TWI789985B - Enameled steel sheet and method of forming the same - Google Patents
Enameled steel sheet and method of forming the same Download PDFInfo
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本發明是關於一種搪瓷鋼片及其製造方法,特別是關於一種具有抗高溫軟化特性的搪瓷鋼片及其製造方法。The invention relates to an enamelled steel sheet and a manufacturing method thereof, in particular to an enamelled steel sheet with high temperature softening resistance and a manufacturing method thereof.
習知冷軋搪瓷鋼片一般係以低碳鋼為材料,藉由降低碳含量以提高成形性。另外,藉由添加鈦、氮及硫等元素添加物,以提升鋼材內部吸附氫氣的能力,進而避免跳鐵現象(或稱為鱗爆(fishscale)現象)。其中,跳鐵現象係由於降溫過程中氫原子在鋼材與搪瓷界面聚集形成氫氣,大量氫氣使得界面壓力過大,進而導致搪瓷層局部剝落的現象。因此,添加前述之元素添加物可使搪瓷層與鋼材密合不易脫落,且後續經過熱軋、冷軋及連續退火製程,可獲得具有低強度及良好深衝性的冷軋成品。The known cold-rolled enamelled steel sheet is generally made of low-carbon steel, and the formability is improved by reducing the carbon content. In addition, by adding elemental additives such as titanium, nitrogen, and sulfur, the ability to absorb hydrogen gas inside the steel is improved, thereby avoiding the phenomenon of iron jumping (or fishscale phenomenon). Among them, the phenomenon of iron jumping is due to the accumulation of hydrogen atoms at the interface between steel and enamel to form hydrogen gas during the cooling process. A large amount of hydrogen gas makes the interface pressure too high, which leads to the phenomenon of local peeling of the enamel layer. Therefore, adding the above-mentioned element additives can make the enamel layer and the steel closely bonded and not easy to fall off, and after subsequent hot rolling, cold rolling and continuous annealing processes, a cold-rolled finished product with low strength and good deep drawability can be obtained.
然而,習知搪瓷鋼片大部分為深衝級用料,故產品的強度低且伸長率高,適於用作鍋具及廚具等複雜外型的器具。若要用於需高強度以抵抗外力衝擊,或需承受內部壓力的器具(例如熱水器內膽)時,則習知搪瓷鋼片的強度無法負荷。一般而言,搪瓷過程中需進行高溫熱處理,以利釉藥溶解以附著於鋼材,但習知搪瓷鋼片經過高溫後,產品強度大幅下降,以致於其耐衝擊性及耐壓性劣化,故不具抗高溫軟化的特性。However, conventional enamel steel sheets are mostly deep-drawing grade materials, so the product has low strength and high elongation, and is suitable for use as utensils with complex shapes such as pots and kitchen utensils. If it is used for appliances that need high strength to resist external shocks or to withstand internal pressure (such as water heater inner tanks), the strength of conventional enamelled steel sheets cannot bear the load. Generally speaking, high-temperature heat treatment is required in the enamelling process to facilitate the dissolution of the glaze and adhere to the steel. However, it is known that the strength of the enamelled steel sheet is greatly reduced after being subjected to high temperature, so that its impact resistance and pressure resistance are deteriorated. Therefore, Not resistant to high temperature softening properties.
有鑑於此,亟須提供一種搪瓷鋼片及其製造方法,以製造具有抗高溫軟化特性的搪瓷鋼片,並兼具良好氫擴散係數。In view of this, there is an urgent need to provide an enamelled steel sheet and a manufacturing method thereof, so as to manufacture an enamelled steel sheet with high temperature softening resistance and good hydrogen diffusion coefficient.
本發明之一態樣是提供一種搪瓷鋼片的製造方法,其係藉由對具有特定成分的鋼胚依序進行熱軋操作、盤捲操作、冷軋操作、調質軋延操作及熱處理操作,以獲得具有抗高溫軟化特性及良好氫擴散係數的搪瓷鋼片。One aspect of the present invention is to provide a manufacturing method of enamelled steel sheet, which is to sequentially perform hot rolling operation, coiling operation, cold rolling operation, quenching and tempering rolling operation and heat treatment operation on a steel billet with specific composition To obtain enamelled steel sheets with high temperature softening properties and good hydrogen diffusion coefficient.
本發明之另一態樣是提供一種搪瓷鋼片,其係以上述態樣的製造方法所製得,且具有高強度及良好氫擴散係數。Another aspect of the present invention is to provide an enamelled steel sheet, which is produced by the manufacturing method of the above aspect, and has high strength and good hydrogen diffusion coefficient.
根據本發明之一態樣,提供一種搪瓷鋼片的製造方法,其包含提供鋼胚。基於鋼胚為100 wt%,鋼胚包括0.04 wt%至0.16 wt%的碳、0.05 wt%至1.50 wt%的錳、0.01 wt%至0.30 wt%的矽、0.01 wt%至0.20 wt%的磷、0.01 wt%至0.30 wt%的銅、0.01 wt%至0.30 wt%的鉻、0.01 wt%至0.10 wt%的鈦、0.01 wt%至0.12 wt%的鋁、0.01 wt%至0.02 wt%的氮、不大於0.03 wt%的硫、不大於0.10 wt%的鎳、其餘為鐵及不可避免的雜質。對鋼胚進行熱軋操作,以獲得完軋鋼材。According to an aspect of the present invention, a method for manufacturing an enamelled steel sheet is provided, which includes providing a steel billet. Based on 100 wt% of the billet, the billet includes 0.04 wt% to 0.16 wt% of carbon, 0.05 wt% to 1.50 wt% of manganese, 0.01 wt% to 0.30 wt% of silicon, 0.01 wt% to 0.20 wt% of phosphorus , 0.01 to 0.30 wt% copper, 0.01 to 0.30 wt% chromium, 0.01 to 0.10 wt% titanium, 0.01 to 0.12 wt% aluminum, 0.01 to 0.02 wt% nitrogen , not more than 0.03 wt% of sulfur, not more than 0.10 wt% of nickel, and the rest are iron and unavoidable impurities. The steel billet is subjected to a hot rolling operation to obtain finished rolled steel.
接著,對完軋鋼材進行盤捲操作,以獲得熱軋鋼捲。盤捲操作之盤捲溫度為550℃至650℃。然後,對熱軋鋼捲進行冷軋操作,以獲得冷軋鋼帶。冷軋操作之裁減率為40%至80%。對冷軋鋼帶進行調質軋延操作,以獲得底材。調質軋延的軋延率為0.5%至3.0%。接著,對底材進行熱處理操作,以獲得搪瓷鋼片。Next, coiling is performed on the finished rolled steel to obtain hot-rolled steel coils. The coiling temperature for the coiling operation is 550°C to 650°C. Then, the hot-rolled steel coil is subjected to a cold-rolling operation to obtain a cold-rolled steel strip. The reduction rate of the cold rolling operation is 40% to 80%. The cold-rolled steel strip is tempered and rolled to obtain a substrate. The rolling ratio of temper rolling is 0.5% to 3.0%. Next, a heat treatment operation is performed on the substrate to obtain an enamelled steel sheet.
根據本發明之一實施例,上述熱軋操作包含對鋼胚進行再加熱步驟,以升溫至1150℃至1300℃。接著,在再加熱步驟之後,對鋼胚進行熱軋步驟,以獲得完軋鋼材。熱軋步驟之完軋溫度不低於Ar3溫度。According to an embodiment of the present invention, the above-mentioned hot rolling operation includes a step of reheating the steel billet to raise the temperature to 1150°C to 1300°C. Next, after the reheating step, the billet is subjected to a hot rolling step to obtain a finished rolled steel product. The finishing temperature of the hot rolling step is not lower than the Ar3 temperature.
根據本發明之一實施例,上述方法更包含在調質軋延操作之前,對冷軋鋼帶進行退火操作。According to an embodiment of the present invention, the above method further includes performing an annealing operation on the cold-rolled steel strip before the temper rolling operation.
根據本發明之一實施例,上述退火操作包含對冷軋鋼帶進行加熱步驟,以達到650℃至850℃。在加熱步驟之後,對冷軋鋼帶於650℃至850℃進行80秒至240秒的持溫步驟。接著,在持溫步驟之後,對冷軋鋼帶進行降溫步驟,以降至室溫。According to an embodiment of the present invention, the above-mentioned annealing operation includes a step of heating the cold-rolled steel strip to reach 650°C to 850°C. After the heating step, the cold-rolled steel strip is subjected to a temperature holding step at 650° C. to 850° C. for 80 seconds to 240 seconds. Next, after the temperature holding step, the cold-rolled steel strip is subjected to a temperature-lowering step to drop to room temperature.
根據本發明之一實施例,上述冷軋操作之裁減率為40%至80%。According to an embodiment of the present invention, the reduction ratio of the above-mentioned cold rolling operation is 40% to 80%.
根據本發明之一實施例,上述熱處理操作包含以850℃至950℃之溫度進行10分鐘至20分鐘。According to an embodiment of the present invention, the above heat treatment operation includes performing at a temperature of 850° C. to 950° C. for 10 minutes to 20 minutes.
根據本發明之一實施例,上述搪瓷鋼片之降伏強度與底材之降伏強度的差值不大於20 MPa。According to an embodiment of the present invention, the difference between the yield strength of the enamelled steel sheet and the yield strength of the substrate is not greater than 20 MPa.
根據本發明之另一態樣,提供一種搪瓷鋼片,其係由上述態樣所述之製造方法所製得。According to another aspect of the present invention, an enamelled steel sheet is provided, which is produced by the manufacturing method described in the above aspect.
根據本發明之一實施例,上述搪瓷鋼片具有不小於300 MPa的降伏強度及不小於400 MPa的抗拉強度。According to an embodiment of the present invention, the enamelled steel sheet has a yield strength not less than 300 MPa and a tensile strength not less than 400 MPa.
根據本發明之一實施例,上述搪瓷鋼片具有6.0×10 -7至9.0×10 -7cm 2/s之氫擴散係數。 According to an embodiment of the present invention, the above-mentioned enamelled steel sheet has a hydrogen diffusion coefficient of 6.0×10 -7 to 9.0×10 -7 cm 2 /s.
應用本發明之搪瓷鋼片及其製造方法,藉由對具有特定成分的鋼胚依序進行熱軋操作、盤捲操作、冷軋操作、調質軋延操作及熱處理操作,並控制盤捲溫度及調質軋延率,以獲得具有抗高溫軟化特性及良好氫擴散係數的搪瓷鋼片。Applying the enamelled steel sheet and its manufacturing method of the present invention, by sequentially performing hot rolling operation, coiling operation, cold rolling operation, quenching and tempering rolling operation and heat treatment operation on the steel billet with specific composition, and controlling the coiling temperature And quenching and tempering rolling rate to obtain enameled steel sheet with high temperature softening resistance and good hydrogen diffusion coefficient.
如本揭露所使用的「大約(around)」、「約(about)」、「近乎 (approximately)」或「實質上(substantially)」一般係代表在所述之數值或範圍的百分之20以內、或百分之10以內、或百分之5以內。As used in this disclosure, "around", "about", "approximately" or "substantially" generally means within 20 percent of the value or range stated , or within 10 percent, or within 5 percent.
承上所述,本發明提供一種搪瓷鋼片及其製造方法,藉由對具有特定成分的鋼胚依序進行熱軋操作、盤捲操作、冷軋操作、調質軋延操作及熱處理操作,並控制盤捲溫度及調質軋延率,以獲得具有抗高溫軟化特性及良好氫擴散係數的搪瓷鋼片。Based on the above, the present invention provides an enamelled steel sheet and its manufacturing method, by sequentially performing hot rolling operation, coiling operation, cold rolling operation, quenching and tempering rolling operation and heat treatment operation on the steel billet with specific composition, And control the coil temperature and quenching and tempering rolling rate to obtain enameled steel sheet with high temperature softening resistance and good hydrogen diffusion coefficient.
請參閱圖1,其係繪示根據本發明一些實施例之搪瓷鋼片的製造方法100的流程圖。首先,進行操作110,提供鋼胚。在一些實施例中,基於鋼胚為100 wt%,鋼胚包含0.04 wt%至0.16 wt%的碳、0.04 wt%至0.16 wt%的碳、0.01 wt%至0.30 wt%的矽、0.01 wt%至0.20 wt%的磷、0.01 wt%至0.30 wt%的銅、0.01 wt%至0.30 wt%的鉻、0.01 wt%至0.10 wt%的鈦、0.01 wt%至0.12 wt%的鋁、0.01 wt%至0.02 wt%的氮、不大於0.03 wt%的硫、不大於0.10 wt%的鎳、其餘為鐵及不可避免的雜質。Please refer to FIG. 1 , which is a flowchart illustrating a
一般而言,鋼胚的碳、錳、矽、磷及硫的含量會影響後續製得之鋼片的強度及成形性。舉例而言,碳含量在0.07 wt%至0.11 wt%及/或錳含量為0.5 wt%至1.0 wt%,可製得具有較高強度的鋼片。然而,若強度太強,又會影響鋼片的成形性,例如若碳含量高於0.16 wt%,則鋼片的成形性不佳。另外,鋼胚的銅、鎳及鉻的含量主要是控制為可有效的防銹,但又不致增加太多成本。鈦含量須控制在上述範圍,以防止跳鐵的情形。鋁及氮的含量會影響析出的氮化鋁(AlN),氮化鋁的析出有助於使鋼片具有抗軟化的功效。Generally speaking, the content of carbon, manganese, silicon, phosphorus and sulfur in the billet will affect the strength and formability of the subsequent steel sheet. For example, a carbon content of 0.07 wt% to 0.11 wt% and/or a manganese content of 0.5 wt% to 1.0 wt% can produce a steel sheet with higher strength. However, if the strength is too strong, the formability of the steel sheet will be affected. For example, if the carbon content is higher than 0.16 wt%, the formability of the steel sheet will be poor. In addition, the content of copper, nickel and chromium in the billet is mainly controlled to effectively prevent rust without increasing the cost too much. The titanium content must be controlled within the above range to prevent iron jumping. The content of aluminum and nitrogen will affect the precipitated aluminum nitride (AlN), and the precipitation of aluminum nitride helps to make the steel sheet have the effect of softening resistance.
接著,進行操作120,對鋼胚進行熱軋操作,以獲得完軋鋼材。在一些實施例中,熱軋操作包含先對鋼胚進行再加熱步驟,以升溫至1150℃至1300℃。然後,對鋼胚進行熱軋步驟,以獲得完軋鋼材。熱軋步驟之完軋溫度不低於Ar3溫度。補充說明的是,Ar3溫度係鋼材在冷卻時,沃斯田鐵開始變態成肥粒鐵的溫度。換言之,本發明之熱軋操作係期望在沃斯田鐵相完成熱軋延。Next, proceed to
然後,進行操作130,對完軋鋼材進行盤捲操作,以獲得熱軋鋼捲。在一些實施例中,盤捲操作之盤捲溫度為550℃至650℃。本發明係使用較習知更高的盤捲溫度進行盤捲操作,其係由於若盤捲溫度太低,則氮化鋁的析出量太少,則後續製得之鋼片的強度太低,無法達到本發明的功效。Then, proceed to
接著,進行操作140,對熱軋鋼捲進行冷軋操作,以獲得冷軋鋼帶。在一些實施例中,冷軋操作的裁減率為40%至80%,較佳為60%至80%。冷軋裁減率在前述範圍,以獲得符合厚度要求的冷軋鋼帶。Next, proceed to
在進行後續操作150之前,可選擇性地對冷軋鋼帶進行退火操作。在一些實施例中,退火操作可在連續退火設備中進行,其包含先對冷軋鋼帶進行加熱步驟,經過約500秒至約800秒,以由室溫升溫至約650℃至約850℃。接著,在約650℃至約850℃進行80秒至240秒的持溫步驟。然後,對冷軋鋼帶進行降溫步驟,以降至室溫。在此實施例中,降溫步驟包含於約15秒至約48秒降溫至約450℃至約560℃;接著,於約12秒至約35秒內,再降溫至約320℃至約400℃;然後,於約310秒至約900秒內,可再降溫至約210℃至約300℃;最後,於約40秒至約130秒降溫至室溫。The cold rolled steel strip may optionally be subjected to an annealing operation prior to
然後,在進行操作140或前述選擇性進行的退火操作後,進行操作150,對冷軋鋼帶進行調質軋延操作,以獲得底材。在一些實施例中,調質軋延的軋延率為0.5%至3.0%,較佳為2.0%至3.0%。當調質軋延的軋延率低於0.5%時,則無法消除降伏點延伸,進而無法獲得具有高降伏強度的底材;反之,若調質軋延的軋延率高於3.0%時,則所得底材的表面粗糙度太高,故後續無法獲得較平整的鋼片。相較於習知製程所製得之底材僅具有不大於200 MPa的降伏強度及不大於300 MPa的抗拉度。在本發明的一些實施例中,底材可具有不小於300 MPa的降伏強度及不小於400 MPa的抗拉強度。在另一些實施例中,底材具有大於約20%的伸長率,較佳是大於約25%的伸長率。Then, after performing
接著,進行操作160,對底材進行熱處理操作,以獲得搪瓷鋼片。在一些實施例中,熱處理操作包含以850℃至950℃之溫度進行10分鐘至20分鐘,且熱處理操作可在一般大氣氣氛中進行。在一些實施例中,搪瓷鋼片具有不小於300 MPa的降伏強度及不小於400 MPa的抗拉強度。Next, proceed to
習知製程中,底材在經過高溫熱處理後所得之搪瓷鋼片的降伏強度會大幅下降,例如下降約75 MPa以上。然而,本發明之底材在經過高溫熱處理後,降伏強度的差值不大於20 MPa。換言之,本發明之搪瓷鋼片具有良好的抗高溫軟化效果。In the conventional process, the yield strength of the enamelled steel sheet obtained after the substrate is subjected to high temperature heat treatment will be greatly reduced, for example, by about 75 MPa or more. However, the difference in yield strength of the substrate of the present invention is not greater than 20 MPa after high-temperature heat treatment. In other words, the enamelled steel sheet of the present invention has good anti-high temperature softening effect.
在一些實施例中,本發明製得之搪瓷鋼片的金相組織主要是肥粒鐵相及高碳波來鐵相,且其晶粒型態為等軸晶。補充說明的是,等軸晶的各向成形度較均勻,故成形後的破裂風險較低。另外,在上述操作150所獲得的底材之晶粒度約11至12號(即平均粒徑為約5 μm至約17 μm),而操作160後的搪瓷鋼片之晶粒度約10至11號(即平均粒徑為約10 μm至約23 μm),即高溫熱處理沒有使晶粒尺寸有顯著變化。一般而言,晶粒尺寸會影響鋼材的強度,故底材強度和搪瓷鋼片的降伏強度差異不大,而其晶粒尺寸相近係由於氮化鋁析出釘紮於晶界上,而有效減緩高溫退火時的晶粒成長行為。In some embodiments, the metallographic structure of the enamelled steel sheet produced by the present invention is mainly ferrite phase and high carbon wavelet iron phase, and its grain shape is equiaxed grain. It is supplemented that the isotropic formability of equiaxed crystals is more uniform, so the risk of fracture after forming is lower. In addition, the grain size of the substrate obtained in the
在一些實施例中,依照ASTM G148規範,上述搪瓷鋼片具有6.0×10 -7至9.0×10 -7cm 2/s之氫擴散係數。應理解的是,氫擴散係數愈小,代表氫在試片中愈不易通過,即在金屬內的氫愈不易擴散。然而,本發明的搪瓷鋼片具有較小的氫擴散係數,顯示其具有較佳的儲氫能力,則應具有較佳的抗跳鐵能力。 In some embodiments, according to ASTM G148 specification, the enamelled steel sheet has a hydrogen diffusion coefficient of 6.0×10 −7 to 9.0×10 −7 cm 2 /s. It should be understood that the smaller the hydrogen diffusion coefficient, the harder it is for hydrogen to pass through the test piece, that is, the harder it is for hydrogen in the metal to diffuse. However, the enamelled steel sheet of the present invention has a relatively small hydrogen diffusion coefficient, which indicates that it has a better hydrogen storage capacity, and therefore should have a better anti-jumping capacity.
以下利用數個實施例以說明本發明之應用,然其並非用以限定本發明,本發明技術領域中具有通常知識者,在不脫離本發明之精神和範圍內,當可作各種之更動與潤飾。 實施例一至三 Several examples are used below to illustrate the application of the present invention, but it is not intended to limit the present invention. Those with ordinary knowledge in the technical field of the present invention can make various modifications and changes without departing from the spirit and scope of the present invention. retouch. Embodiment one to three
實施例一至三使用的鋼胚包含0.04 wt%至0.16 wt%的碳、0.01 wt%至0.30 wt%的矽、0.01 wt%至0.20 wt%的磷、0.01 wt%至0.30 wt%的銅、0.01 wt%至0.30 wt%的鉻、0.01 wt%至0.10 wt%的鈦、0.01 wt%至0.12 wt%的鋁、0.01 wt%至0.02 wt%的氮、不大於0.03 wt%的硫、不大於0.10 wt%的鎳、其餘為鐵及不可避免的雜質。然後,對鋼胚依序進行再加熱步驟、熱軋步驟以及盤捲操作,以獲得熱軋鋼捲,其中再加熱步驟的溫度為1160℃至1240℃,完軋溫度為850至910℃,盤捲溫度為550℃至650℃。The steel blank used in Examples 1 to 3 contains 0.04 wt% to 0.16 wt% of carbon, 0.01 wt% to 0.30 wt% of silicon, 0.01 wt% to 0.20 wt% of phosphorus, 0.01 wt% to 0.30 wt% of copper, 0.01 wt% to 0.30 wt% chromium, 0.01 wt% to 0.10 wt% titanium, 0.01 wt% to 0.12 wt% aluminum, 0.01 wt% to 0.02 wt% nitrogen, not more than 0.03 wt% sulfur, not more than 0.10 wt% of nickel, the rest is iron and unavoidable impurities. Then, the billets are sequentially subjected to reheating steps, hot rolling steps and coiling operations to obtain hot-rolled steel coils, wherein the temperature in the reheating step is 1160°C to 1240°C, the temperature for finishing rolling is 850°C to 910°C, and the coiling The temperature is 550°C to 650°C.
接著,對熱軋鋼捲進行冷軋操作後,於室溫下進行連續退火操作,並於退火降至室溫後進行調質軋延,以獲得實施例一的底材,其中冷軋裁減率為50%至60%,且調質軋延率為2.0%至2.5%。實施例二及三皆使用與實施例一相同的材料及製程。Next, after cold-rolling the hot-rolled steel coil, carry out continuous annealing operation at room temperature, and perform quenching and tempering rolling after the annealing is lowered to room temperature, so as to obtain the substrate of Example 1, wherein the cold-rolling reduction rate is 50% to 60%, and the quenching and tempering rolling rate is 2.0% to 2.5%. Embodiments 2 and 3 all use the same materials and processes as
實施例一至三的底材再利用約870℃的溫度進行 約10分鐘的高溫熱處理,氣氛選用一般大氣,以分別製得實施例一至三的搪瓷鋼片。 比較例一及二 The substrates of Examples 1 to 3 were subjected to a high-temperature heat treatment at a temperature of about 870°C for about 10 minutes, and the atmosphere was selected as general air, so as to obtain the enamelled steel sheets of Examples 1 to 3 respectively. Comparative Examples 1 and 2
比較例一及二使用的鋼胚包含小於0.01 wt%的碳、0.05 wt%至0.30 wt%的錳、小於0.05 wt%的矽、小於0.05 wt%的的磷、小於0.05 wt%的銅、小於0.05 wt%的鉻、0.05 wt%至0.20 wt%的鈦、0.01 wt%至0.09 wt%的鋁、0.005 wt%至0.02 wt%的氮、小於0.03 wt%的硫、小於0.05 wt%的鎳、其餘為鐵及不可避免的雜質。比較例一及二係使用與上述實施例一相同的製程,差異僅在於盤捲溫度為500℃,且調質軋延率為1%。所製得之比較例一及二的底材再經過與上述實施例一相同條件的高溫熱處理,以製得比較例一及二的搪瓷鋼片。The steel blanks used in Comparative Examples 1 and 2 contained less than 0.01 wt% of carbon, 0.05 to 0.30 wt% of manganese, less than 0.05 wt% of silicon, less than 0.05 wt% of phosphorus, less than 0.05 wt% of copper, less than 0.05 wt% chromium, 0.05 wt% to 0.20 wt% titanium, 0.01 wt% to 0.09 wt% aluminum, 0.005 wt% to 0.02 wt% nitrogen, less than 0.03 wt% sulfur, less than 0.05 wt% nickel, The rest is iron and unavoidable impurities. Comparative Examples 1 and 2 used the same manufacturing process as the above-mentioned Example 1, the only difference being that the coiling temperature was 500° C., and the temper rolling ratio was 1%. The prepared substrates of Comparative Examples 1 and 2 were then subjected to high-temperature heat treatment under the same conditions as in the above-mentioned Example 1 to obtain enamelled steel sheets of Comparative Examples 1 and 2.
以下表1為實施例一至三及比較例一及二之底材及搪瓷鋼片,分別經過拉伸試驗後所得之降伏強度、抗拉強度及伸長率的結果。Table 1 below shows the results of the yield strength, tensile strength and elongation of the substrates and enameled steel sheets of Examples 1 to 3 and Comparative Examples 1 and 2 respectively after tensile tests.
表1 Table 1
由上表1可看出,相較於比較例一及二,實施例一至三之底材的降伏強度及抗拉強度較大。經過高溫熱處理後的搪瓷鋼片,實施例一至三的降伏強度變化量(下降量)皆小於20 MPa,然而,比較例一及二的降伏強度變化量係大於75 MPa。換言之,實施例一至三的降伏強度無明顯下降。It can be seen from Table 1 above that compared with Comparative Examples 1 and 2, the yield strength and tensile strength of the substrates of Examples 1 to 3 are higher. After the enamelled steel sheet after high temperature heat treatment, the yield strength variation (decrease) of Examples 1 to 3 is all less than 20 MPa, yet, the yield strength variation of Comparative Examples 1 and 2 is greater than 75 MPa. In other words, the yield strength of Examples 1 to 3 did not decrease significantly.
圖2A及圖2B係分別為實施例一的底材及搪瓷鋼片的金相圖片;而圖2C及圖2D係分別為比較例一的底材及搪瓷鋼片的金相圖片。由圖2A及圖2B可看出,底材之晶粒度約11至12號,而搪瓷鋼片的晶粒度約10至11號,即實施例一的底材在經過高溫熱處理後的晶粒會稍微變大,但差異不太大,故其強度表現相近。在圖2C及圖2D中,比較例一之底材的晶粒度約8至9號(即平均粒徑為約20 μm至約50 μm),而搪瓷鋼片的晶粒度約7至8號(即平均粒徑為約30 μm至約70 μm),但圖2D中可看到部分區域有明顯晶粒異常成長的情形,例如線200所框列的區域,故比較例一的搪瓷鋼片之降伏強度與底材差異較大。2A and 2B are the metallographic pictures of the substrate and the enamelled steel sheet of Example 1 respectively; and FIG. 2C and 2D are the metallographic pictures of the substrate and the enameled steel sheet of Comparative Example 1 respectively. It can be seen from Figure 2A and Figure 2B that the grain size of the substrate is about No. 11 to No. 12, while the grain size of the enameled steel sheet is about No. 10 to No. 11, that is, the grain size of the substrate in Example 1 after high-temperature heat treatment. The grains will be slightly larger, but the difference is not too large, so the strength performance is similar. In Figure 2C and Figure 2D, the grain size of the substrate of Comparative Example 1 is about No. 8 to No. 9 (that is, the average grain size is about 20 μm to about 50 μm), while the grain size of the enameled steel sheet is about 7 to 8 (that is, the average particle size is about 30 μm to about 70 μm), but in Figure 2D, it can be seen that some areas have obvious abnormal grain growth, such as the area framed by
另外,將實施例一至三及比較例一及二的搪瓷鋼片用以進行氫滲透試驗,其係採ASTM G148規範,利用電化學充氫試驗方法,以獲得滲氫曲線與氫擴散係數。圖3係分別為實施例一及比較例一的搪瓷鋼片經氫滲透試驗所得的氫滲透曲線310及320。由圖3可看出實施例一的氫滲透時間(t b1)較比較例一的氫滲透時間(t b2)大,表示氫擴散通過實施例一之搪瓷鋼片的厚度所需時間較長。藉由下式(1),利用上述之氫滲透時間(t b)及搪瓷鋼片的厚度(L)可計算出氫擴散係數(DH): (1) 氫擴散係數愈小,代表氫於試片中愈不易通過,即氫愈不易擴散。實施例一至三所計算出的氫擴散係數為6.0×10 -7cm 2/s至9.0×10 -7cm 2/s;而比較例一及二所計算出的氫擴散係數為1.0×10 -6cm 2/s至4.0×10 -6cm 2/s。實施例一至三的氫擴散係數較比較例一及二的氫擴散係數小一個數量級以上,顯然實施例一至三的搪瓷鋼片有較佳的儲氫能力,故應具有較佳的抗跳鐵能力。 In addition, the enamelled steel sheets of Examples 1 to 3 and Comparative Examples 1 and 2 were used for hydrogen permeation test, which adopted the ASTM G148 standard, and used the electrochemical hydrogen charging test method to obtain the hydrogen permeation curve and hydrogen diffusion coefficient. FIG. 3 shows the hydrogen permeation curves 310 and 320 respectively obtained from the hydrogen permeation test of the enameled steel sheets of the first embodiment and the first comparative example. It can be seen from Fig. 3 that the hydrogen permeation time (t b1 ) of Example 1 is longer than that of Comparative Example 1 (t b2 ), indicating that the time required for hydrogen to diffuse through the thickness of the enamelled steel sheet of Example 1 is longer. According to the following formula (1), the hydrogen diffusion coefficient (DH) can be calculated using the above hydrogen permeation time (t b ) and the thickness (L) of the enamel steel sheet: (1) The smaller the hydrogen diffusion coefficient, the harder it is for hydrogen to pass through the test piece, that is, the harder it is for hydrogen to diffuse. The hydrogen diffusion coefficients calculated in Examples 1 to 3 are 6.0×10 -7 cm 2 /s to 9.0×10 -7 cm 2 /s; while the hydrogen diffusion coefficients calculated in Comparative Examples 1 and 2 are 1.0×10 - 6 cm 2 /s to 4.0×10 -6 cm 2 /s. The hydrogen diffusion coefficients of Examples 1 to 3 are more than an order of magnitude smaller than those of Comparative Examples 1 and 2. Obviously, the enamelled steel sheets of Examples 1 to 3 have better hydrogen storage capacity, so they should have better anti-iron jumping ability .
根據以上實施例,應用本發明之搪瓷鋼片的製造方法,藉由控制鋼胚的組成成分、製程中的盤捲溫度及調質軋延率,而獲得具有抗高溫軟化特性的搪瓷鋼片,故其不會因高溫熱處理而使降伏強度顯著下降,因此具有足夠的強度。再者,本發明之搪瓷鋼片還具有較小的氫擴散係數,表示有良好的儲氫能力,故對於搪瓷常見的跳鐵缺陷有較佳的預防能力。According to the above examples, by applying the manufacturing method of the enamelled steel sheet of the present invention, the enameled steel sheet with high temperature softening resistance is obtained by controlling the composition of the steel billet, the coil temperature in the manufacturing process, and the quenching and tempering rolling rate. Therefore, it will not significantly reduce the yield strength due to high temperature heat treatment, so it has sufficient strength. Furthermore, the enamelled steel sheet of the present invention also has a small hydrogen diffusion coefficient, which means it has a good hydrogen storage capacity, so it has a better preventive ability against iron jump defects common in enamel.
雖然本發明已以數個實施例揭露如上,然其並非用以限定本發明,在本發明所屬技術領域中任何具有通常知識者,在不脫離本發明之精神和範圍內,當可作各種之更動與潤飾,因此本發明之保護範圍當視後附之申請專利範圍所界定者為準。Although the present invention has been disclosed as above with several embodiments, it is not intended to limit the present invention. Anyone with ordinary knowledge in the technical field of the present invention can make various embodiments without departing from the spirit and scope of the present invention. Changes and modifications, so the scope of protection of the present invention should be defined by the scope of the appended patent application.
100:方法
110,120,130,140,150,160:操作
200:線
310,320:氫滲透曲線
t
b1,t
b2:氫滲透時間
100:
根據以下詳細說明並配合附圖閱讀,使本揭露的態樣獲致較佳的理解。需注意的是,如同業界的標準作法,許多特徵並不是按照比例繪示的。事實上,為了進行清楚討論,許多特徵的尺寸可以經過任意縮放。 [圖1]係繪示根據本發明一些實施例之搪瓷鋼片的製造方法的流程圖。 [圖2A]及[圖2B]係分別為實施例一的底材及搪瓷鋼片的金相圖片。 [圖2C]及[圖2D]係分別為比較例一的底材及搪瓷鋼片的金相圖片。 [圖3]係繪示實施例一及比較例一的搪瓷鋼片經氫滲透試驗所得的氫滲透曲線圖。 According to the following detailed description and reading together with the accompanying drawings, the aspects of the present disclosure can be better understood. It is to be noted that, as is the standard practice in the industry, many features are not drawn to scale. In fact, the dimensions of many of the features are arbitrarily scaled for clarity of discussion. [ FIG. 1 ] is a flowchart illustrating a method of manufacturing an enamelled steel sheet according to some embodiments of the present invention. [FIG. 2A] and [FIG. 2B] are metallographic pictures of the substrate and the enamelled steel sheet of Example 1, respectively. [Fig. 2C] and [Fig. 2D] are metallographic pictures of the substrate and enameled steel sheet of Comparative Example 1, respectively. [ FIG. 3 ] is a graph showing the hydrogen permeation curves obtained by the hydrogen permeation test of the enameled steel sheets of Example 1 and Comparative Example 1.
國內寄存資訊(請依寄存機構、日期、號碼順序註記) 無 國外寄存資訊(請依寄存國家、機構、日期、號碼順序註記) 無 Domestic deposit information (please note in order of depositor, date, and number) none Overseas storage information (please note in order of storage country, institution, date, and number) none
100:方法 100: method
110,120,130,140,150,160:操作 110,120,130,140,150,160: operation
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US20160201154A1 (en) * | 2013-09-10 | 2016-07-14 | Nippon Steel & Sumitomo Metal Corporation | Cold-rolled steel sheet for vitreous enameling, method for producing the same, and enameled product |
WO2019221286A1 (en) * | 2018-05-17 | 2019-11-21 | 日本製鉄株式会社 | Steel plate and enameled product |
CN110832101A (en) * | 2017-07-06 | 2020-02-21 | 株式会社Posco | Ultrahigh-strength hot-rolled steel sheet with reduced material variation and excellent surface quality, and method for producing same |
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US20160201154A1 (en) * | 2013-09-10 | 2016-07-14 | Nippon Steel & Sumitomo Metal Corporation | Cold-rolled steel sheet for vitreous enameling, method for producing the same, and enameled product |
CN110832101A (en) * | 2017-07-06 | 2020-02-21 | 株式会社Posco | Ultrahigh-strength hot-rolled steel sheet with reduced material variation and excellent surface quality, and method for producing same |
WO2019221286A1 (en) * | 2018-05-17 | 2019-11-21 | 日本製鉄株式会社 | Steel plate and enameled product |
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