shown a schematic view of the structure of the high strength lubricating galvanized steel sheet of the present invention. The high strength lubricating galvanized steel sheet 10 of the present invention comprises a steel substrate 11, a zinc coating 12 and a chromium-free coating layer 13.
該鋼底材11具有一表面11S。在本實施態樣中，該鋼底材11係為碳含量小於0.1%、鈮含量為0.01%至0.1%、錳含量為0.1%至1.0%、抗拉強度大於或等於400 MPa、降伏強度大於或等於295 MPa及伸長率大於或等於18%之高強度低合金鋼底材，如碳錳鋼、低碳鋼等。當鈮含量不足0.01%時，係無法降低煉鋼過程之表面缺陷及達到抗拉強度之目標下限；當鈮含量超過0.1%時，雖有助於提升抗拉強度及降伏強度，卻會降低伸長率。當錳含量不足0.1%時，係無法達到抗拉強度之目標下限；當錳含量超過1.0%時，係會造成熱浸鍍鋅過程鍍敷性不佳，影響外觀品質。The steel substrate 11 has a surface 11S. In this embodiment, the steel substrate 11 has a carbon content of less than 0.1%, a niobium content of 0.01% to 0.1%, a manganese content of 0.1% to 1.0%, a tensile strength of greater than or equal to 400 MPa, and a bulk strength greater than or equal to 400 MPa. Or a high-strength low-alloy steel substrate equal to 295 MPa and an elongation greater than or equal to 18%, such as carbon-manganese steel, low-carbon steel, and the like. When the niobium content is less than 0.01%, the surface defects of the steelmaking process and the target lower limit of the tensile strength cannot be lowered; when the niobium content exceeds 0.1%, although the tensile strength and the lodging strength are improved, the elongation is lowered. rate. When the manganese content is less than 0.1%, the target lower limit of tensile strength cannot be achieved; when the manganese content exceeds 1.0%, the plating property of the hot dip galvanizing process is poor, which affects the appearance quality.
該鋅鍍層12設置於該鋼底材11之表面11S。在本實施態樣中，該鋅鍍層12具有一粗糙表面12S。The zinc plating layer 12 is provided on the surface 11S of the steel substrate 11. In this embodiment, the zinc plating layer 12 has a rough surface 12S.
該無鉻塗覆層13設置於該鋅鍍層12上，在本實施態樣中，該無鉻塗覆層13係覆蓋該鋅鍍層12之該粗糙表面12S。此外，為增加該無鉻塗覆層13與該粗糙表面12S之密著性，該粗糙表面12S之平均粗糙度(Ra值)應控制在0.5微米至1.5微米。當平均粗糙度(Ra值)小於0.5微米時，雖有利於降低表面摩擦係數，但會減弱該無鉻塗覆層13與該鋅鍍層12的密著性；當平均粗糙度(Ra值)大於1.5微米時，係會導致該無鉻塗覆層13之披覆性不足，進而降低鋼板之耐蝕性及潤滑性。The chromium-free coating layer 13 is disposed on the zinc plating layer 12. In the embodiment, the chromium-free coating layer 13 covers the rough surface 12S of the zinc plating layer 12. Further, in order to increase the adhesion of the chromium-free coating layer 13 to the rough surface 12S, the average roughness (Ra value) of the rough surface 12S should be controlled to be 0.5 μm to 1.5 μm. When the average roughness (Ra value) is less than 0.5 μm, although it is advantageous to lower the surface friction coefficient, the adhesion of the chromium-free coating layer 13 to the zinc plating layer 12 is weakened; when the average roughness (Ra value) is greater than When the thickness is 1.5 μm, the coating property of the chromium-free coating layer 13 is insufficient, and the corrosion resistance and lubricity of the steel sheet are lowered.
在本實施態樣中，該無鉻塗覆層13之厚度應控制在0.05微米至2.0微米。當該無鉻塗覆層13之厚度小於0.05微米時，將使該無鉻塗覆層13的耐蝕性及潤滑性不佳；當該無鉻塗覆層13之厚度超過2.0微米時，雖可提昇耐蝕性及潤滑性，卻會造成鋼板表面外觀不佳，且會增加製作成本。In this embodiment, the thickness of the chromium-free coating layer 13 should be controlled to be from 0.05 micrometers to 2.0 micrometers. When the thickness of the chromium-free coating layer 13 is less than 0.05 micrometer, the corrosion resistance and lubricity of the chromium-free coating layer 13 will be poor; when the thickness of the chromium-free coating layer 13 exceeds 2.0 micrometers, Improve corrosion resistance and lubricity, but it will result in poor appearance of the steel surface and increase production costs.
在本實施態樣中，該無鉻塗覆層13係由一潤滑型水性金屬表面處理劑塗覆於該鋅鍍層12上並經加熱乾燥後所形成。該潤滑型水性金屬表面處理劑包括水性無鉻組成物、水溶性或水分散性有機樹脂以及蠟添加物。In the present embodiment, the chromium-free coating layer 13 is formed by applying a lubricating aqueous metal surface treatment agent to the zinc plating layer 12 and drying it by heating. The lubricating aqueous metal surface treatment agent includes an aqueous chromium-free composition, a water-soluble or water-dispersible organic resin, and a wax additive.
該水性無鉻組成物包括水溶性鋯化合物、矽化合物、含氟化合物及磷酸化合物。The aqueous chromium-free composition includes a water-soluble zirconium compound, a cerium compound, a fluorine-containing compound, and a phosphoric acid compound.
該水溶性鋯化合物(A)係可選自硝酸鋯、硝酸氧鋯、硫酸鋯、醋酸鋯、氟鋯酸、碳酸鋯銨、碳酸鋯鈉、碳酸鋯鉀及其彼此組合中的其中一種The water-soluble zirconium compound (A) may be selected from the group consisting of zirconium nitrate, zirconyl nitrate, zirconium sulfate, zirconium acetate, fluorozirconic acid, ammonium zirconium carbonate, sodium zirconium carbonate, potassium zirconium carbonate and combinations thereof.
該矽化合物(B)係可選自水分散性微粒二氧化矽、矽烷偶合劑、表面改質具反應官能基之微粒二氧化矽及其彼此組合中的其中一種The ruthenium compound (B) may be selected from the group consisting of water-dispersible fine particle cerium oxide, decane coupling agent, surface-modified granule cerium oxide, and one of them.
在本實施態樣中，該水分散性微粒二氧化矽係為膠態二氧化矽或粉末二氧化矽，且二氧化矽粒子之平均粒徑小於100奈米。In this embodiment, the water-dispersible fine particle cerium oxide is colloidal cerium oxide or powdered cerium oxide, and the cerium oxide particles have an average particle diameter of less than 100 nm.
該矽烷偶合劑係可選自γ-氨基丙基三甲氧基矽烷、γ-氨基丙基三乙氧基矽烷、γ-環氧丙烷基丙基三甲氧矽烷、γ-環氧丙烷基丙基三乙氧基矽烷、N-(β-氨基乙基)-γ-氨基丙基甲基二乙氧基矽烷、N-(β-氨基乙基)-γ-氨基丙基三甲氧基矽烷、N-(β-氨基乙基)-γ-氨基丙基三乙氧基矽烷、γ-環氧丙烷基丙基甲基二乙氧基矽烷及其彼此組合中的其中一種。在本實施態樣中，該矽烷偶合劑在水解縮合後，將形成二維或三維Si-O-Si交聯結構；同時，Si-O鍵亦與該鋅鍍層12形成化學鍵結，使該潤滑型水性金屬表面處理劑與該鋅鍍層12之間具有良好的附著性，且讓所形成之該無鉻塗覆層13的整體結構更為緻密。此外，若導入含低極性官能基團之矽烷偶合劑，更可增加該無鉻塗覆層13之滑順觸感。The decane coupling agent may be selected from the group consisting of γ-aminopropyltrimethoxydecane, γ-aminopropyltriethoxydecane, γ-propylene oxide propyltrimethoxy decane, and γ-propylene oxide propyl trisole. Ethoxy decane, N-(β-aminoethyl)-γ-aminopropylmethyldiethoxydecane, N-(β-aminoethyl)-γ-aminopropyltrimethoxydecane, N- (β-Aminoethyl)-γ-aminopropyltriethoxydecane, γ-glycidylpropylmethyldiethoxydecane, and a combination thereof. In this embodiment, the decane coupling agent will form a two-dimensional or three-dimensional Si-O-Si crosslinked structure after hydrolysis and condensation; at the same time, the Si-O bond also forms a chemical bond with the zinc plating layer 12 to make the lubrication. The type of the aqueous metal surface treatment agent has good adhesion to the zinc plating layer 12, and the overall structure of the chromium-free coating layer 13 formed is more dense. Further, if a decane coupling agent containing a low polar functional group is introduced, the smooth touch of the chromium-free coating layer 13 can be further increased.
該表面改質具反應官能基之微粒二氧化矽可藉由該水分散性微粒二氧化矽及該矽烷偶合劑交互反應而成。該具反應官能基之微粒二氧化矽除可提升該無鉻塗覆層13交聯緻密性外，亦可藉由微粒二氧化矽本身之硬度及表面斥水性提高該無鉻塗覆層13之耐磨耗性及潤滑性。The surface modified particulate cerium oxide having a reactive functional group can be formed by interactively reacting the water-dispersible fine particle cerium oxide and the decane coupling agent. The particulate cerium oxide having a reactive functional group can improve the cross-linking density of the chromium-free coating layer 13, and can also improve the chromium-free coating layer 13 by the hardness and surface water repellency of the particulate cerium oxide itself. Abrasion resistance and lubricity.
較佳地，該矽化合物(B)之含有量相對於該水溶性鋯化合物(A)的質量比(B/A)係介於0.2至1.2之間。當質量比(B/A)小於0.2時，雖然仍會於該鋅鍍層12上形成該無鉻塗覆層13，惟該無鉻塗覆層13之耐蝕性、耐鹼洗性及耐磨耗性並不佳；當質量比(B/A)大於1.2時，該潤滑型水性金屬表面處理劑的成本會提高，但該無鉻塗覆層13之性質並未有明顯改善，且該無鉻塗覆層13之乾燥性亦會變得不佳。Preferably, the content of the cerium compound (B) is from 0.2 to 1.2 in terms of the mass ratio (B/A) of the water-soluble zirconium compound (A). When the mass ratio (B/A) is less than 0.2, although the chromium-free coating layer 13 is still formed on the zinc plating layer 12, the corrosion resistance, alkali-resistant washing property and abrasion resistance of the chromium-free coating layer 13 are obtained. The quality is not good; when the mass ratio (B/A) is more than 1.2, the cost of the lubricating aqueous metal surface treatment agent is increased, but the properties of the chromium-free coating layer 13 are not significantly improved, and the chromium-free layer The dryness of the coating layer 13 may also become poor.
該含氟化合物(C)具有至少一個以上氟離子基團，在本實施態樣中，該含氟化合物係可選自氟化鋯銨、氟化鋯鉀、氟鋯酸、氟鈦酸銨、氟鈦酸、氟矽酸、氫氟酸及氟化氫銨中的其中一種。較佳地，該含氟化合物(C)之含有量相對於該水溶性鋯化合物(A)的質量比(C/A)係介於0.08至0.5之間。當質量比(C/A)小於0.08時，所形成之該無鉻塗覆層13的耐鹼洗性不佳；當質量比(C/A)大於0.5時，其所形成之該無鉻塗覆層13的性質並未有明顯改善，且其過量副產物亦不利該無鉻塗覆層13之乾燥性及耐蝕性。The fluorine-containing compound (C) has at least one fluorine ion group. In the embodiment, the fluorine-containing compound may be selected from ammonium zirconium fluoride, potassium zirconium fluoride, fluorozirconic acid, ammonium fluorotitanate, One of fluorotitanate, fluoroantimonic acid, hydrofluoric acid, and ammonium hydrogen fluoride. Preferably, the content of the fluorine-containing compound (C) is from 0.08 to 0.5 in terms of the mass ratio (C/A) of the water-soluble zirconium compound (A). When the mass ratio (C/A) is less than 0.08, the alkali-free washing property of the chromium-free coating layer 13 formed is not good; when the mass ratio (C/A) is more than 0.5, the chromium-free coating layer is formed. The properties of the coating 13 are not significantly improved, and excessive by-products thereof are also detrimental to the dryness and corrosion resistance of the chromium-free coating layer 13.
該磷酸化合物(D)係可選自下列物質中的一種：磷酸；磷酸二氫鹽、磷酸一氫鹽、磷酸鹽；三聚磷酸；縮合磷酸鹽，如三聚磷酸鹽、偏磷酸鹽；1-羥基甲烷-1,1-二膦酸、1-羥基乙烷-1,1-二膦酸、1-羥基丙烷-1,1-二膦酸、氨基三亞甲基膦酸、2-膦酸丁烷-1,2,4-三羧酸；以及前述鹽類的組合。較佳地，該磷酸化合物(D)之含有量相對於該水溶性鋯化合物(A)的質量比(D/A)係介於0.1至0.5之間。當質量比(D/A)小於0.1時，將影響該無鉻塗覆層13與該鋅鍍層12之間的附著性；當質量比(D/A)大於0.5時，該無鉻塗覆層13之耐蝕性會變得不佳。The phosphoric acid compound (D) may be selected from one of the following: phosphoric acid; dihydrogen phosphate, monohydrogen phosphate, phosphate; tripolyphosphoric acid; condensed phosphate such as tripolyphosphate, metaphosphate; -hydroxymethane-1,1-diphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid, 1-hydroxypropane-1,1-diphosphonic acid, aminotrimethylenephosphonic acid, 2-phosphonic acid Butane-1,2,4-tricarboxylic acid; and combinations of the foregoing salts. Preferably, the content of the phosphoric acid compound (D) is from 0.1 to 0.5 with respect to the mass ratio (D/A) of the water-soluble zirconium compound (A). When the mass ratio (D/A) is less than 0.1, the adhesion between the chromium-free coating layer 13 and the zinc plating layer 12 is affected; when the mass ratio (D/A) is more than 0.5, the chromium-free coating layer Corrosion resistance of 13 will become poor.
該水溶性或水分散性有機樹脂(R)為含有可使其單獨溶於水中或在水中分散的官能基之樹脂。在本實施態樣中，該水溶性或水分散性有機樹脂係可選自聚氨酯樹脂，其由聚酯多元醇、聚醚多元醇等多元醇與二異氰酸酯反應配製而成並在水中穩定地分散或溶解。或者，在另一實施例中，該水溶性或水分散性有機樹脂係可選自壓克力樹脂，其由丙烯酸、甲基丙烯酸、丙烯酸酯、甲基丙烯酸酯等單體乳液聚合而成，該壓克力樹脂另包含壓克力接枝環氧樹脂共聚合體、壓克力接枝聚脲樹脂共聚合體、壓克力接枝聚烯烴樹脂共聚合體或其彼此組合，且該壓克力樹脂之平均分子量範圍係介於10,000至1,000,000之間，而其平均粒徑係介於0.1微米至2微米之間。The water-soluble or water-dispersible organic resin (R) is a resin containing a functional group which can be dissolved in water alone or dispersed in water. In this embodiment, the water-soluble or water-dispersible organic resin may be selected from a polyurethane resin prepared by reacting a polyol such as a polyester polyol or a polyether polyol with a diisocyanate and stably dispersed in water. Or dissolve. Alternatively, in another embodiment, the water-soluble or water-dispersible organic resin may be selected from acrylic resin, which is obtained by emulsion polymerization of monomers such as acrylic acid, methacrylic acid, acrylate, methacrylate, and the like. The acrylic resin further comprises an acrylic graft epoxy resin copolymer, an acrylic graft polyurea resin copolymer, an acrylic graft polyolefin resin copolymer or a combination thereof, and the acrylic resin The average molecular weight range is between 10,000 and 1,000,000 and the average particle size is between 0.1 and 2 microns.
該水溶性或水分散性有機樹脂可選擇性添加於該潤滑型水性金屬表面處理劑中，且較佳地，該有機樹脂(R)固成份相對於整體固成份之比係介於0.01至0.9之間。當有機樹脂固成份佔整體固成份小於0.01時，所形成之該無鉻塗覆層13將無法進一步提升潤滑性；當有機樹脂(R)固成份佔整體固成份大於0.9時，係會造成該無鉻塗覆層13之乾燥性不足。The water-soluble or water-dispersible organic resin may be selectively added to the lubricating aqueous metal surface treatment agent, and preferably, the ratio of the solid resin (R) solid content to the overall solid content is between 0.01 and 0.9. between. When the solid content of the organic resin is less than 0.01, the chromium-free coating layer 13 formed cannot further improve the lubricity; when the solid content of the organic resin (R) accounts for more than 0.9, the system causes the The dryness of the chromium-free coating layer 13 is insufficient.
在該潤滑型水性金屬表面處理劑塗覆於該鋅鍍層12後，濕的潤滑型水性金屬表面處理劑的塗層在乾燥過程中，交聯劑會與上述水溶性或水分散性之有機樹脂反應而硬化塗層。交聯劑之材料可選用只要可藉由加熱等方式而與水溶性或水分散性之有機樹脂進行反應予以硬化的材料即可。在一或多個實施態樣中，交聯劑可選自於由多異氰酸酯化合物、親水改性多異氰酸酯化合物、親水改性封閉型多異氰酸酯化合物、三聚氰胺樹脂及其改性化合物、碳化二亞胺及其改性化合物、或其組合所組成之一族群。After the lubricating aqueous metal surface treatment agent is applied to the zinc plating layer 12, the coating of the wet lubricating aqueous metal surface treatment agent, during the drying process, the crosslinking agent and the above water-soluble or water-dispersible organic resin Reacts to harden the coating. The material of the crosslinking agent may be selected as long as it can be cured by reaction with a water-soluble or water-dispersible organic resin by heating or the like. In one or more embodiments, the crosslinking agent may be selected from the group consisting of polyisocyanate compounds, hydrophilically modified polyisocyanate compounds, hydrophilically modified blocked polyisocyanate compounds, melamine resins and modified compounds thereof, carbodiimides. A group consisting of its modified compounds, or a combination thereof.
較佳地，交聯劑之固成分相對於有機樹脂之固成分之比小於0.15。因為當交聯劑之固成分占有機樹脂之固成分大於0.15時，雖會促進塗層交聯緻密性、提高硬度及耐磨耗特性，但會造成水性金屬表面處理劑之黏度上升、不利塗裝控制及劣化塗層性能之疑慮。Preferably, the ratio of the solid content of the crosslinking agent to the solid content of the organic resin is less than 0.15. Because when the solid content of the crosslinking agent accounts for more than 0.15 of the solid content of the organic resin, although the crosslinking property of the coating is promoted, the hardness and the wear resistance characteristics are improved, but the viscosity of the aqueous metal surface treatment agent is increased, and the coating is unfavorable. Contains concerns about the performance of controlled and degraded coatings.
該蠟添加物(E)係可選自聚乙烯蠟、聚四氟乙烯蠟及其彼此組合中的其中一種。在本實施態樣中，該蠟添加物之型態係可選自如下的其中一種：蠟粉及蠟乳液。The wax additive (E) may be selected from the group consisting of polyethylene wax, polytetrafluoroethylene wax, and combinations thereof. In this embodiment, the form of the wax additive may be selected from one of the following: a wax powder and a wax emulsion.
該蠟添加物包含複數個蠟微粒，較佳地，該等蠟微粒之平均粒徑係介於0.05微米至10微米之間。當平均粒徑小於0.05微米時，將使該無鉻塗覆層13之潤滑性改善效果不足；當平均粒徑大於10微米時，將使該等蠟微粒易沉降，造成塗料安定性及產線操作性不佳。The wax additive comprises a plurality of wax particles, preferably, the wax particles have an average particle size of between 0.05 microns and 10 microns. When the average particle diameter is less than 0.05 μm, the lubricity improving effect of the chromium-free coating layer 13 is insufficient; when the average particle diameter is larger than 10 μm, the wax particles are easily settled, resulting in coating stability and production line. Poor operation.
該蠟添加物(E)固成份相對於整體固成份之比係介於0.005至0.03之間。當蠟添加物固成份佔整體固成份小於0.005時，所形成之該無鉻塗覆層13將無法提供較低之動摩擦係數及合適潤滑性；當蠟添加物固成份佔整體固成份大於0.03時，則會造成該無鉻塗覆層13之耐蝕性劣化。The ratio of the wax additive (E) solid component to the overall solid component is between 0.005 and 0.03. When the solid content of the wax additive is less than 0.005, the chromium-free coating layer 13 formed will not provide a lower dynamic friction coefficient and suitable lubricity; when the solid content of the wax additive accounts for more than 0.03 of the total solid content The corrosion resistance of the chromium-free coating layer 13 is deteriorated.
較佳地，該潤滑型水性金屬表面處理劑之pH值係介於6.0至11.0之間。當pH值低於6.0時，將使該潤滑型水性金屬表面處理劑較不穩定且容易形成沈澱物；而當pH值高於11.0時，該潤滑型水性金屬表面處理劑所形成之該無鉻塗覆層13的耐蝕性不佳，其會影響鋼板表面外觀。Preferably, the lubricating aqueous metal surface treatment agent has a pH of between 6.0 and 11.0. When the pH value is lower than 6.0, the lubricating type aqueous metal surface treatment agent is made unstable and easily forms a precipitate; and when the pH value is higher than 11.0, the lubricating type aqueous metal surface treatment agent forms the chromium-free layer. The corrosion resistance of the coating layer 13 is poor, which affects the appearance of the surface of the steel sheet.
該潤滑型水性金屬表面處理劑係可透過多種方式來調整pH值，例如可視需求利用酸液或鹼液來調整。此外，該潤滑型水性金屬表面處理劑亦可視需求添加表面調節助劑（例如：濕潤劑、流平劑）、分散劑及消泡劑等，以提升塗料安定性及鋼板表面外觀品質。The lubricating aqueous metal surface treatment agent can adjust the pH value in various ways, for example, by using an acid solution or an alkali solution as needed. In addition, the lubricating aqueous metal surface treatment agent may also add a surface conditioning aid (for example, a wetting agent, a leveling agent), a dispersing agent and an antifoaming agent as needed to improve the stability of the coating and the appearance quality of the steel sheet surface.
圖2顯示本發明高強度潤滑鍍鋅鋼板之製造方法之流程圖。圖3A顯示本發明高強度潤滑鍍鋅鋼板之製造方法中之一鋼底材之示意圖。配合參閱圖2之步驟S21及圖3A，提供一鋼底材11，該鋼底材11具有一表面11S。在本實施態樣中，該鋼底材11係為碳含量小於0.1%、鈮含量為0.01%至0.1%、錳含量為0.1%至1.0%、抗拉強度大於或等於400 MPa、降伏強度大於或等於295 MPa及伸長率大於或等於18%之高強度低合金鋼底材，如碳錳鋼、低碳鋼等。此外，該鋼底材11之製造工序包括將低碳鋼胚經熱軋、酸洗、冷軋製程後，在連續熱浸鍍鋅產線之退火爐升溫至750~850℃，持溫維持30~150秒後，冷卻至450~500℃溫度區間。2 is a flow chart showing a method of manufacturing the high strength lubricating galvanized steel sheet of the present invention. Fig. 3A is a view showing a steel substrate of a method for producing a high-strength lubricating galvanized steel sheet according to the present invention. Referring to step S21 and FIG. 3A of FIG. 2, a steel substrate 11 having a surface 11S is provided. In this embodiment, the steel substrate 11 has a carbon content of less than 0.1%, a niobium content of 0.01% to 0.1%, a manganese content of 0.1% to 1.0%, a tensile strength of greater than or equal to 400 MPa, and a bulk strength greater than or equal to 400 MPa. Or a high-strength low-alloy steel substrate equal to 295 MPa and an elongation greater than or equal to 18%, such as carbon-manganese steel, low-carbon steel, and the like. In addition, the manufacturing process of the steel substrate 11 includes heating the low carbon steel embryo by hot rolling, pickling, and cold rolling, and heating the furnace in a continuous hot dip galvanizing line to 750 to 850 ° C, maintaining the temperature of 30. After ~150 seconds, cool to 450~500 °C temperature range.
另外，在此步驟中，該鋼底材11可進行一清洗及脫脂步驟，以清潔該鋼底材11之表面11S。Further, in this step, the steel substrate 11 can be subjected to a cleaning and degreasing step to clean the surface 11S of the steel substrate 11.
圖3B顯示依據本發明高強度潤滑鍍鋅鋼板之製造方法形成一鋅鍍層於鋼底材之表面之示意圖。配合參閱圖2之步驟S22及圖3B，形成一鋅鍍層12於該鋼底材11之表面11S。在此步驟中，該鋼底材11係浸入一鋅浴中進行熱浸鍍鋅，以形成該鋅鍍層12於該鋼底材11之表面11S。較佳地，該鋅浴的溫度為450℃至480℃。Figure 3B is a schematic view showing the formation of a zinc coating on the surface of a steel substrate in accordance with the method of manufacturing a high strength lubricating galvanized steel sheet according to the present invention. Referring to step S22 and FIG. 3B of FIG. 2, a zinc plating layer 12 is formed on the surface 11S of the steel substrate 11. In this step, the steel substrate 11 is immersed in a zinc bath for hot dip galvanizing to form the zinc plating layer 12 on the surface 11S of the steel substrate 11. Preferably, the temperature of the zinc bath is from 450 ° C to 480 ° C.
此外，在形成該鋅鍍層12後可進行一調質軋延處理，以使該鋅鍍層12形成一粗糙表面12S。在本實施態樣中，該調質軋延處理之伸長率為0.5%至2.0%，而軋延工輥之種類並無特別限定，如噴砂工輥、靜電加工工輥等皆可。此外，該粗糙表面12S之平均粗糙度(Ra值)控制在0.5微米至1.5微米為佳。In addition, after the zinc plating layer 12 is formed, a quenching and rolling process may be performed to form the zinc plating layer 12 to form a rough surface 12S. In the present embodiment, the elongation of the temper rolling treatment is 0.5% to 2.0%, and the type of the rolling roll is not particularly limited, and may be, for example, a blasting roller or an electrostatic processing roller. Further, the average roughness (Ra value) of the rough surface 12S is preferably controlled to be 0.5 μm to 1.5 μm.
圖3C顯示依據本發明高強度潤滑鍍鋅鋼板之製造方法形成一無鉻塗覆層於鋅鍍層上之示意圖。配合參閱圖2之步驟S23及圖3C，形成一無鉻塗覆層13於該鋅鍍層12上，以製得高強度潤滑鍍鋅鋼板10。在此步驟中，該無鉻塗覆層13係覆蓋該鋅鍍層12之該粗糙表面12S。而形成該無鉻塗覆層13之步驟係包括：3C is a schematic view showing the formation of a chromium-free coating layer on a zinc plating layer in accordance with the method for producing a high-strength lubricating galvanized steel sheet according to the present invention. Referring to step S23 and FIG. 3C of FIG. 2, a chromium-free coating layer 13 is formed on the zinc plating layer 12 to produce a high-strength lubricating galvanized steel sheet 10. In this step, the chromium-free coating layer 13 covers the rough surface 12S of the zinc plating layer 12. The steps of forming the chromium-free coating layer 13 include:
將一潤滑型水性金屬表面處理劑塗覆於該鋅鍍層12上，該潤滑型水性金屬表面處理劑包括水性無鉻組成物、水溶性或水分散性有機樹脂以及蠟添加物；及Applying a lubricating aqueous metal surface treatment agent to the zinc plating layer 12, the lubricating aqueous metal surface treatment agent comprising an aqueous chromium-free composition, a water-soluble or water-dispersible organic resin, and a wax additive;
對該潤滑型水性金屬表面處理劑進行一加熱乾燥步驟，以形成該無鉻塗覆層13於該鋅鍍層12上。較佳地，該加熱乾燥步驟的溫度為50℃至250℃。The lubricating aqueous metal surface treatment agent is subjected to a heat drying step to form the chromium-free coating layer 13 on the zinc plating layer 12. Preferably, the temperature of the heat drying step is from 50 ° C to 250 ° C.
上述之水性無鉻組成物、水溶性或水分散性有機樹脂以及蠟添加物之細部說明同[0019]~[0034]之記載，在此不另贅述。The details of the above-described aqueous chromium-free composition, water-soluble or water-dispersible organic resin, and wax additive are described in the following [0019] to [0034], and are not described herein.
本發明係利用該潤滑型水性金屬表面處理劑來抑制陽極及陰極的氧化還原反應。其中，利用水溶性鋯化合物滲進矽化合物體結構間，經加熱乾燥後，矽醇鍵與鋯離子吸附(及/或交聯)形成該無鉻塗覆層13的骨架；藉由添加有機樹脂於該潤滑型水性金屬表面處理劑中，一旦乾燥，便與上述無機骨架形成不易溶解於水之有機-無機複合型無鉻塗覆層，提升屏障效果以抑制腐蝕進行。The present invention utilizes the lubricating aqueous metal surface treatment agent to suppress the redox reaction of the anode and the cathode. Wherein, the water-soluble zirconium compound is infiltrated into the body structure of the ruthenium compound, and after drying by heating, the sterol bond and the zirconium ion are adsorbed (and/or crosslinked) to form a skeleton of the chromium-free coating layer 13; by adding an organic resin In the lubricating aqueous metal surface treatment agent, once dried, an organic-inorganic composite chromium-free coating layer which is not easily dissolved in water is formed with the inorganic skeleton, and the barrier effect is enhanced to suppress corrosion.
同時，上述有機-無機複合型無鉻塗覆層因具較低表面能，故可提供滑順觸感，並避免指紋印或油漬污染產品外觀。再者，藉由無機組份中微粒二氧化矽之本身玻璃質特性，可進一步提升該無鉻塗覆層13之硬度、減緩長期摩擦作業中損耗該無鉻塗覆層13及刮傷材料表面。At the same time, the above-mentioned organic-inorganic composite type chromium-free coating layer can provide a smooth touch feeling and avoid the appearance of fingerprints or oil stains due to the lower surface energy. Furthermore, by the inherent glassy characteristics of the particulate cerium oxide in the inorganic component, the hardness of the chromium-free coating layer 13 can be further improved, and the surface of the chromium-free coating layer 13 and the scratched material can be reduced in long-term friction work. .
該潤滑型水性金屬表面處理劑中之蠟添加物可提供該無鉻塗覆層13所需之潤滑性，主要貢獻來自：(1)塗層乾燥過程中軟化蠟微粒硬度，促使部分蠟分布於該無鉻塗覆層13上層並達到成形加工時潤滑之目的；及(2)高熔點蠟微粒不受乾燥過程影響，反因本身硬度高且粒徑略高於乾膜厚度，達到類似軸承潤滑之功效。The wax additive in the lubricating aqueous metal surface treatment agent can provide the lubricity required for the chromium-free coating layer 13, and the main contribution comes from: (1) the hardness of the softened wax particles during the drying process of the coating, and the partial wax distribution is promoted. The upper layer of the chromium-free coating layer 13 is used for the purpose of lubrication during forming processing; and (2) the high melting point wax particles are not affected by the drying process, and the self-hardness is high and the particle diameter is slightly higher than the dry film thickness to achieve similar bearing lubrication. The effect.
另外，藉由該無鉻塗覆層13形成於鋼板之表面，其成品不僅具潤滑功效可應用於滑軌用途上，其自潤滑特性亦有助於減少下游業者加工成形過程中潤滑油及切削油之用量，且亦可減少脫脂液用量而降低客戶作業及廢液處理成本。In addition, the chromium-free coating layer 13 is formed on the surface of the steel sheet, and the finished product is not only lubricated and can be applied to the rails, and the self-lubricating property also helps to reduce lubricating oil and cutting during processing in the downstream industry. The amount of oil used can also reduce the amount of degreasing liquid and reduce the cost of customer operations and waste disposal.
本發明之高強度潤滑鍍鋅鋼板10具有優異機械強度及具備良好之外觀品質，且藉由該無鉻塗覆層13可有效阻隔腐蝕因子的入侵，同時讓鋼板表面具備均勻外觀、良好之耐蝕性、耐鹼洗性、潤滑性及耐磨耗性。此外，本發明使用之潤滑型水性金屬表面處理劑係為無鉻處理劑，因此，不會對環境造成污染，符合環保要求。The high-strength lubricating galvanized steel sheet 10 of the present invention has excellent mechanical strength and good appearance quality, and the chromium-free coating layer 13 can effectively block the invasion of corrosion factors, and at the same time, the steel sheet surface has a uniform appearance and good corrosion resistance. Properties, alkali washability, lubricity and wear resistance. Further, the lubricating type aqueous metal surface treatment agent used in the present invention is a chromium-free treatment agent, and therefore, it does not cause environmental pollution and meets environmental protection requirements.
茲以下列實例予以詳細說明本發明，唯並不意謂本發明僅侷限於此等實例所揭示之內容。The invention is illustrated by the following examples, which are not intended to be limited to the scope of the invention.
發明例Invention example 1~14(1~14( 以下標註為Labeled below E1~E14)E1~E14) 之共同製法：Common method:
1. 潤滑型水性金屬表面處理劑：1. Lubricating waterborne metal surface treatment agent:
依據表1之組成種類及含量比例，分別將水溶性鋯化合物、矽化合物、含氟化合物、磷酸化合物、有機樹脂及蠟添加物加以混合，接著再加入水攪拌均勻，以分別製得發明例1~14之潤滑型水性金屬表面處理劑。According to the composition type and the content ratio of Table 1, the water-soluble zirconium compound, the cerium compound, the fluorine-containing compound, the phosphoric acid compound, the organic resin and the wax additive were respectively mixed, and then water was added and stirred uniformly to obtain the inventive example 1 respectively. ~14 lubricated waterborne metal surface treatment agent.
2. 經表面處理之金屬材料：2. Surface treated metal materials:
分別取一熱浸鍍鋅鋼板(GI)，其底材合金元素組份及Ra值如表1所示；將其表面進行鹼脫脂處理、水洗及乾燥，然後利用＃3棒塗覆器（RDS 3號），將上述所製得之潤滑型水性金屬表面處理劑塗佈於金屬本體之表面，再將經塗佈有潤滑型水性金屬表面處理劑之金屬本體放置於熱循環型烘箱中，以板溫100℃進行乾燥，待乾燥一段時間，即分別製得發明例1~14之經表面處理之金屬材料。Take a hot dip galvanized steel sheet (GI), the substrate alloying element composition and Ra value are shown in Table 1; the surface is subjected to alkali degreasing treatment, water washing and drying, and then using #3 rod applicator (RDS) No. 3), the lubricating water-based metal surface treatment agent prepared above is applied to the surface of the metal body, and the metal body coated with the lubricating aqueous metal surface treatment agent is placed in a heat cycle type oven to The sheet temperature was dried at 100 ° C, and after drying for a while, the surface-treated metal materials of Inventive Examples 1 to 14 were respectively obtained.
比較例Comparative example 1~6(1~6 ( 以下標註為Labeled below C1~C6)C1~C6) 之共同製法：Common method:
1. 潤滑型水性金屬表面處理劑：1. Lubricating waterborne metal surface treatment agent:
除了依據表1改變成分組成及用量之外，其餘製備過程皆與發明例1~14相同，最後分別製得比較例1~4之潤滑型水性金屬表面處理劑，比較例5~6則選自兩款商業用水性耐指紋塗料。Except for changing the composition and amount according to Table 1, the other preparation processes were the same as those of Invention Examples 1 to 14, and finally the lubricating aqueous surface treatment agents of Comparative Examples 1 to 4 were respectively prepared, and Comparative Examples 5 to 6 were selected from Two commercial water-based fingerprint resistant coatings.
2. 經表面處理之金屬材料：2. Surface treated metal materials:
除了分別選用比較例1~6之潤滑型水性金屬表面處理劑外，其餘製備過程皆與發明例1~14相同，最後分別製得比較例1~6之經表面處理之金屬材料。 表1.發明例與比較例之潤滑型水性金屬表面處理劑的組成
[[ 測試test ]]
將上述發明例1~14與比較例1~6所製得之鋼板（金屬材料）分別進行以下測試，所得結果分別如表2所示。 表2.發明例與比較例之測試結果
1. 表面外觀：1. Surface appearance:
對各樣品的表面外觀進行目視檢視及評價。若外觀良好、無點狀，標註為「○」；若外觀看到少量點狀分佈，標註為「△」；若外觀看到多量點狀或線狀分佈，標註為「Í」。The surface appearance of each sample was visually inspected and evaluated. If the appearance is good and there is no dot, it is marked as "○"; if the appearance sees a small number of dot-like distribution, it is marked as "△"; if the appearance sees a large number of dotted or linear distribution, it is marked as "Í".
2. 耐蝕性：2. Corrosion resistance:
採用JIS Z-2371標準方法之鹽水噴霧試驗，在試驗72小時後，以目視評估鋼板表面之白鏽發生面積，當白鏽發生面積越小時，表示耐蝕性越佳。若白鏽發生面積≧50%則判定耐蝕性不佳，標註為「Í」；若30%≦白鏽發生面積≦50%，則判定耐蝕性差，標註為「△」；若10%≦白鏽發生面積≦30%，則判定耐蝕性尚可，標註為「○」；若白鏽發生面積＜10%，則判定耐蝕性佳，標註為「◎」。The salt spray test using the standard method of JIS Z-2371, visually evaluated the area of white rust on the surface of the steel sheet after 72 hours of the test, and the smaller the area where the white rust occurred, the better the corrosion resistance. If the area of white rust is ≧50%, it is judged that the corrosion resistance is not good, and it is marked as “Í”; if 30% ≦ white rust occurs in area ≦50%, it is judged that the corrosion resistance is poor, and it is marked as “△”; if 10% ≦ white rust When the occurrence area is 30%, the corrosion resistance is judged to be "○", and if the white rust occurrence area is <10%, the corrosion resistance is judged to be good, and it is marked as "◎".
3. 耐鹼洗性：3. Alkali washability:
將上述所製得之經表面處理之鋼板浸於日本巴卡萊公司製造的鹼洗脫脂劑Parclean 364S(20 g/L)，且調整65℃的脫脂劑水溶液2分鐘後水洗並冷風乾燥。後續採用JIS Z-2371標準方法之鹽水噴霧試驗，在試驗72小時後，以目視評估鋼板表面之白鏽發生面積，當白鏽發生面積越小時，表示鹼洗後耐鹼洗性越佳。若白鏽發生面積≧50%則判定耐鹼洗性不佳，標註為「Í」；若30%≦白鏽發生面積≦50%，則判定耐鹼洗性差，標註為「△」；若10%≦白鏽發生面積≦30%，則判定耐鹼洗性尚可，標註為「○」；若白鏽發生面積＜10%，則判定耐鹼洗性佳，標註為「◎」。The surface-treated steel sheet prepared above was immersed in an alkali-releasing agent Parclean 364S (20 g/L) manufactured by Baccarat, Japan, and adjusted to a degreasing agent aqueous solution at 65 ° C for 2 minutes, washed with water and dried by cold air. Subsequently, the salt spray test using the standard method of JIS Z-2371 was carried out, and the area of white rust on the surface of the steel sheet was visually evaluated after 72 hours of the test. When the area where the white rust occurred was small, the alkali-resistant washing property after alkali washing was better. If the area of white rust is ≧50%, it is judged that the alkali-resistant washing property is not good, and it is marked as “Í”; if the area of 5% white rust is ≦50%, it is judged that the alkali-resistant washing property is poor, and it is marked as “△”; When the area of occurrence of white rust is ≦30%, it is judged that the alkali-resistant washing property is acceptable, and it is marked as "○". If the area of white rust is <10%, it is judged that the alkali-resistant washing property is good, and it is marked as "◎".
4. 潤滑性：4. Lubricity:
在發明例1~14與比較例1~6所分別製得未經塗油處理之鋼板表面上，以直徑5 mm不鏽鋼球作為探頭，並以荷重200克、移動速率300 mm/min，來回測試第4次及第20次之動摩擦係數(μk )。In the inventions 1 to 14 and the comparative examples 1 to 6, respectively, the surface of the uncoated oil-treated steel sheet was used as a probe with a diameter of 5 mm stainless steel ball, and tested with a load of 200 g and a moving rate of 300 mm/min. The fourth and 20th kinetic friction coefficient (μ k ).
◎：來回測試第4次及第20次之動摩擦係數(μk )≦0.10。◎: The coefficient of friction (μ k ) ≦ 0.10 of the 4th and 20th times was tested back and forth.
○：來回測試第4次及第20次之動摩擦係數(μk )；0.10＜μk ≦0.15。○: The coefficient of friction (μ k ) of the 4th and 20th times was tested back and forth; 0.10 < μ k ≦ 0.15.
△：來回測試第4次及第20次之動摩擦係數(μk )；0.15＜μk ≦0.25。△: The coefficient of friction (μ k ) of the 4th and 20th times was tested back and forth; 0.15 < μ k ≦ 0.25.
Í：來回測試第4次及第20次之動摩擦係數(μk )＞0.25。Í: The coefficient of friction (μ k ) of the 4th and 20th passes was tested back and forth >0.25.
5. 耐磨耗性：5. Wear resistance:
在發明例1~14與比較例1~6所分別製得未經塗油處理之鋼板表面上，以直徑5 mm不鏽鋼球作為探頭，並以荷重200克、移動速率300 mm/min，來回測試第100次之動摩擦係數(μk )。In the inventions 1 to 14 and the comparative examples 1 to 6, respectively, the surface of the uncoated oil-treated steel sheet was used as a probe with a diameter of 5 mm stainless steel ball, and tested with a load of 200 g and a moving rate of 300 mm/min. The 100th moment of friction coefficient (μ k ).
◎：來回測試第100次之動摩擦係數(μk )≦0.10。◎: The coefficient of friction (μ k ) ≦ 0.10 of the 100th time was tested back and forth.
○：來回測試第100次之動摩擦係數(μk )；0.10＜μk ≦0.15。○: The coefficient of friction (μ k ) of the 100th time was tested back and forth; 0.10 < μ k ≦ 0.15.
△：來回測試第100次之動摩擦係數(μk )；0.15＜μk ≦0.25。△: The coefficient of friction (μ k ) of the 100th time was tested back and forth; 0.15 < μ k ≦ 0.25.
Í：來回測試第100次之動摩擦係數(μk )＞0.25。Í: The coefficient of friction (μ k ) of the 100th pass back and forth is >0.25.
由表2之結果可知，發明例1~14所製得之鋼板皆同時具有良好外觀及具備良好的耐蝕性、耐鹼洗性、潤滑性及耐磨耗性；反觀比較例1~6所製得之鋼板，其具有任意一項以上較差之耐蝕性、耐鹼洗性、潤滑性及耐磨耗性。As can be seen from the results of Table 2, the steel sheets obtained in Inventive Examples 1 to 14 all have good appearance and good corrosion resistance, alkali-resistant washing property, lubricity and abrasion resistance; in contrast, Comparative Examples 1 to 6 were produced. The obtained steel sheet has any one of the above-mentioned poor corrosion resistance, alkali-resistant washing property, lubricity and wear resistance.
上述實施例僅為說明本發明之原理及其功效，並非限制本發明，因此習於此技術之人士對上述實施例進行修改及變化仍不脫本發明之精神。本發明之權利範圍應如後述之申請專利範圍所列。The above embodiments are merely illustrative of the principles and effects of the present invention, and are not intended to limit the scope of the present invention. The scope of the invention should be as set forth in the appended claims.
10‧‧‧高強度潤滑鍍鋅鋼板10‧‧‧High-strength lubricated galvanized steel sheet
11‧‧‧鋼底材11‧‧‧Steel substrate
11S‧‧‧表面11S‧‧‧ surface
12‧‧‧鋅鍍層12‧‧‧Zinc plating
12S‧‧‧粗糙表面12S‧‧‧Rough surface
13‧‧‧無鉻塗覆層13‧‧‧Chromium-free coating
S21~S23‧‧‧步驟S21~S23‧‧‧Steps
圖1顯示本發明高強度潤滑鍍鋅鋼板之結構示意圖。Fig. 1 is a view showing the structure of a high-strength lubricating galvanized steel sheet according to the present invention.
圖2顯示本發明高強度潤滑鍍鋅鋼板之製造方法之流程圖。2 is a flow chart showing a method of manufacturing the high strength lubricating galvanized steel sheet of the present invention.
圖3A顯示本發明高強度潤滑鍍鋅鋼板之製造方法中之一鋼底材之示意圖。Fig. 3A is a view showing a steel substrate of a method for producing a high-strength lubricating galvanized steel sheet according to the present invention.
圖3B顯示依據本發明高強度潤滑鍍鋅鋼板之製造方法形成一鋅鍍層於鋼底材之表面之示意圖。Figure 3B is a schematic view showing the formation of a zinc coating on the surface of a steel substrate in accordance with the method of manufacturing a high strength lubricating galvanized steel sheet according to the present invention.
圖3C顯示依據本發明高強度潤滑鍍鋅鋼板之製造方法形成一無鉻塗覆層於鋅鍍層上之示意圖。3C is a schematic view showing the formation of a chromium-free coating layer on a zinc plating layer in accordance with the method for producing a high-strength lubricating galvanized steel sheet according to the present invention.
Claims (32)
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| TWI726763B (en) * | 2020-07-07 | 2021-05-01 | 中國鋼鐵股份有限公司 | Self-bonding coated electrical steel sheet, laminated core, and method for producing the same |
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| TWI507563B (en) * | 2012-10-17 | 2015-11-11 | China Steel Corp | A chromium-free surface treatment liquid for steel and a steel surface treatment method using the treatment liquid |
| JP5825244B2 (en) * | 2012-10-31 | 2015-12-02 | Ｊｆｅスチール株式会社 | Hot-dip galvanized steel sheet |
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| TWI726763B (en) * | 2020-07-07 | 2021-05-01 | 中國鋼鐵股份有限公司 | Self-bonding coated electrical steel sheet, laminated core, and method for producing the same |
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