WO2010150537A1 - 耐食性と疲労特性に優れた橋梁用高強度Zn-Alめっき鋼線及びその製造方法 - Google Patents
耐食性と疲労特性に優れた橋梁用高強度Zn-Alめっき鋼線及びその製造方法 Download PDFInfo
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- WO2010150537A1 WO2010150537A1 PCT/JP2010/004176 JP2010004176W WO2010150537A1 WO 2010150537 A1 WO2010150537 A1 WO 2010150537A1 JP 2010004176 W JP2010004176 W JP 2010004176W WO 2010150537 A1 WO2010150537 A1 WO 2010150537A1
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- steel wire
- plating
- plated steel
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- Y10T428/12799—Next to Fe-base component [e.g., galvanized]
Definitions
- the present invention relates to a high-strength Zn—Al-plated steel wire for bridges suitable for main cables such as suspension bridges and cable-stayed bridges, a manufacturing method thereof, and a wire for high-strength Zn—Al-plated steel wires for bridges.
- This application includes Japanese Patent Application No. 2009-151303 filed in Japan on June 25, 2009, Japanese Patent Application No. 2009-151304 filed in Japan on June 25, 2009, and Japanese Patent Application No. 2009-151304 on June 25, 2009. Priority is claimed based on Japanese Patent Application No. 2009-151438 filed in Japan, the contents of which are incorporated herein by reference.
- Steel wires for bridges used in suspension bridges, cable stayed bridges, etc. are manufactured by subjecting the wire material after hot rolling to patenting, wire drawing, and surface treatment such as hot-dip Zn plating. Yes.
- the patenting process is a heat treatment for securing the strength of the steel wire and improving the cold workability of the wire drawing.
- the wire rod after hot rolling is kept as it is in an atmosphere such as air (Stelmore method), molten salt, or boiling water, or after reheating the wire rod, it is put into a Pb bath or the like. A dipping method or the like is employed.
- the strength of the steel wire is adjusted by cold drawing, and surface treatment is applied to improve the corrosion resistance.
- the surface treatment for improving the corrosion resistance of the steel wire is hot-dip Zn plating.
- suspension bridges and cable-stayed bridges are expected to be used for a long period of more than 100 years, and it is an important issue to improve the corrosion resistance of steel wires for bridges. Therefore, steel wires that have been subjected to hot-dip Zn—Al plating with higher corrosion resistance instead of hot-dip Zn plating have been proposed (see, for example, Patent Documents 1 to 3).
- hot-dip Zn-Al plating in the same process as conventional hot-dip Zn plating. This is because the ammonium chloride flux used for the production of hot-dip Zn-plated steel wire is decomposed in a Zn—Al plating bath containing Al. For example, when a hot-dip Zn—Al plated steel wire is manufactured by the flux method using ammonium chloride, defects such as non-plating may occur.
- the Fe—Zn alloy layer formed at the interface between the hot-dip Zn-plated steel wire and the steel wire further grows when immersed in a hot-dip Zn—Al plating bath at around 450 ° C.
- a hot-dip Zn—Al plating bath at around 450 ° C.
- this method has been proposed a method of suppressing the growth of the Fe—Zn alloy layer by performing hot Zn—Al plating after electro Zn plating (see, for example, Patent Document 6).
- this method is also disadvantageous in terms of manufacturing cost because it requires more steps.
- JP-A-5-156418 Japanese Patent Laid-Open No. 7-18590 Japanese Patent Laid-Open No. 6-235054 JP 2002-371343 A JP 2003-129205 A JP 2003-155549 A JP-A-8-53779
- One embodiment of the present invention solves the problems in producing a Zn—Al plated steel wire having excellent corrosion resistance by a one-bath method, refines the Al-rich phase (Al-rich primary crystal) of the plating layer, and The formation of an alloy layer at the interface between the steel wire and the steel wire is suppressed, and a molten Zn—Al-based plated steel wire for bridges having high corrosion resistance and fatigue properties significantly exceeding those of a conventional Zn—Al plated steel wire is provided.
- a wire diameter used in a suspension bridge or a cable-stayed bridge is 4 to 8 mm, and a tensile strength is 1500 MPa to 1800 MPa, 1800 MPa to 2000 MPa, or 2000 MPa, It is possible to provide a high-strength Zn-Al plated steel wire for bridges having excellent corrosion resistance and fatigue characteristics obtained by applying Zn-Al plating to the surface of the steel wire.
- the other aspect of this invention can provide the manufacturing method of the said plated steel wire, and the wire which is the raw material of the said plated steel wire.
- the present invention is a high-strength Zn-Al plating in which fatigue strength is also improved by applying one-step Zn-Al plating using a flux to a high-strength steel wire, that is, Zn-Al plating excellent in corrosion resistance by a one-bath method. It is a plated steel wire.
- Inventors of the present invention in this plated steel wire, the structure of the plated layer of Zn—Al plating and the state of the alloy layer formed at the interface between the plated layer and the steel wire are important for achieving both corrosion resistance and fatigue characteristics. I found out.
- the inventors have further found out that it is important to optimally control the structure of the wire rod, which is a material, in order to prevent the ductility from being lowered due to the increase in strength of the plated steel wire for bridges.
- the present invention has been made based on these findings.
- the gist of the present invention is as follows.
- a plated steel wire includes a steel wire; a plated main body layer, and an Fe—Al-based alloy generated layer generated at an interface between the surface layer of the steel wire and the plated main body layer.
- a high-strength Zn-Al-plated steel wire for bridges comprising: Zn-Al plating, wherein the composition of the parent phase of the steel wire is mass% and C is 0.70% or more and 1.2% or less, Si is 0.01% or more and 2.5% or less, Mn is 0.01% or more and 0.9% or less, P is 0.02% or less, S is 0.02% or less, and N is 0.01 %, And the balance contains Fe and unavoidable impurities; in the metallographic composition of the parent phase of the steel wire, it is the type of the structure containing the most drawn wire pearlite structure; the Zn-Al plating
- the average component composition is 3.0% by mass, contains Al in the range of 3.0 to 15.0%, and contains Fe in 3.0%
- the primary crystal diameter in the plating main body layer is 10 ⁇ m or less; the fraction of the drawn pearlite structure in the metal structure composition of the parent phase of the steel wire May be 90% or more.
- the metal structure composition of Fe-Al alloy produced layer, the columnar crystals of Al 3.2 Fe layer and Al 5 Fe 2 columnar crystals of It may be the type of tissue that contains the most layers.
- the average composition of the Zn—Al plating may further include 0.01% to 2.0% of Si by mass%.
- an Al 3.2 Fe layer in the metallographic composition of the Fe—Al-based alloy generation layer, an Al 3.2 Fe layer, an Al 5 Fe 2 columnar crystal layer, and an Fe—Al It may be a type of structure containing the largest amount of -Si granular crystal layers.
- the composition of the parent phase of the steel wire is further mass%, Cr is 0% or more and 0.5% or less, Ni Is 0% to 1.0%, Cu is 0% to 0.5%, Mo is 0% to 0.5%, V is 0% to 0.5%, and B is 0% to 0.5%. You may contain 1 type (s) or 2 or more types among 0070% or less.
- the component composition of the parent phase of the steel wire is further mass%, Al is 0% or more and 0.1% or less, Ti 0% or more and 0.1% or less, Nb 0% or more and 0.05% or less, and Zr 0% or more and 0.1% or less.
- the minimum value of the number of twists until breakage by a torsion test may be 18 times or more.
- the ratio of the partial flake tensile fatigue limit to the tensile strength may be 0.22 or more.
- a production method is a method for producing a plated steel wire according to any one of (1) to (10) above, wherein the steel wire is drawn at a temperature of 250 ° C. or lower.
- the steel material after the wire drawing is mass%, and Al is 3.0% or more and 15.0% or less.
- the method for producing a plated steel wire according to the above (11) includes a step of hot rolling a steel material; and a patenting treatment in which the steel material is immersed in a salt bath of 500 ° C. or more and 600 ° C. or less following the hot rolling. And may also be included.
- the molten Zn—Al bath further contains, by mass%, Si: 2.0% or less. ), (5), and (7) to (10) may be produced.
- the amount of Al in the molten Zn-Al bath is 6.0% to 15.0% by mass%
- the plated steel wire of any of (6) to (10) above may be manufactured.
- a roller straightening process and a heat treatment of holding at 400 to 500 ° C. for 1 to 60 s One or both may be applied.
- % of the composition means “mass%”.
- a plated steel wire having a tensile strength of 1500 MPa to 1800 MPa is “1500 MPa class”
- a plated steel wire having a tensile strength of 1800 MPa to 2000 MPa is “1800 MPa class”
- a plated steel wire having a tensile strength of over 2000 MPa are classified as “2000 MPa class”.
- C is an element effective for increasing the tensile strength after the patenting treatment and increasing the work hardening rate during wire drawing.
- the addition of C makes it possible to increase the strength of the steel wire with less wire drawing distortion and contribute to the improvement of fatigue characteristics.
- the C content is limited to a range of 0.70 to 1.2%.
- the C content may be further limited to a range of 0.70 to 0.95%.
- the C content may be further limited to a range of 0.8 to 1.0%.
- the C content may be further limited to a range of 0.9 to 1.2%.
- the amount of C of the plated steel wire is equal to or more than the lower limit of the above range, the tensile strength of the wire after the patenting treatment is sufficiently secured when other alloy elements are added, and the wire drawing work hardening rate is also sufficiently large. Value, and the desired high strength steel wire for bridges can be obtained.
- the amount of C is less than or equal to the upper limit of the above range, the processing cost for reducing the center segregation is in an acceptable range.
- the Si amount is limited to 0.01 to 2.5%.
- the Si content may be further limited to a range of 0.01 to 0.5%.
- the Si content may be further limited to a range of 0.5 to 1.5%, more preferably 0.7 to 1.5%.
- the Si content may be further limited to a range of more than 0.8 to 2.5%. Since Si is a deoxidizer and is an element effective for strengthening ferrite in pearlite, the amount of Si is set to be not less than the lower limit of the above range. On the other hand, even if Si exceeding the upper limit of the above range is added, the effect is saturated. Since Si is also effective in suppressing the strength reduction of the steel wire when heated in the plating bath, it is more preferable to add 0.1% or more.
- the amount of Mn is limited to 0.01 to 0.9%.
- the Mn content may be further limited to a range of 0.01 to 1.5%.
- the Mn content may be further limited to a range of 0.1 to 1.2%.
- the Mn content may be further limited to a range of 0.1 to 0.9%. Since Mn is an element effective for deoxidation and desulfurization, it is added at least the lower limit of the above range.
- Mn is added to 0.3% or more in the 1500 MPa class and 1800 MPa class, and Mn is added to 0.2% or more in the 2000 MPa class. preferable.
- P is an impurity and is limited to 0.02% or less in order to suppress a decrease in ductility.
- the upper limit of the P amount is preferably 0.01% or less.
- S is an impurity, and is limited to 0.02% or less in order to suppress a decrease in hot workability.
- the upper limit of the amount of S is preferably 0.01% or less.
- N is an impurity, and if contained excessively, the ductility is lowered, so it is limited to 0.01% or less. In addition, the upper limit of preferable N amount is 0.007% or less. In order to make the crystal grain size finer by using nitrides such as Al, Ti, Nb, and Zr, the N content is preferably 0.001% or more.
- one or more of Cr, Ni, Cu, Mo, V, and B can be further contained in order to increase the strength after the patenting treatment.
- Cr is an effective element that refines the lamella spacing of pearlite, increases the tensile strength after the patenting treatment, and improves the wire drawing work hardening rate. However, if more than 0.5% of Cr is added, the ductility may be lowered due to the improvement in strength, so the upper limit is preferably made 0.5% or less. In addition, it is preferable to add 0.01% or more of Cr in order to improve fatigue characteristics and prevent strength reduction during hot-dip plating.
- Ni is an element that improves hardenability, and is an element that is effective in reducing the lamella spacing during the patenting process and improving the strength after the patenting process. However, even if Ni over 1.0% is added, the effect is saturated, so the upper limit is preferably made 1.0% or less. Ni is also effective in improving the drawing processability of pearlite, and it is preferable to add 0.01% or more.
- Cu like Ni, is an element effective for refining the lamella spacing during the patenting process and for improving the strength after the patenting process. In order to obtain pearlite having good wire drawing workability, it is preferable to add Cu by 0.01% or more. However, even if Cu over 0.5% is added, the effect is saturated, so the upper limit is preferably made 0.5% or less.
- Mo is also an element that improves hardenability.
- the addition of Mo is effective for improving the tensile strength after the patenting treatment, and it is preferable to add 0.01% or more. On the other hand, even if Mo over 0.5% is added, the effect is saturated, so the upper limit is preferably made 0.5% or less.
- V is an element that increases the tensile strength after patenting by precipitation strengthening. Further, the addition of V is also effective for suppressing a decrease in strength at the time of hot dipping, and it is preferable that the amount of V is 0.01% or more. On the other hand, if adding more than 0.5% V, the ductility may be lowered, so the upper limit is preferably made 0.5% or less.
- B is an element that increases the tensile strength after the patenting treatment due to the effect of improving hardenability. In order to improve hardenability, 0.0001% or more of addition is preferable. On the other hand, even if B is added in excess of 0.0070%, an effect commensurate with the added amount is not exhibited. Therefore, the upper limit of the B amount is preferably 0.0070% or less.
- one kind of Al, Ti, Nb and Zr is used. Or 2 or more types can be contained.
- Al is an element effective for deoxidation, and contributes to prevention of coarsening of crystal grains through the formation of nitrides. However, since the effect is saturated even if Al over 0.1% is added, the upper limit is preferably made 0.1% or less. In order to refine the prior austenite grain size and improve the wire drawing workability of the steel wire after the pearlite transformation, the amount of Al added is preferably 0.001% or more.
- Ti is an element effective for deoxidation, and contributes to the improvement of strength and the prevention of coarsening of crystal grains by the formation of carbides and nitrides.
- the carbonitride of Ti becomes coarse and may deteriorate the wire drawing workability and fatigue characteristics, so the upper limit is preferably made 0.1% or less. .
- Nb is an element that forms carbides and nitrides like Ti. It is an effective element for refining austenite grains by Nb carbide and nitride.
- Nb carbide and nitride an effective element for refining austenite grains by Nb carbide and nitride.
- addition of 0.001% or more of Nb is preferable.
- the upper limit of the Nb content is preferably 0.05% or less.
- Zr is an element that forms carbides and nitrides as well as Ti and Nb, and is 0.001% to improve the wire drawing workability of the steel wire after pearlite transformation and improve the ductility of the steel wire. It is preferable to add the above. On the other hand, even if adding more than 0.1% of Zr, the effect is saturated, so the upper limit is preferably made 0.1% or less.
- the wire-drawn pearlite structure is contained most as compared with other structures such as ferrite and bainite. More preferably, in this plated steel wire, the metal structure is substantially composed of drawn pearlite.
- the “drawn pearlite structure” means a pearlite structure after wire drawing workability that does not contain coarse pearlite, and preferably does not contain coarse pearlite.
- the metal structure that is substantially drawn pearlite refers to a metal structure in which a structure other than pearlite is not observed by observation with an optical microscope.
- a structure other than pearlite can be confirmed by a scanning electron microscope (SEM) or the like.
- the fraction of the drawn pearlite structure is preferably 90% or more (this fraction may be 100% or less).
- the fraction of the drawn pearlite structure is preferably 92% or more.
- a more preferable fraction of the drawn pearlite structure is 95% or more.
- the fraction of the drawn pearlite structure greatly depends on the salt bath temperature in the patenting process. In the 1500 MPa class, when the salt bath temperature is 500 ° C.
- the occurrence frequency of the bainite structure can be suitably suppressed.
- the salt bath temperature is preferably 520 ° C. or higher.
- the cooling rate is preferably 10 ° C./s or more.
- the structure fraction of the wire-drawn pearlite is observed with a SEM at a magnification of 5000 times, about 10 fields of view are photographed, the area fraction of the wire-drawn pearlite structure is measured by image processing, The average value is obtained.
- the measurement of the structural fraction of the drawn pearlite is performed at a position d / 4 from the surface layer of the steel wire with respect to the diameter d of the steel wire.
- the Zn—Al plating (Zn—Al plating layer) according to one embodiment of the present invention includes a plating layer (plating body layer; Zn—Al alloy layer) mainly composed of a Zn—Al alloy and an Fe—Al metal. It consists of an alloy layer (Fe—Al-based alloy generation layer) mainly composed of a compound. This Fe—Al-based alloy generation layer is generated at the interface between the parent phase (steel wire) of the Zn—Al-plated steel wire and the plating body layer in the course of processing.
- the Fe—Al-based alloy generation layer is formed in direct contact with both the steel wire and the plating body layer.
- the layer interposed between the steel wire and the plating main body layer is only the Fe—Al-based alloy generation layer, and other than this, the plated steel wire Layers with a size and thickness that affect the corrosion resistance and fatigue properties of the material are not included.
- the Zn—Al-plated steel wire according to one aspect of the present invention includes a steel wire, a plating body layer, and an Fe—Al-based alloy formed between the steel wire and the plating body layer. And consists of layers.
- the components of Zn—Al plating specified below include components of a plating layer (plating body layer) and an alloy layer (Fe—Al based alloy generation layer).
- Al is an element that enhances corrosion resistance by forming a dense oxide film on the surface of the plating, not the effect of sacrificial corrosion protection like Zn.
- the Al-rich phase is precipitated before the Zn-rich phase during solidification (that is, an Al-rich primary crystal is formed), and the surface has a dense oxide film. Corrosion protection and corrosion resistance are significantly improved.
- it is preferable to set the Al content of the Zn—Al plating to 8% or more.
- the present inventors have found that the Zn—Al based alloy layer of the Zn—Al plated iron wire has an influence on workability and fatigue characteristics.
- the Zn—Al-based alloy layer in the plating layer surrounds the primary crystal Al-rich phase 1 having a face-centered cubic structure (fcc) mainly composed of Al and Zn, and the primary crystal.
- the eutectic portion 2 containing a relatively large amount of Zn is included.
- the eutectic portion 2 includes a eutectic structure of a hexagonal close-packed structure (hcp) of Zn and a face-centered cubic lattice (fcc) of Al.
- the primary crystal Al-rich phase 1 is an ⁇ Al phase (including an ⁇ 1Al phase) in which Zn is dissolved.
- a primary Zn-rich phase described later is a Zn phase in which Al is dissolved.
- the primary crystal Al-rich phase or the primary crystal Zn-rich phase which is the primary crystal of the Zn—Al-based alloy layer, becomes coarse, when the plated iron wire is bent, It was found that cracks occurred in the Zn—Al-based alloy layer along the boundary with the Zn-rich phase. Therefore, the Al rich phase preferably has a fine structure (crystal grain size).
- the upper limit of the Al content of the Zn—Al plating is limited to 15%.
- the amount of Al in the Zn—Al plating layer can be controlled by the Al concentration in the plating bath.
- Fe contained in the Zn—Al plating diffuses from the surface of the steel wire and forms an alloy layer (Fe—Al based alloy generation layer) mainly containing Fe and Al at the interface between the plating and the steel wire. ing. Therefore, the Fe of Zn—Al plating varies with the thickness of the alloy layer (Fe—Al based alloy generation layer).
- the Fe content of the Zn—Al plating exceeds 3.0%, the alloy layer is too thick and the fatigue characteristics are likely to deteriorate. Therefore, in order to achieve both adhesion and fatigue characteristics between the plating and the steel wire, the Fe content of the Zn—Al plating is limited to 3.0% or less. In order to improve the fatigue characteristics, it is preferable to reduce the thickness of the alloy layer.
- the amount of Fe in the Zn—Al plating it is more preferable to limit the amount of Fe in the Zn—Al plating to a certain amount or less.
- the Fe amount In the 1500 MPa class, it is preferable to limit the Fe amount to 3.0% or less.
- the Fe amount In the 1800 MPa class and the 2000 MPa class, it is preferable to limit the Fe amount to 2.0% or less.
- the Zn—Al plating preferably contains 0.01% or more of Fe.
- Si content of the Zn—Al plating is controlled by the Si content of the Zn—Al plating bath.
- Si is an element that suppresses the growth of an alloy layer (Fe—Al-based alloy generation layer) generated at the interface between the steel wire and the plating.
- the amount of Si contained in the Zn—Al plating is preferably 0.05% or more.
- the amount of Si in the Zn—Al plating exceeds 2.0%, the effect of suppressing the increase in the thickness of the alloy layer is saturated, the plating itself becomes hard, and the fatigue strength may decrease. Therefore, it is preferable to limit the upper limit of the amount of Si in the Zn—Al plating to 2.0% or less. In order to further increase the fatigue strength, it is preferable to limit the upper limit of the Si content of the Zn—Al plating to 1.5% or less.
- Si when Si is contained, the effects of the temperature of the plating bath and the cooling rate on the growth of the alloy layer are alleviated. Therefore, when the temperature of the plating bath is high or the cooling rate is slow, it is preferable to contain Si in order to suppress the growth of the alloy layer.
- the chemical components of Zn—Al plating are dissolved by immersing in an acid to which a pickling corrosion inhibitor is added for several minutes at room temperature, and then the solution is inductively coupled plasma (ICP) emission spectroscopic analysis, atomic absorption method. Can be done by.
- ICP inductively coupled plasma
- JIS H0401 JIS H0401 is possible.
- hexamethylenetetramine is dissolved in hydrochloric acid
- plating is dissolved in a test solution diluted with water
- the solution is chemically analyzed by ICP.
- the plating layer and the alloy layer Fe—Al alloy generation layer
- the measurement may be performed by subjecting the plated steel wire to a process such as bending, mechanically peeling the plated layer and the alloy layer from the steel wire, and performing chemical analysis of the peeled Zn—Al plating.
- the balance excluding Al, Si, and Fe is Zn and inevitable impurities.
- the inevitable impurities mean elements inevitably mixed in the process of plating, such as Mg, Cr, Pb, Sb, Sn, Cd, Ni, Mn, Cu, and Ti.
- the content of these inevitable impurities is preferably 1% or less in total.
- the structure of the plating layer is a solidified structure.
- the Zn-rich layer primary Zn-rich phase
- the primary crystal Al-rich phase that is the primary crystal is precipitated, and then a Zn-rich phase (eutectic) is formed so as to fill it.
- the diameter of the primary crystal of the plating layer is limited to 10 ⁇ m or less so as not to adversely affect the fatigue strength. Furthermore, in order to increase the fatigue strength, the primary crystal diameter is preferably 5 ⁇ m or less.
- the refinement of the primary crystal is performed by lowering the temperature of the plating bath, increasing the cooling rate after plating, and balancing the two.
- the temperature of the plating bath should be lowered, and the cooling rate after plating, that is, the cooling rate when the steel wire is pulled up from the plating bath and cooled is increased. It is necessary to carry out while combining these.
- the lower limit of the primary crystal diameter is preferably 1 ⁇ m or more due to operational restrictions such as the temperature of the plating bath and the cooling rate after plating.
- Primary crystals may be circular, but are usually oval.
- the diameter of the primary crystal is obtained as an average value of the major axis and the minor axis.
- the diameter of the primary crystal may be obtained by subjecting a SEM structural photograph to image processing and obtaining an equivalent circle diameter.
- the morphology of the primary crystal may be dendritic.
- the diameter of the primary crystal is measured as the width of the dendrite.
- the primary crystal diameter can be measured using an SEM. In the present invention, 10 fields of view or more are photographed at 2000 times, the diameter of the primary crystal is measured, and the average value is obtained.
- the thickness of the alloy layer (Fe—Al based alloy generation layer) present at the interface between the Zn—Al plated plating layer and the steel wire matrix exceeds 5 ⁇ m, the fatigue characteristics of the Zn—Al plated steel wire are reduced.
- the upper limit is limited to 5 ⁇ m.
- the thickness of the alloy layer is preferably 3 ⁇ m or less.
- the practical lower limit of the thickness of this alloy layer is 10 nm.
- the lower limit of the thickness of the alloy layer is preferably 0.05 ⁇ m or more.
- the Si content in the plating layer is increased, the temperature of the plating bath is lowered, the steel wire to be plated It can be performed by shortening the dipping time, increasing the cooling rate after plating, and balancing these. For example, even when the temperature of the plating bath is high or the cooling rate is slowed, the thickness of the alloy layer can be reduced to 5 ⁇ m or less by increasing the Si content.
- the thickness of the alloy layer (Fe—Al-based alloy generation layer) is measured using a transmission electron microscope (TEM).
- TEM observation is performed at a magnification of 5000 to 20000 depending on the thickness of the alloy layer, and a structure photograph of 10 fields of view or more is taken according to the magnification to obtain an average value of the thickness of the alloy layer.
- the presence of the alloy layer at the interface between the plating layer and the parent phase of the steel wire can be confirmed by TEM observation and energy dispersive X-ray spectroscopy (EDS).
- EDS energy dispersive X-ray spectroscopy
- the alloy layer can also be confirmed by a high-resolution field emission scanning electron microscope (FE-SEM) and EDS.
- the alloy portion of the alloy layer (Fe—Al-based alloy generation layer) according to one embodiment of the present invention has a Zn-free alloy or a low-Zn alloy (substantially free of Zn) as described in detail below.
- This Fe—Al-based alloy generation layer has excellent fatigue characteristics and is less susceptible to fatigue failure than the Fe—Zn—Al alloy layer A described above.
- the alloy portion of the alloy layer includes an Al 3.2 Fe columnar crystal layer and an Al 5 Fe 2 columnar crystal layer when the Zn—Al plating does not contain Si. That is, in the metallographic composition of the alloy layer, this is the type of structure containing the most two types of columnar crystals. That is, the alloy layer has a multi-layer structure, the steel wire side layer (lower layer) has a high Fe ratio and alloyed Al 5 Fe 2 , and the plating side layer (upper layer) has a low degree of alloying . 2 Fe. When such a multi-layer structure is formed, it is presumed that the internal stress of the layer itself and the stress difference at the interface between the lower layer and the upper layer are reduced, and the adhesion of the plating is further improved.
- the Zn—Al plating contains Si
- an alloy layer (referred to as a columnar crystal layer) composed of the Al 3.2 Fe columnar crystal layer and the Al 5 Fe 2 columnar crystal layer described above, and a plating layer In between, a layer composed of Al—Fe—Si granular crystals (referred to as a granular crystal layer) is formed. Therefore, in Zn—Al plating to which Si is added, it is considered that the granular crystal layer suppresses the diffusion of Fe from the steel wire to the Zn—Al plating and suppresses the growth of the columnar crystal layer. Moreover, it is estimated that a granular crystal layer relieves
- the influence of the temperature of the plating bath and the cooling rate on the formation of the granular crystal layer due to the inclusion of Si is small.
- the cause of this is not clear, but the generation of granular crystals due to the inclusion of Si is effective in suppressing the growth of the alloy layer even when the temperature of the plating bath and the cooling rate vary.
- the columnar crystals of Al 5 Fe 2 , columnar crystals of Al 3.2 Fe, and granular crystals of Al—Fe—Si can be identified and identified by TEM observation and electron diffraction.
- the alloy layer may have a phase composed of fine granular Zn or Zn—Al.
- Phase composed of the Zn or Zn-Al is, Al 3.2 Fe columnar crystal grain boundary, Al 5 Fe 2 columnar crystal grain boundaries, the interface between the upper layer and the lower layer of the columnar crystal layer, the columnar crystal layer and the particulate Present at the interface with the crystal layer.
- the number of twists is the number of twists to break in the torsion test, and is an index of ductility of the steel wire.
- the present inventors have revealed for the first time that when the number of twists is 18 or more, the ductility of the Zn—Al-plated steel wire is high and the fatigue characteristics, particularly the corrosion fatigue characteristics, are significantly improved. Therefore, it is preferable that the torsion test is performed using 50 test pieces, preferably 100 test pieces, the number of twists of all the test pieces is 18 times or more, and the minimum value of the number of twists is 18 times or more.
- the torsion test is performed using a test piece that can obtain a grip interval 100 times the wire diameter. Grasp both ends of a test piece taken from a Zn—Al plated steel wire at an interval of 100 times the wire diameter, and rotate one of the grips in the same direction while tightening to the extent that it does not bend. A torsion test is performed at a torsion speed of 10 rpm, and the number of twists at the time of fracture is evaluated. Further, 50 torsional test pieces, preferably 100 torsional test pieces are continuously collected from the manufactured Zn—Al-plated steel wire and subjected to the torsion test.
- the ratio between the fatigue limit and the tensile strength is preferably 0.22 or more. This is because the design stress increases as the tensile strength of the plated steel wire increases. When the ratio between the fatigue limit and the tensile strength is 0.22 or more, the merit of increasing the fatigue strength is increased and the life of the bridge is increased. In order to further enhance the durability of the bridge, the ratio between the fatigue limit and the tensile strength is more preferably 0.25 or more.
- the fatigue characteristics of the Zn—Al plated steel wire are evaluated by a partial swing tensile fatigue test.
- the minimum stress is fixed according to the tensile strength of the plated steel wire, the maximum stress is changed, and the fatigue limit (the value obtained by subtracting the minimum stress from the maximum stress) is obtained at 2 million cycles.
- the minimum stress is based on 490 MPa of a 1500 MPa steel wire, and the minimum stress is changed according to the tensile strength. For example, in the case of a 1600 MPa steel wire, the minimum stress is calculated as 490 ⁇ 1600/1500 and is set to 523 MPa.
- the minimum stress is calculated as 490 ⁇ 1800/1500 and is set to 588 MPa.
- the minimum stress is calculated as 490 ⁇ 2100/1500 and is set to 686 MPa.
- the wire is a material before cold drawing, and is manufactured by subjecting the rolled wire to a patenting treatment after hot rolling.
- the metal wire composition of the parent phase of the steel wire is a type of structure containing the most wire drawing pearlite structure. More preferably, the entire structure of the wire material is substantially pearlite. Further, the pearlite structure fraction of the wire before drawing is almost the same as the fraction of the drawn pearlite structure of the Zn—Al plated steel wire. Therefore, when the fraction of the non-pearlite structure such as ferrite and bainite of the wire before wire drawing increases, the fatigue characteristics and ductility of the Zn—Al plated steel wire may decrease, and the pearlite structure fraction of the wire is 92 % Or more is preferable. A more preferable pearlite structure fraction is 95% or more.
- the pearlite tissue fraction is a value obtained by taking an image of 10 or more fields of view with an SEM magnification of 2000, measuring the area fraction of the pearlite tissue by image processing, and obtaining the average value.
- the place to observe is a position of d / 4 from the surface layer of a wire (d: Diameter of a steel wire).
- the pearlite of the wire before drawing can be estimated from the pearlite fraction of the Zn—Al plated steel wire.
- the block size of the pearlite structure is a factor that affects the wire drawing workability of the wire, the number of twists and the fatigue characteristics of the Zn-Al plated steel wire after the wire drawing.
- the block size of the pearlite structure is 25 ⁇ m or less, it is possible to suppress a decrease in wire drawing workability, the number of twists, and fatigue characteristics. Therefore, the preferable upper limit of the block size of the pearlite structure is 25 ⁇ m or less.
- the block size of the pearlite structure can be generally measured by an etch pit method or an electron backscatter diffraction image method (EBSD: Electron Back Scatter Diffraction Pattern Method).
- EBSD Electron Back Scatter Diffraction Pattern Method
- the EBSD method is employed in order to accurately measure the block size of the pearlite structure.
- the block size of the pearlite structure is measured at a position d / 4 (d: diameter of the steel wire) from the surface layer of the wire, and the average value of the three fields of view is obtained.
- the block size is affected by hot rolling finishing temperature, cooling rate after hot rolling, and alloying elements such as Mo, V, B, Al, Ti, Nb, and Zr. Therefore, the block size of the pearlite structure is controlled by adjusting the production conditions, the type and addition amount of the alloy element according to the capability of the hot rolling mill.
- the cementite thickness in the pearlite structure of the wire affects the ductility of the steel wire after wire drawing and also affects the fatigue properties of the Zn-Al plated steel wire.
- the cementite thickness of the Zn-Al plated steel wire increases, the workability of the cementite during wire drawing decreases. As a result, the frequency with which the number of twists of the Zn—Al plated steel wire deteriorates increases, and the fatigue characteristics slightly decrease. Therefore, the cementite thickness of the wire is preferably 0.03 ⁇ m or less.
- the cementite thickness increases as the C content increases even at the same lamellar spacing. Further, the cementite thickness and C content of the pearlite structure of the Zn-Al plated steel wire after wire drawing are affected by the cementite thickness and C content of the wire. Therefore, the relationship between the cementite thickness and C content of the wire, the number of twists and the fatigue characteristics of the Zn—Al plated steel wire was investigated. As a result, in the 1800 MPa class, if the cementite thickness is 0.03 ⁇ m or less and the C content is 0.027 ⁇ C% or less, even with a high-strength Zn—Al-plated steel wire, the number of twists and fatigue characteristics are good.
- the amount of C is set to 0.026 ⁇ C% or less.
- the cementite thickness of the wire is 0.03 ⁇ m or less and 0.027 ⁇ C% or less (1800 MPa class) or 0.026 ⁇ C% or less (2000 MPa class).
- the measurement of the cementite thickness of the wire of the present invention is performed using TEM.
- a sample used for TEM observation is taken from the overlapping portion of the rolled wire wound in a coil shape after hot rolling, and the region of d / 4 (d is the diameter of the wire) is used as an observation field.
- d is the diameter of the wire
- a field of view perpendicular to the cementite plate is selected, a photograph is taken at 10,000 to 20000 times, and the cementite thickness is obtained with an average value of 10 fields of view or more.
- the strength of the steel wire after wire drawing also increases.
- the tensile strength of the wire is 1250 MPa or more, a drop in ductility can be suppressed when the tensile strength of the Zn—Al-plated steel wire is increased to over 1800 MPa by wire drawing.
- the tensile strength of the wire is 1350 MPa or more, a drop in ductility can be suppressed when the tensile strength of the Zn—Al plated steel wire is more than 2000 MPa by wire drawing.
- the tensile test of the wire rod according to the present invention is carried out by dividing one turn of the wire wound in a coil shape into 12 equal parts and collecting a tensile test piece.
- a test piece is taken from three coils and subjected to a total of 36 tensile tests to obtain the maximum value and the minimum value of the tensile strength.
- the Zn—Al plated steel wire of the present invention is manufactured by a hot-rolling patenting treatment, wire drawing, flux treatment by a one-bath method, and a hot-dip Zn—Al plating step.
- the wire rod of the present invention is a rolled patten in which a steel slab is hot-rolled and the hot-rolled wire rod is cooled as it is in a salt bath of 500 to 600 ° C. in the 1500 MPa class, 520 to 600 ° C. in the 1800 MPa class and 2000 MPa class. It is manufactured by applying a ting process.
- a reheat patenting process in which a hot-rolled wire is reheated and immersed in a Pb bath is often employed.
- the strength of the wire material (rolled patenting material) manufactured by the rolling patenting process is higher than that of the wire material (reheated patenting material) manufactured by the reheating patenting process. Therefore, the wire rod of the present invention can increase the strength of the steel wire with a small wire drawing strain, and the number of twists and fatigue characteristics of the Zn—Al plated steel wire are remarkably improved.
- Cooling rate after hot rolling If the cooling rate after hot rolling until the wire is immersed in a salt bath is too slow, a coarse pearlite structure is likely to occur during cooling. Therefore, in order to improve the wire drawing workability, the cooling rate is preferably 10 ° C./s or more.
- Salt bath temperature For a steel wire of 1600 MPa class, the salt bath temperature is preferably 500 to 600 ° C. In the case of a steel wire of 1800 MPa class or 2000 Mpa class, the temperature of the salt bath is preferably 520 to 600 ° C.
- the salt bath temperature is set to the above lower limit temperature or more, the occurrence frequency of a bainite structure that deteriorates the wire drawing workability and fatigue characteristics can be suppressed.
- the salt bath temperature is set to the upper limit temperature or less, suitable fineness of the pearlite structure can be ensured. Therefore, in order to improve the strength, ductility and fatigue characteristics of the Zn—Al plated steel wire, it is preferable to limit the temperature of the salt bath to the above range.
- cold wire drawing is performed using the wire material that has been subjected to the rolling patenting process as a raw material.
- Wire drawing strain When the wire of the present invention is used as a raw material, in order to control the strength of the Zn-Al plated steel wire, in the 1500 MPa class, the wire drawing strain is 1.3 to 2.0 as a true strain. The range is preferable, and in the 1800 MPa class and 2000 MPa class, the true strain is preferably in the range of 1.5 to 2.0.
- the wire drawing strain for controlling the strength of the Zn-Al plated steel wire includes the strength of the wire after the patenting treatment, the composition of the steel that changes the work hardening rate during the wire drawing, and the reduction of each die. It varies depending on the drawing conditions such as surface area and drawing speed.
- the Zn—Al plated steel wire of the present invention is drawn by adjusting the drawing strain appropriately within the above range.
- the true strain of the wire drawing is a value represented by 2 ⁇ ln (wire diameter before wire drawing / wire diameter after wire drawing) (ln indicates a natural logarithm).
- the temperature of the steel wire during wire drawing is preferably controlled to 250 ° C. or lower in order to suppress decomposition of cementite and C diffusion.
- the temperature of the steel wire at the time of wire drawing is 250 ° C. or less, an increase in the C concentration in the ferrite is suppressed, and excellent ductility can be ensured.
- the temperature of the steel wire can be measured by a contact thermometer, a radiation thermometer, or the like.
- the method of controlling the temperature of the steel wire during the wire drawing process is to apply cooling wire drawing technology, decrease the wire drawing speed, use a wire drawing lubricant with a low friction coefficient, an appropriate die shape, and an appropriate 1 die.
- cooling wire drawing technology decreases wire drawing speed
- wire drawing lubricant with a low friction coefficient
- an appropriate die shape decreases wire drawing speed
- wire drawing lubricant with a low friction coefficient
- an appropriate die shape a low friction coefficient
- an appropriate 1 die an appropriate 1 die.
- the steel wire is held at 400 to 500 ° C. for 1 to 60 s.
- the steel wire is held at 450 to 550 ° C. for 1 to 60 s.
- Roller straightening has the effect of reducing the residual distortion of the steel wire and increasing the number of twists that deteriorate with increasing strength. As a result, the fatigue characteristics of the Zn—Al plated steel wire can be finally improved.
- Heat treatment also exhibits the effect of reducing the residual strain of the steel wire and improving the number of twists and fatigue characteristics.
- the temperature of the heat treatment be equal to or higher than the lower limit temperature of the above temperature range.
- it is preferable to set the heating temperature to not more than the upper limit temperature of the above temperature range.
- the holding time is preferably 60 s or less.
- a heating method for example, a normal heat treatment method such as a heating furnace or immersion in a temperature-controlled bath can be employed.
- the above steel wire is subjected to roller straightening and the above heat treatment, and then Zn—Al plating is performed.
- Zn—Al plating it is possible to use means such as immersing a steel wire as a base material in a molten metal bath containing Zn—Al and, if necessary, Si at the same mixing ratio as the composition of a predetermined plating layer. it can.
- alkaline degreasing treatment and pickling treatment for the purpose of improving the plating wettability and plating adhesion of the steel wire to be plated. is there.
- Flux treatment is performed before the steel wire to be plated is immersed in the plating bath.
- a flux containing ammonium chloride as a main component has been used.
- the plating does not adhere sufficiently. This is because the ammonium chloride flux decomposes in a Zn—Al plating bath containing Al.
- the pre-plating process using Zn plating is not performed. Instead, fluxes containing components other than ammonium chloride were developed. By using the flux described below, Zn—Al plating can be efficiently attached.
- Flux treatment Zinc chloride, ammonium chloride, alkali metal chloride, fluoride, tin chloride, etc. are used for flux treatment.
- the flux is preferably composed mainly of zinc chloride and containing potassium chloride and tin fluoride, and may further contain one or more of ammonium chloride, alkali metal chloride, and tin chloride. After performing the flux treatment, the steel wire to be plated is dried and immersed in a plating bath.
- the composition of the flux is not particularly limited.
- the flux total concentration is 10 to 40% aqueous solution, Zn 2+ ions 30 to 40%, K + ions 8 to 12%, Sn 2+ ions 2 to 3%, It is sufficient to use a material in which Cl ⁇ ions and F ⁇ ions are 45 to 60% in total and the pH is in the range of 0.5 to 2.0.
- the immersion time of the flux is preferably 0.5 s or longer.
- a treatment method other than the flux a method is used in which a steel wire to be plated is subjected to heat reduction annealing using a combined heat treatment of a non-oxidation furnace and a reduction furnace or a total reduction furnace, and then immersed in a plating bath and pulled up. May be.
- a method in which a predetermined plating adhesion amount control is performed by a gas wiping method or the like and then a cooling process is continuously applied can be used.
- the Al concentration of the Zn—Al plating bath is adjusted within a range of 3.0 to 15.0% depending on the desired amount of Al in the Zn—Al plating.
- the Al content is preferably 6.0% or more, and more preferably 8.0% or more.
- Si is contained in the Zn—Al plating, 2.0% or less is added depending on the amount of Si in the desired Zn—Al plating.
- the actual lower limit of the amount of Si added is 0.01% or more.
- the Si amount is preferably 1.5% or less.
- the composition of the molten Zn—Al plating bath can be determined by taking a sample from the plating bath, dissolving it in a hydrochloric acid stock solution, and conducting chemical analysis.
- the alloy layer thickness at the interface can be controlled by adjusting the plating bath temperature, the steel wire immersion time, the cooling rate after plating, and the like.
- the conditions for forming a plating layer having an appropriate interfacial alloy layer are not particularly limited because the optimum conditions are somewhat different depending on the type of the steel wire, the plating bath components, and the temperature thereof.
- the solidification temperature is about 420 ° C. Therefore, after immersing the steel wire in a molten metal bath at 440 to 520 ° C. for 1 to 60 s. It is preferable to cool at a cooling rate of 10 to 20 ° C./s.
- the plating bath of the present invention has a solidification temperature that varies depending on the bath composition, and the solidification temperature range is about 390 to 450 ° C.
- the immersion time is 1 to 60 s, and the cooling rate after solidification is 5 to 50 ° C./s.
- the immersion time in the plating bath it is preferable to set the immersion time in the plating bath to 15 s or less and the cooling rate to 10 ° C./s or more.
- the steel material which consists of was hot-rolled and used as the wire.
- the wire was cooled as it was in a salt bath at 525 ° C. and subjected to a patenting treatment. Further, this wire was cold drawn to produce a steel wire having a wire diameter of 4.9 mm.
- the steel wire was degreased and pickled, immersed in a 60 ° C. flux aqueous solution for 10 seconds, dried, and then plated under the conditions shown in Tables 1 to 3. The plating thickness was adjusted to 50 ⁇ m by wiping.
- a 7% NH 4 Cl aqueous solution was used as a flux for hot-dip Zn plating.
- Test No. Nos. 76 to 79 are samples subjected to hot dip galvanizing instead of Zn—Al plating.
- Test No. Samples 85 to 90 are samples to which a two-bath method in which Zn-Al alloy plating is performed immediately after Zn plating and without flux treatment.
- the plating compositions in Tables 1 and 2 are: 1 mL of commercially available pickling corrosion inhibitor, 140 mL of HCl, and immersion in HCl prepared by dissolving them in 1 L of pure water for several minutes at room temperature, so that the plating layer and alloy The layer (Fe—Al-based alloy production layer) was dissolved and determined by ICP analysis.
- the plated steel wire was observed with an SEM, and the wire drawing perlite structure fraction of the base material and the primary crystal diameter of the plating layer were measured. Further, the alloy layer (Fe—Al-based alloy generation layer) was observed by TEM, the thickness of the alloy layer was measured, and the state of the interface alloy layer was evaluated.
- the evaluation of the state of the interface alloy layer is as follows. A: The interface alloy layer is composed of three layers of Al 5 Fe 2 columnar crystals, Al 3.2 Fe columnar crystals, and Fe—Al—Si granular crystals. B: The interface alloy layer is Al 5 Fe 2 , Al. 3.2 Two layers of Fe columnar crystals and Al columnar crystals C: One layer of interface alloy layer of Fe—Al column D: Interface alloy layer of Zn—Fe or Zn—Fe—Al 1 layer consisting of
- the corrosion resistance of the plated steel wire was evaluated by performing a salt spray test (JIS Z 2371) for 360 hours using the plated steel wire cut to a length of 100 mm, and performing the time until the occurrence of red rust.
- the meanings of the symbols are as follows. A: Time to red rust occurrence is 360 hours or more B: Time to red rust occurrence is 300 hours to less than 360 hours C: Time to red rust occurrence is 240 hours to less than 300 hours D: Time to red rust occurrence is less than 240 hours Tables 1 to 3 show the plating composition, corrosion test results, and interface alloy layer observation results.
- Plating No. Reference numerals 77 to 80 denote hot dip galvanizing.
- Plating No. 86-91 is a two-bath method.
- Table 4 shows the chemical components of the test materials. Hot rolling was performed using these test materials, and after hot rolling, the sample was cooled as it was in a salt bath and subjected to a patenting treatment.
- the steel A of Table 4 is the same component as the steel used in 1st Example.
- the obtained wire was cold drawn to obtain a high carbon steel wire having a wire diameter of 4.5 to 7.3 mm and was subjected to hot-dip Zn—Al plating by a single bath method. For comparison, two baths of molten Zn—Al plating (after molten Zn plating and then molten Zn—Al plating) and molten Zn plating were performed.
- the hot dipping was performed by degreasing and pickling the steel wire, dipping in a 60 ° C. flux aqueous solution for 10 seconds, drying, and dipping in a hot dipping bath having a predetermined chemical composition for 5 to 15 seconds.
- the temperature of the hot dip bath was 450 to 500 ° C., and the cooling rate after hot dip plating varied depending on the wire diameter, but any hot dip plating was adjusted to 10 to 20 ° C./s.
- the thickness of the hot-dip plating was adjusted by wiping so that all platings were about 50 ⁇ m.
- the two-bath Zn—Al plating was produced by performing a hot dip Zn plating at 450 ° C. and then immediately immersing in a hot dip Zn—Al plating bath without flux treatment. Note that the same flux as in the first example was used for one bath of molten Zn—Al plating and molten Zn plating.
- the fatigue limit of the plated steel wire was evaluated by a partial single swing tensile fatigue test. Based on 490 MPa, the minimum stress is fixed according to the tensile strength of the plated steel wire, the maximum stress is changed, and the fatigue limit (the value obtained by subtracting the minimum stress from the maximum stress) is obtained at 2 million cycles. It was.
- the torsional characteristics were evaluated by collecting 100 torsional test pieces continuously from the manufactured Zn-Al plated steel wire and conducting a torsion test. In the torsion test, both ends of the test piece are gripped at an interval of 100 times the wire diameter, and one side of the gripping part is rotated in the same direction at a twisting speed of 10 rpm while being strained so as not to bend. The number of twists was evaluated. 100 torsion tests were conducted and the minimum number of twists was investigated.
- test no. 1 to 32 are examples of the present invention, and others are comparative examples.
- 90% or more of the pearlite structure was drawn.
- the comparative example it had a pearlite structure that was all drawn.
- 40 and 42 it was less than 90%.
- the Zn—Al plated steel wires of the examples of the present invention all have excellent corrosion resistance, a good number of twists, a high fatigue limit / tensile strength ratio, and excellent fatigue properties.
- a Zn—Al alloy plated steel wire has been realized.
- Test No. which is a comparative example.
- 33 to 38 are conventional hot-dip Zn-plated steel wires. This is an example in which the number of twists and fatigue properties are good, but the corrosion resistance is poor.
- Test No. 39 and 40 are examples in which the chemical composition of the steel wire is inappropriate.
- Test No. No. 39 is an example in which the ultimate tensile strength of 1500 MPa or more was not obtained because the C content was too small.
- Test No. No. 40 is an example in which the fraction of the bainite structure is too high because the Mn content is too high, and as a result, the number of twists is reduced and the fatigue characteristics are deteriorated.
- Test No. Nos. 41 and 42 are examples in which the patenting temperature using a salt bath after hot rolling is inappropriate.
- Test No. No. 41 is an example in which the intended tensile strength of 1500 MPa or more was not obtained because the patenting temperature was too high.
- test no. No. 42 is an example in which the patenting temperature was too low, the bainite structure fraction increased, resulting in a decrease in the number of twists and deterioration in fatigue characteristics.
- Test No. Nos. 43 to 46 are examples of conventional Zn-Al alloy plated steel wires using two baths. In both cases, the corrosion resistance is good, but because the alloy layer (Fe—Al-based alloy formation layer) is thick, the fatigue characteristics are deteriorated, and the ratio of fatigue limit / tensile strength is 0. This is an example of not reaching 22 or more.
- Test No. 33 to 38 are hot dip galvanizing.
- Test No. 43 to 46 are two bath methods.
- Table 9 shows chemical components of the specimens according to the third example. Hot rolling was performed using these test materials, and after hot rolling, the sample was cooled as it was in a salt bath and subjected to a patenting treatment. The structure of the obtained wire was subjected to SEM observation and TEM observation, and the pearlite fraction and cementite thickness were measured. The tensile strength was measured according to JIS Z 2241. Also, the difference in tensile strength is the difference between the maximum value and the minimum value of the tensile strength obtained by collecting a total of 36 tensile tests by collecting test pieces from three coils. Table 10 shows the temperature of the patenting treatment, the pearlite fraction of the wire, the cementite thickness, the tensile strength, and the difference in tensile strength. Table 10 also shows a calculated value of 0.027 ⁇ C.
- the wire was cold drawn to obtain a high carbon steel wire having a wire diameter of 4.5 to 7.3 mm and was subjected to hot-dip Zn—Al plating by a one-bath method.
- hot-dip Zn—Al plating by a one-bath method.
- two baths of molten Zn—Al plating (after molten Zn plating and then molten Zn—Al plating) and molten Zn plating were performed.
- the temperature during wire drawing was measured with a radiation thermometer.
- the roller straightening process and the heat processing were performed as needed.
- the hot dipping was performed by degreasing and pickling the steel wire, dipping in a 60 ° C. flux aqueous solution for 10 seconds, drying, and dipping in a hot dipping bath having a predetermined chemical composition for 5 to 15 seconds.
- the temperature of the hot dipping bath is 450 to 500 ° C., and the cooling rate after hot dipping varies depending on the wire diameter. Except for 64 ', all the hot dippings were adjusted to 10 to 20 ° C / s.
- the thickness of the hot-dip plating was adjusted by wiping so that all platings were about 50 ⁇ m.
- the two-bath Zn—Al plating was produced by performing a hot dip Zn plating at 450 ° C. and then immediately immersing in a hot dip Zn—Al plating bath without flux treatment.
- An aqueous solution having a pH of 1.0 adjusted to 45 to 50% in total was used. Further, a 7% NH 4 Cl aqueous solution was used as a flux for hot-dip Zn plating.
- Tables 11 to 13 show the production conditions and the plating composition of the plated steel wire.
- the plating composition consists of 1 mL of commercially available pickling corrosion inhibitor, 140 mL of HCl, and immersion in HCl prepared by dissolving them in 1 L of pure water for several minutes at room temperature, so that the plating layer and the alloy layer (Fe—Al It was determined by dissolving the alloy-based alloy generation layer) and performing ICP analysis.
- the plated steel wire was observed with an SEM, and the drawn pearlite structure fraction of the base material and the diameter of the primary crystal of the plating were measured.
- the alloy layer was observed by TEM, the thickness of the alloy layer was measured, and the state of the interface alloy layer was evaluated. The evaluation of the state of the interface alloy layer is as follows.
- the interface alloy layer is composed of Al 5 Fe 2 and Al 3.2 Fe columnar crystals and Fe—Al—Si granular crystals
- B: The interface alloy layer is Al 5 Fe 2 and Al 3.2 Fe columnar Two layers consisting of columnar crystals of crystal Al
- D One layer where the interface alloy layer consists of Zn-Fe or Zn-Fe-Al Fatigue of plated steel wire
- the limit was evaluated by a partial swing tensile fatigue test. Based on 490 MPa, the minimum stress is fixed according to the tensile strength of the plated steel wire, the maximum stress is changed, and the fatigue limit (the value obtained by subtracting the minimum stress from the maximum stress) is obtained at 2 million cycles. It was.
- the torsional characteristics were evaluated by collecting 100 torsional test pieces continuously from the manufactured Zn-Al plated steel wire and conducting a torsion test. In the torsion test, both ends of the test piece are gripped at an interval of 100 times the wire diameter, and one side of the gripping part is rotated in the same direction at a twisting speed of 10 rpm while being strained so as not to bend. The number of twists was evaluated. 100 torsion tests were conducted and the minimum number of twists was investigated.
- the corrosion resistance of the plated steel wire was evaluated by performing a salt spray test (JIS Z 2371) for 360 hours using a plated steel wire cut to a length of 100 mm, and the time until red rust occurred.
- JIS Z 2371 a salt spray test
- Time to red rust occurrence is 360 hours or more
- B Time to red rust occurrence is 300 hours to less than 360 hours
- C Time to red rust occurrence is 240 hours to less than 300 hours
- D Time to red rust occurrence is less than 240 hours
- the results are shown in Tables 14-16.
- the symbols in the width column of the primary crystal (dendrid) are as follows. A: Primary crystal (dendrid) width is 5 ⁇ m or less B: Primary crystal (dendrid) width is 10 ⁇ m or less
- D Primary crystal (dendrid) width exceeds 10 ⁇ m
- Reference numerals 1 'to 47' are examples of the present invention.
- 48 'to 72' are comparative examples.
- Tables 14 and 15 by using the plating composition of the present invention and adjusting the bath temperature, the immersion time, and the cooling rate, the thickness and initial thickness of the alloy layer satisfying the range required by the present invention.
- Zn-Al plating composition and structure with crystal diameters are obtained, both of which have excellent corrosion resistance and good number of twists, high fatigue limit / tensile strength ratio, high strength with excellent fatigue properties Zn-Al plated steel wire can be realized.
- No. which is a comparative example.
- 48 'to 50' are all examples in which the chemical composition of the steel wire is inappropriate.
- No. 48 ' has a low C content, and the tensile strength of the Zn-Al plated steel wire is reduced.
- No. No. 49 ' is an example in which the Si content was too low, the strength decreased during hot dipping, and the intended tensile strength was not reached.
- No. 50 ' is too high in Mn content, so bainite is generated in the patented wire, and the pearlite fraction does not reach the specified value, resulting in an increase in the difference between the maximum and minimum tensile strength. This is an example in which the torsional characteristics and fatigue characteristics deteriorated (see wire No. R1 ′ in Table 10).
- Reference numerals 51 ′, 52 ′, and 55 ′ are examples in which the wire rod is subjected to a patenting process by air cooling after hot rolling (see wire rod Nos. A2 ′, B2 ′, and M ⁇ b> 2 ′ in Table 10).
- Table 10 the difference between the maximum value and the minimum value of the cementite thickness and tensile strength of the wire is increased.
- Table 16 torsional characteristics and fatigue characteristics are deteriorated.
- No. which is a comparative example. 56 ′ to 58 ′ are examples in which the steel wire temperature at the time of wire drawing is inappropriate (refer to wire Nos. H1 ′, O2 ′, K2 ′ in Table 10), and the steel wire temperature exceeds 250 ° C. Therefore, torsional characteristics and fatigue characteristics are degraded.
- No. which is a comparative example. 59 'and 60' are examples in which the heat treatment after wire drawing is inappropriate. No. No. 59 'has a heating temperature too high. 60 'is an example in which the strength of the plated steel wire did not reach its purpose because the heating time was too long. Furthermore, no. 59 'is an example in which the heating temperature was too high, so that a part of the structure became a spheroidized cementite structure and the torsional characteristics were deteriorated.
- 61 'to 65' are examples in which the chemical component of Zn-Al plating is inappropriate.
- 62 ' since the Al content is too low, the corrosion resistance is lowered.
- No. 63 ' is an example in which the fatigue characteristics deteriorated because the Si content in the plating was too high.
- No. 64 ' is an example in which the alloy layer is grown by slowing the cooling rate after hot dipping, and the fatigue characteristics are deteriorated because the Fe content in the plating is too high.
- no. 65 ' is an example in which both the corrosion resistance and the fatigue characteristics are deteriorated because the Al content is low and the Si content is too high.
- Reference numerals 66 'to 68' are examples of steel wires subjected to conventional hot dip galvanizing. This is an example in which the intended plated steel wire having high corrosion resistance could not be realized because of Zn plating.
- Reference numerals 69 'to 72' are examples of Zn-Al plated steel wires by the conventional two-bath method. In all cases, the corrosion resistance is good, but the fatigue characteristics are degraded due to the thick alloy layer, and the ratio of fatigue limit / tensile strength did not reach the desired 0.22 or higher. is there. (Fourth embodiment)
- Table 17 shows the chemical components of the test materials. Using these test materials, hot rolling at a finishing temperature of 950 ° C. was performed, and after hot rolling, the sample was cooled as it was in a salt bath and subjected to a patenting treatment. For comparison, when the finishing temperature of hot rolling was 1090 ° C., a patenting process was further performed by air cooling after hot rolling to produce a wire rod.
- the SEM observation and the TEM observation were performed on the structure of the obtained wire, and the pearlite fraction and the cementite thickness were measured.
- the block size of the pearlite structure was measured by EBSD.
- the tensile strength was measured in accordance with JIS Z 2241.
- the difference in tensile strength is the difference between the maximum value and the minimum value of the tensile strength obtained by collecting a total of 36 tensile tests by collecting test pieces from three coils.
- Table 18 shows the temperature of the patenting treatment, the pearlite fraction of the wire, the cementite thickness, the tensile strength, and the difference in tensile strength. Table 18 also shows a calculated value of 0.026 ⁇ C.
- the wire was cold drawn to obtain a high carbon steel wire having a wire diameter of 4.3 to 7.3 mm, and was subjected to hot-dip Zn-Al plating by a single bath method.
- two baths of molten Zn—Al plating (after molten Zn plating and then molten Zn—Al plating) and molten Zn plating were performed.
- the temperature during wire drawing was measured with a radiation thermometer.
- the roller straightening process and the heat processing were performed as needed.
- the hot dip plating was performed by degreasing and pickling the steel wire, dipping in a 60 ° C. flux aqueous solution for 10 seconds, drying, and dipping in a hot dip plating bath having a predetermined chemical composition for 5 to 15 seconds.
- the temperature of the hot dipping bath is 450 to 500 ° C., and the cooling rate after hot dipping varies depending on the wire diameter. Except for 84 ′′, all the hot dippings were adjusted to 10 to 20 ° C./s.
- the hot dipping was performed by degreasing and pickling the steel wire, dipping in a 60 ° C. flux aqueous solution for 10 seconds, drying, and dipping in a hot dipping bath having a predetermined chemical composition for 30 seconds.
- Hot dip plating was performed at a bath temperature of 450 to 470 ° C., and the cooling rate after hot dip plating varied with the wire diameter, but all hot dip plating was adjusted to be around 15 ° C./second. Furthermore, the thickness of the hot-dip plating was adjusted by wiping so that all platings were about 50 ⁇ m. Further, the two-bath Zn—Al plating was produced by performing a hot dip Zn plating at 450 ° C. and then immediately immersing in a hot dip Zn—Al plating bath without flux treatment.
- An aqueous solution having a pH of 1.0 adjusted to 45 to 50% in total was used. Further, a 7% NH 4 Cl aqueous solution was used as a flux for hot-dip Zn plating.
- Tables 19 to 21 show the production conditions and the plating composition of the plated steel wire.
- the plating composition is 1 mL of commercially available pickling corrosion inhibitor, 140 mL of HCl, and dissolved in 1 L of pure water to immerse the plating layer and alloy layer for several minutes at room temperature, It was determined by ICP analysis.
- the plated steel wire was observed with an SEM, and the wire drawing perlite structure fraction of the base material and the primary crystal diameter of the plating layer were measured.
- the alloy layer was observed by TEM, the thickness of the alloy layer was measured, and the state of the interface alloy layer was evaluated. The evaluation of the state of the interface alloy layer is as follows.
- the interface alloy layer (Fe—Al-based alloy generation layer) is composed of three layers composed of columnar crystals of Al 5 Fe 2 and Al 3.2 Fe and granular crystals of Fe—Al—Si
- the interface alloy layer is Al 5 Fe 2 , Al 3.2 Fe columnar crystals
- Two layers composed of Al columnar crystals C: Interfacial alloy layer composed of Fe—Al columnar crystals
- the fatigue limit of the plated steel wire was evaluated by a partial single swing tensile fatigue test. Based on 490 MPa, the minimum stress is fixed according to the tensile strength of the plated steel wire, the maximum stress is changed, and the fatigue limit (the value obtained by subtracting the minimum stress from the maximum stress) is obtained at 2 million cycles. It was.
- the torsional characteristics were evaluated by collecting 100 torsional test pieces continuously from the manufactured Zn-Al plated steel wire and conducting a torsion test. In the torsion test, both ends of the test piece are gripped at an interval of 100 times the wire diameter, and one side of the gripping part is rotated in the same direction at a twisting speed of 10 rpm while being strained so as not to bend. The number of twists was evaluated. 100 torsion tests were conducted and the minimum number of twists was investigated.
- the corrosion resistance of the plated steel wire was evaluated by performing a salt spray test (JIS Z 2371) for 360 hours using a plated steel wire cut to a length of 100 mm, and the time until red rust occurred.
- JIS Z 2371 a salt spray test
- Time to red rust occurrence is 360 hours or more
- B Time to red rust occurrence is 300 hours to less than 360 hours
- C Time to red rust occurrence is 240 hours to less than 300 hours
- D Time to red rust occurrence is less than 240 hours
- the results are shown in Tables 22-24.
- the symbols in the width column of the primary crystal (dendrid) are as follows.
- B: Primary crystal (dendrid) width is 10 ⁇ m or less
- D Primary crystal (dendrid) width exceeds 10 ⁇ m
- No. which is a comparative example.
- 56 ′′ to 61 ′′ are examples in which the chemical composition of the steel wire is inappropriate.
- No. 56 ′′ has a low C content, and the tensile strength of the Zn—Al plated steel wire is lowered.
- No. No. 58 ′′ is an example in which the tensile strength of the plated steel wire is reduced because the Si content is too low, resulting in a large decrease in strength when immersed in a hot dipping bath.
- 59 ′′ is an example in which pro-eutectoid cementite is generated at the grain boundary during the patenting process because the C content is too high, and as a result, the torsional characteristics and fatigue characteristics deteriorate.
- no. 61 ′′ is an example in which the tensile strength of the plated steel wire is reduced because the content of each component is appropriate, but the value of 105 ⁇ C + 9 ⁇ Si-2 ⁇ Mn + 17 ⁇ Cr is low.
- 62 ′′ to 64 ′′ are examples in which the wire rod is subjected to a patenting process by air cooling after hot rolling (see wire rod Nos. B2 ′′, F2 ′′, J2 ′′ in Table 18).
- no. 62 '' has a low tensile strength of patenting treatment, the difference between the maximum and minimum values of tensile strength increases, and further, the tensile strength of the plated steel wire does not reach its purpose, and the torsional characteristics and fatigue characteristics Has also deteriorated.
- No. 63 ′′ is an example in which the cementite thickness is extremely large, the wire drawing workability is deteriorated, and the wire breakage occurs during the wire drawing.
- No. No. 64 ′′ is an example in which the cementite thickness is increased, the difference between the maximum value and the minimum value of the tensile strength is increased, and the torsional characteristics and fatigue characteristics of the plated steel wire are deteriorated.
- 72 ′′ and 73 ′′ are examples in which the heat treatment after wire drawing is inappropriate.
- No. No. 72 ′′ has a heating temperature that is too high.
- 73 ′′ is an example in which the strength of the plated steel wire did not reach the purpose because the heating time was too long.
- no. No. 71 ′′ is an example in which a part of the structure becomes a spheroidized cementite structure because the heating temperature is too high, and the torsional characteristics and fatigue characteristics deteriorate.
- Nos. 77 ′′ to 80 ′′ are examples of Zn—Al plated steel wires by the conventional two-bath method. These have good corrosion resistance, but the fatigue properties are deteriorated due to the thick alloy layer (Fe-Al alloy formation layer) and the poor state of the alloy layer at the interface. This is an example in which the strength ratio did not reach the desired 0.22 or more.
- 81 ′′ to 85 ′′ are examples in which the chemical component of Zn—Al plating is inappropriate.
- No. 81 '' and No. No. 82 ′′ is an example in which corrosion resistance could not be ensured because the Al content was too low.
- No. 83 ′′ is an example in which the fatigue characteristics are deteriorated because the Si content in the plating is too high.
- No. 84 ′′ is an example in which the cooling rate after plating is slow and the alloy layer has grown, and the fatigue characteristics are deteriorated because the Fe content in the plating is too high.
- no. 85 ′′ is an example in which both the corrosion resistance and the fatigue characteristics are deteriorated because the Al content is low and the Si content is too high.
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Abstract
Description
本願は、2009年6月25日に日本に出願された特願2009-151303号、2009年6月25日に日本に出願された特願2009-151304号、および2009年6月25日に日本に出願された特願2009-151438号に基づき優先権を主張し、その内容をここに援用する。
(2) 上記(1)のめっき鋼線で、前記めっき本体層中の初晶の径が10μm以下であり;前記鋼線の母相の前記金属組織組成における前記伸線加工パーライト組織の分率が90%以上であってもよい。
(3) 上記(1)又は(2)のめっき鋼線で、前記Fe-Al系合金生成層の金属組織組成において、Al3.2Feの柱状晶の層とAl5Fe2の柱状晶の層が最も多く含まれる種類の組織であってもよい。
(4) 上記(1)又は(2)のめっき鋼線で、前記Zn-Alめっきの平均組成が、更に、質量%で、Siを0.01%以上2.0%以下含んでもよい。
(5) 上記(4)のめっき鋼線で、前記Fe-Al系合金生成層の金属組織組成において、Al3.2Feの層と、Al5Fe2の柱状晶の層と、Fe-Al-Siの粒状晶の層とが最も多く含まれる種類の組織であってもよい。
(6) 上記(1)~(5)の何れかのめっき鋼線で、前記Zn-Alめっきの平均組成のAl量が、質量%で、6.0以上15.0%以下であってもよい。
(7) 上記(1)~(6)の何れかのめっき鋼線で、前記鋼線の前記母相の成分組成が、更に、質量%で、Crを0%以上0.5%以下、Niを0%以上1.0%以下、Cuを0%以上0.5%以下、Moを0%以上0.5%以下、Vを0%以上0.5%以下、Bを0%以上0.0070%以下、のうち1種又は2種以上を含有してもよい。
(8) 上記(1)~(7)の何れかのめっき鋼線で、前記鋼線の前記母相の成分組成が、更に、質量%で、Alを0%以上0.1%以下、Tiを0%以上0.1%以下、Nbを0%以上0.05%以下、Zrを0%以上0.1%以下、のうちの1種又は2種以上を含有してもよい。
(9) 上記(1)~(8)の何れかのめっき鋼線で、ねじり試験による破断までのねじり回数の最小値が18回以上であってもよい。
(10)上記(1)~(9)の何れかのめっき鋼線で、部分片振り引張り疲れ限度と引張強さとの比が、0.22以上であってもよい。
(11)本発明の一態様にかかる製造方法は、上記(1)~(10)の何れかのめっき鋼線を製造する方法であって、前記鋼線の伸線加工を250℃以下の温度で行う伸線処理と;前記鋼線の酸洗処理と;前記鋼線のフラックス処理と;前記フラックス処理後の前記鋼線に対するZn-Alめっき処理と;を含み、前記Zn-Alめっき処理が、前記めっき鋼線を製造する方法に含まれる唯一の前記鋼線のめっき処理である。
(12) 上記(11)のめっき鋼線の製造方法で、前記Zn-Alめっき処理では、前記伸線加工後の前記鋼材を、質量%で、Alを3.0%以上15.0%以下、含有する溶融Zn-Al浴に浸漬してもよい。
(13) 上記(11)のめっき鋼線の製造方法は、鋼材を熱間圧延する工程と;熱間圧延に続いて500℃以上600℃以下のソルト浴中に前記鋼材を浸漬するパテンティング処理と;をさらに有してもよい。
(14) 上記(11)~(13)のいずれかのめっき鋼線の製造方法で、溶融Zn-Al浴が、更に、質量%で、Si:2.0%以下を含有し、上記(4)、(5)、(7)~(10)のいずれかのめっき鋼線が製造されてもよい。
(15) 上記(11)~(13)のいずれかのめっき鋼線の製造方法で、溶融Zn-Al浴のAl量が、質量%で、6.0%以上15.0%以下であり、上記(6)~(10)のいずれかのめっき鋼線が製造されてもよい。
(16) 上記(11)~(15)のいずれかのめっき鋼線の製造方法で、前記伸線加工の後に、更に、ローラー矯直加工、400~500℃で1~60s保持する加熱処理の一方または双方を施してもよい。
なお、本明細書において、引張強度が1500MPa以上1800MPa以下のめっき鋼線を「1500MPaクラス」、引張強度が1800MPa以上2000MPa以下のめっき鋼線を「1800MPaクラス」、引張強度が2000MPa超のめっき鋼線を「2000MPaクラス」、と分類する。
本発明の一態様にかかる鋼線では、C量を0.70~1.2%の範囲に限定する。なお、1500MPaクラスのめっき鋼線ではC量を0.70~0.95%の範囲に更に限定してもよい。1800MPaクラスのめっき鋼線ではC量を0.8~1.0%の範囲に更に限定してもよい。2000MPaクラスのめっき鋼線ではC量を0.9~1.2%の範囲に更に限定してもよい。
めっき鋼線のC量が上記範囲の下限値以上であれば、その他の合金元素を添加した時パテンティング処理後の線材の引張強さが十分に確保され、また伸線加工硬化率も十分大きい値となり、目的とする高強度の橋梁用鋼線を得ることできる。一方、C量が、上記範囲の上限値以下であれば、中心偏析を軽減するための処理コストが許容できる範囲となる。
Siは、めっき浴で加熱された際の、鋼線の強度低下の抑制にも有効であるため、0.1%以上を添加することが更に、好ましい。
Mnは、脱酸及び脱硫に有効な元素であるため、上記範囲の下限値以上を添加する。鋼の焼入性を向上させ、パテンティング処理後の引張強度を高めるためには、0.1%以上を添加することが更に好ましい。一方、Mn量が上記範囲の上限値以下であれば、偏析度が増加せず、パテンティング処理時にねじり回数を低下させるベイナイトの発生が抑制される。なお、焼入れ性を高め、他の合金成分の添加量を低減するためには、1500MPaクラスおよび1800MPaクラスではMnを0.3%以上、2000MPaクラスではMnを0.2%以上添加することが更に好ましい。
一方、本発明の一態様にかかる合金層(Fe-Al系合金生成層)の合金部分は、下に詳述するように、実質的にZnを含まない、無Zn合金ないし低Znの合金(Al-Fe柱状晶)である。この合金層近辺に少量の残留Znが含まれる場合であっても、Znは、AlおよびFeの合金の柱状晶の間隙に単独で存在する。従って、合金層の合金部分は、実質的にAlおよびFeの合金からなる。このFe-Al系合金生成層は、上記のFe-Zn-Al合金層Aと比較して、疲労特性に優れ、疲労破壊が発生しにくい。
合金層の合金部分は、Zn-AlめっきがSiを含有しない場合は、Al3.2Feの柱状晶の層と、Al5Fe2の柱状晶の層とからなる。つまり、合金層の金属組織組成において、上記の2種の柱状晶が最も多く含まれる種類の組織である。即ち、合金層は複層構造であり、鋼線側の層(下層)はFe比率が高く合金化が進んだAl5Fe2、めっき側の層(上層)は合金化度の低いAl3.2Feとなる。このような複層構造を形成すると、層自体の内部応力の低下及び下層と上層との界面の応力差が低減され、めっきの密着性が更に向上すると推定される。
ソルト浴温度を上記の下限温度以上にすれば、伸線加工性や疲労特性を劣化させるベイナイト組織の発生頻度を抑制できる。一方、ソルト浴温度を上記上限温度以下にすれば、パーライト組織の好適な微細性が確保できる。したがって、Zn-Alめっき鋼線の強度、延性及び疲労特性を向上させるために、ソルト浴の温度を上記範囲に制限することが好ましい。
従来の技術である、二浴式のZn-Al合金めっき方法では、塩化アンモニウムを主成分とするフラックスが用いられていた。しかし、従来の塩化アンモニウムフラックス処理後に、Zn-Al合金めっき浴を行っても、めっきが十分に付着しない。これは、塩化アンモニウムフラックスが、Alを含むZn-Alめっき浴中で分解するためである。従来技術では、この問題を回避するために、Znめっきによる前めっき処理を行う必要が生じる。このため、全体として2度のめっき工程を含む、二浴式のZn-Al合金めっき方法が行われていた。
本発明の一態様にかかる方法では、Znめっきによる前めっき処理を行わない。これに替わって、塩化アンモニウム以外の成分を含むフラックスが開発された。以下に記載するフラックスを用いることで、Zn-Alめっきを効率的に付着させることができる。
フラックス処理:フラックス処理には、塩化亜鉛、塩化アンモニウム、アルカリ金属の塩化物、ふっ化物、塩化すず等を用いる。フラックスは、塩化亜鉛を主成分とし、塩化カリウム、ふっ化すずを含むものが好ましく、塩化アンモニウム、アルカリ金属の塩化物、塩化すずの1種又は2種以上を更に含有してもよい。フラックス処理を施した後、被めっき鋼線を乾燥させ、めっき浴に浸漬する。フラックスの組成は、特に限定しないが、例えば、フラックス全濃度が10~40%水溶液で、Zn2+イオンが30~40%、K+イオンが8~12%、Sn2+イオンが2~3%、Cl-イオンとF-イオンが合計で45~60%になり、かつpHが0.5~2.0の範囲に収まるものを使用すればよい。フラックスの浸漬時間は0.5s以上とすることが好ましい。
(第1実施例)
A:界面合金層がAl5Fe2の柱状晶と、Al3.2Feの柱状晶と、Fe-Al-Siの粒状晶とからなる3層
B:界面合金層がAl5Fe2、Al3.2Feの柱状晶と、Alの柱状晶とからなる2層
C:界面合金層がFe-Alの柱状晶からなる1層
D:界面合金層がZn-Fe、もしくはZn-Fe-Alからなる1層
A:赤錆発生までの時間が360時間以上
B:赤錆発生までの時間が300時間以上360時間未満
C:赤錆発生までの時間が240時間以上300時間未満
D:赤錆発生までの時間が240時間未満
表1~3にめっき組成と腐食試験結果、界面合金層観察結果を示す。
以下、別の実施例により本発明の別の一態様の効果を更に具体的に説明する。
本発明の要求される範囲を満たす合金層の厚さ及び初晶の径を有するものが耐疲労性に優れることは、以下の実施例により示される。
(第2実施例)
表9に第3実施例に係る供試材の化学成分を示す。これらの供試材を用いて熱間圧延を行い、熱間圧延後にそのままソルト浴に冷却してパテンティング処理を施した。得られた線材の組織をSEM観察及びTEM観察を行い、パーライト分率及びセメンタイトの厚みを測定した。引張強さは、JIS Z 2241に準拠して測定した。また、引張強さの差は、3巻のコイルから試験片を採取して、合計36本の引張試験を行い、その引張強さの最大値と最小値の差である。表10に、パテンティング処理の温度、線材のパーライト分率及びセメンタイトの厚み、引張強さ、引張強さの差を示す。また、表10には、0.027×Cの計算値も示した。
B:界面合金層がAl5Fe2、Al3.2Fe の柱状晶Alの柱状晶からなる2層
C:界面合金層がFe-Alの柱状晶からなる1層
D:界面合金層がZn-Fe、もしくはZn-Fe-Alからなる1層
めっき鋼線の疲れ限度は、部分片振り引張り疲労試験で評価した。490MPaを基準とし、めっき鋼線の引張強度に応じて最小応力を固定し、最大応力を変化させて、繰返し数が200万サイクルでの疲れ限度(最大応力から最小応力を引いた値)を求めた。
B:赤錆発生までの時間が300時間以上360時間未満
C:赤錆発生までの時間が240時間以上300時間未満
D:赤錆発生までの時間が240時間未満
結果を表14~16に示す。なお、初晶(デンドライド)の幅の欄の記号は、下記のとおりである。
A:初晶(デンドライド)幅が5μm以下
B:初晶(デンドライド)幅が10μm以下
D:初晶(デンドライド)幅が10μm超
(第4実施例)
溶融めっきは、鋼線を脱脂、酸洗後、60℃のフラックス水溶液に10秒浸漬し、乾燥後、所定の化学組成の溶融めっき浴に30秒浸漬する工程で行った。溶融めっきは浴温度が450~470℃で行い、溶融めっき後の冷却速度は線径によって異なるが、いずれの溶融めっきも15℃/秒前後になるように調整した。
更に、溶融めっき厚みは、ワイピングにより、いずれのめっきも約50μmになるように調整した。また、二浴のZn-Alめっきは、450℃の溶融Znめっきを施した後、フラックス処理なしで直ちに溶融Zn-Alめっき浴に浸漬する工程で製造した。
B:界面合金層がAl5Fe2、Al3.2Fe の柱状晶Alの柱状晶からなる2層
C:界面合金層がFe-Alの柱状晶からなる1層
D:界面合金層がZn-Fe、もしくはZn-Fe-Alからなる1層
B:赤錆発生までの時間が300時間以上360時間未満
C:赤錆発生までの時間が240時間以上300時間未満
D:赤錆発生までの時間が240時間未満
結果を表22~24に示す。なお、初晶(デンドライド)の幅の欄の記号は、下記のとおりである。
A:初晶(デンドライド)幅が5μm以下
B:初晶(デンドライド)幅が10μm以下
D:初晶(デンドライド)幅が10μm超
Claims (16)
- 鋼線と;
めっき本体層、及び、前記鋼線の表層と前記めっき本体層との界面に生成したFe-Al系合金生成層を有するZn-Alめっきと;
を含む橋梁用高強度Zn-Alめっき鋼線であって、
前記鋼線の母相の成分組成が、質量%で、
Cを0.70%以上1.2%以下、
Siを0.01%以上2.5%以下、
Mnを0.01%以上0.9%以下、含有し、
Pを0.02%以下、
Sを0.02%以下、
Nを0.01%以下、に制限し、
残部がFe及び不可避的不純物を含み;
前記鋼線の母相の金属組織組成において、伸線加工パーライト組織が最も多く含まれる種類の組織であり;
前記Zn-Alめっきの平均成分組成が、質量%で、
Alを3.0以上15.0%以下含有し、
Feを3.0%以下に制限し;
前記Fe-Al系合金生成層の厚さが5μm以下である;
ことを特徴とする耐食性と疲労特性に優れた橋梁用高強度Zn-Alめっき鋼線。 - 前記めっき本体層中の初晶の径が10μm以下であり;
前記鋼線の母相の前記金属組織組成における前記伸線加工パーライト組織の分率が90%以上である;ことを特徴とする請求項1に記載の耐食性と疲労特性に優れた橋梁用高強度Zn-Alめっき鋼線。 - 前記Fe-Al系合金生成層の金属組織組成において、Al3.2Feの柱状晶の層とAl5Fe2の柱状晶の層が最も多く含まれる種類の組織であることを特徴とする請求項1又は2に記載の耐食性と疲労特性に優れた橋梁用高強度Zn-Alめっき鋼線。
- 前記Zn-Alめっきの平均組成が、更に、質量%で、Siを0.01%以上2.0%以下含むことを特徴とする請求項1又は2に記載の耐食性と疲労特性に優れた橋梁用高強度Zn-Alめっき鋼線。
- 前記Fe-Al系合金生成層の金属組織組成において、Al3.2Feの層と、Al5Fe2の柱状晶の層と、Fe-Al-Siの粒状晶の層とが最も多く含まれる種類の組織であることを特徴とする請求項4に記載の耐食性と疲労特性に優れた橋梁用高強度Zn-Alめっき鋼線。
- 前記Zn-Alめっきの平均組成のAl量が、質量%で、6.0以上15.0%以下であることを特徴とする請求項1~5の何れか1項に記載の耐食性と疲労特性に優れた橋梁用高強度Zn-Alめっき鋼線。
- 前記鋼線の前記母相の成分組成が、更に、質量%で、
Crを0%以上0.5%以下、
Niを0%以上1.0%以下、
Cuを0%以上0.5%以下、
Moを0%以上0.5%以下、
Vを0%以上0.5%以下、
Bを0%以上0.0070%以下、のうち1種又は2種以上を含有することを特徴とする請求項1~6の何れか1項に記載の耐食性と疲労特性に優れた橋梁用高強度Zn-Alめっき鋼線。 - 前記鋼線の前記母相の成分組成が、更に、質量%で、
Alを0%以上0.1%以下、
Tiを0%以上0.1%以下、
Nbを0%以上0.05%以下、
Zrを0%以上0.1%以下、のうちの1種又は2種以上を含有することを特徴とする請求項1~7の何れか1項に記載の耐食性と疲労特性に優れた橋梁用高強度Zn-Alめっき鋼線。 - ねじり試験による破断までのねじり回数の最小値が18回以上であることを特徴とする請求項1~8の何れか1項に記載の耐食性と疲労特性に優れた橋梁用高強度Zn-Alめっき鋼線。
- 部分片振り引張り疲れ限度と引張強さとの比が、0.22以上であることを特徴とする請求項1~9の何れか1項に記載の耐食性と疲労特性に優れた橋梁用高強度Zn-Alめっき鋼線。
- 請求項1~10の何れか1項に記載のZn-Alめっき鋼線を製造する方法であって、
前記鋼線の伸線加工を250℃以下の温度で行う伸線処理と;
前記鋼線の酸洗処理と;
前記鋼線のフラックス処理と;
前記フラックス処理後の前記鋼線に対するZn-Alめっき処理と;
を含み、
前記Zn-Alめっき処理が、前記めっき鋼線を製造する方法に含まれる唯一の前記鋼線のめっき処理であることを特徴とする耐食性と疲労特性に優れた橋梁用高強度Zn-Alめっき鋼線の製造方法。 - 請求項11に記載のZn-Alめっき鋼線の製造方法であって、
前記Zn-Alめっき処理では、前記伸線加工後の前記鋼材を、質量%で、Alを3.0%以上15.0%以下、含有する溶融Zn-Al浴に浸漬する;
ことを特徴とする耐食性と疲労特性に優れた橋梁用高強度Zn-Alめっき鋼線の製造方法。 - 請求項11に記載のZn-Alめっき鋼線の製造方法であって、
鋼材を熱間圧延する工程と;
熱間圧延に続いて500℃以上600℃以下のソルト浴中に前記鋼材を浸漬するパテンティング処理と;をさらに有することを特徴とする耐食性と疲労特性に優れた橋梁用高強度Zn-Alめっき鋼線の製造方法。 - 溶融Zn-Al浴が、更に、質量%で、Si:2.0%以下を含有し、
請求項4、5、7~10の何れか1項に記載のZn-Alめっき鋼線を製造する、
ことを特徴とする請求項11~13のいずれか一項に記載の耐食性と疲労特性に優れた橋梁用高強度Zn-Alめっき鋼線の製造方法。 - 溶融Zn-Al浴のAl量が、質量%で、6.0%以上15.0%以下であり、
請求項6~10の何れか1項に記載のZn-Alめっき鋼線を製造する、
ことを特徴とする請求項11~13のいずれか一項に記載の耐食性と疲労特性に優れた橋梁用高強度Zn-Alめっき鋼線の製造方法。 - 前記伸線加工の後に、更に、ローラー矯直加工、400~500℃で1~60s保持する加熱処理の一方または双方を施すことを特徴とする請求項11~15の何れか1項に記載の耐食性と疲労特性に優れた橋梁用高強度Zn-Alめっき鋼線の製造方法。
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WO2018012625A1 (ja) * | 2016-07-14 | 2018-01-18 | 新日鐵住金株式会社 | 鋼線 |
JP2020059888A (ja) * | 2018-10-10 | 2020-04-16 | 日本製鉄株式会社 | 溶融めっき線およびその製造方法 |
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Citations (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH05106002A (ja) * | 1991-08-22 | 1993-04-27 | Mitsui Mining & Smelting Co Ltd | 溶融亜鉛合金めつき被覆物 |
JPH05156418A (ja) | 1991-12-06 | 1993-06-22 | Tokyo Seiko Co Ltd | 疲労性の良好な亜鉛−アルミニウム合金めっき鉄鋼線状材及びその製造法 |
JPH06235054A (ja) | 1993-02-09 | 1994-08-23 | Nippon Steel Corp | 吊構造用高強度鋼線の製造方法 |
JPH0718590A (ja) | 1993-06-30 | 1995-01-20 | Tokyo Seiko Co Ltd | ワイヤロープ |
JPH0853737A (ja) * | 1994-08-11 | 1996-02-27 | Kobe Steel Ltd | 高強度高靭性溶融めっき鋼線およびその製造方法 |
JPH0853743A (ja) * | 1994-08-11 | 1996-02-27 | Kobe Steel Ltd | 高強度高靭性溶融めっき鋼線の製造方法 |
JPH0853779A (ja) | 1994-08-11 | 1996-02-27 | Kobe Steel Ltd | 溶融Zn−Alめっき鋼線の製造方法 |
JP2002235159A (ja) * | 2001-02-07 | 2002-08-23 | Kokoku Kousensaku Kk | Al−Zn合金めっき線およびその製造方法 |
JP2002371343A (ja) | 2001-04-09 | 2002-12-26 | Nippon Steel Corp | 高耐食性を有し加工性に優れた溶融めっき鋼線 |
JP2003129205A (ja) | 2001-10-16 | 2003-05-08 | Nippon Steel Corp | 高耐食性を有し加工性に優れためっき鋼材およびその製造方法 |
JP2003155549A (ja) | 2001-11-19 | 2003-05-30 | Nippon Steel Corp | 高耐食性を有し加工性に優れた亜鉛合金めっき鋼材とその製造方法 |
JP2008169478A (ja) * | 2006-12-11 | 2008-07-24 | Nippon Steel Corp | 溶融めっき鋼材とその製造方法 |
WO2008093466A1 (ja) * | 2007-01-31 | 2008-08-07 | Nippon Steel Corporation | 捻回特性に優れるpws用めっき鋼線及びその製造方法 |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4389463A (en) * | 1981-07-23 | 1983-06-21 | United Technologies Corporation | Zinc-aluminum hot dip coated ferrous article |
JPS59173257A (ja) * | 1983-03-18 | 1984-10-01 | Sumitomo Electric Ind Ltd | 溶融亜鉛めつき特別強力鋼線の製造法 |
JPH079056B2 (ja) * | 1990-11-30 | 1995-02-01 | 田中亜鉛鍍金株式会社 | 乾式フラックス法による溶融金属めっき用フラックス及びこのフラックスを用いた溶融金属めっき鋼材の製造方法 |
JP2500947B2 (ja) * | 1991-01-28 | 1996-05-29 | 新日本製鐵株式会社 | 吊構造用高強度鋼線の製造方法 |
EP0602265A1 (en) | 1991-08-22 | 1994-06-22 | Mitsui Mining & Smelting Co., Ltd. | Hot dip zinc-aluminum alloy coating process |
JPH0641709A (ja) * | 1992-07-28 | 1994-02-15 | Tokyo Seiko Co Ltd | 耐食性高張力鋼線条体 |
JP2963091B1 (ja) * | 1998-08-20 | 1999-10-12 | 東鋼業株式会社 | 溶融亜鉛−アルミニウム合金めっき方法 |
JP2000265255A (ja) * | 1999-03-16 | 2000-09-26 | Nisshin Steel Co Ltd | 耐熱性を改善した溶融Zn−Al系合金めっき鋼板およびその製造法 |
JP4374356B2 (ja) | 2005-06-29 | 2009-12-02 | 新日本製鐵株式会社 | 伸線特性に優れた高強度線材及びその製造方法、並びに伸線特性に優れた高強度鋼線 |
-
2010
- 2010-06-23 JP JP2010540981A patent/JP4782246B2/ja active Active
- 2010-06-23 CN CN2010800024561A patent/CN102137949B/zh not_active Expired - Fee Related
- 2010-06-23 KR KR1020117004678A patent/KR101302291B1/ko active IP Right Grant
- 2010-06-23 WO PCT/JP2010/004176 patent/WO2010150537A1/ja active Application Filing
- 2010-06-23 US US13/261,050 patent/US9243315B2/en not_active Expired - Fee Related
- 2010-06-23 EP EP10791859.1A patent/EP2447389A4/en not_active Withdrawn
Patent Citations (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH05106002A (ja) * | 1991-08-22 | 1993-04-27 | Mitsui Mining & Smelting Co Ltd | 溶融亜鉛合金めつき被覆物 |
JPH05156418A (ja) | 1991-12-06 | 1993-06-22 | Tokyo Seiko Co Ltd | 疲労性の良好な亜鉛−アルミニウム合金めっき鉄鋼線状材及びその製造法 |
JPH06235054A (ja) | 1993-02-09 | 1994-08-23 | Nippon Steel Corp | 吊構造用高強度鋼線の製造方法 |
JPH0718590A (ja) | 1993-06-30 | 1995-01-20 | Tokyo Seiko Co Ltd | ワイヤロープ |
JPH0853737A (ja) * | 1994-08-11 | 1996-02-27 | Kobe Steel Ltd | 高強度高靭性溶融めっき鋼線およびその製造方法 |
JPH0853743A (ja) * | 1994-08-11 | 1996-02-27 | Kobe Steel Ltd | 高強度高靭性溶融めっき鋼線の製造方法 |
JPH0853779A (ja) | 1994-08-11 | 1996-02-27 | Kobe Steel Ltd | 溶融Zn−Alめっき鋼線の製造方法 |
JP2002235159A (ja) * | 2001-02-07 | 2002-08-23 | Kokoku Kousensaku Kk | Al−Zn合金めっき線およびその製造方法 |
JP2002371343A (ja) | 2001-04-09 | 2002-12-26 | Nippon Steel Corp | 高耐食性を有し加工性に優れた溶融めっき鋼線 |
JP2003129205A (ja) | 2001-10-16 | 2003-05-08 | Nippon Steel Corp | 高耐食性を有し加工性に優れためっき鋼材およびその製造方法 |
JP2003155549A (ja) | 2001-11-19 | 2003-05-30 | Nippon Steel Corp | 高耐食性を有し加工性に優れた亜鉛合金めっき鋼材とその製造方法 |
JP2008169478A (ja) * | 2006-12-11 | 2008-07-24 | Nippon Steel Corp | 溶融めっき鋼材とその製造方法 |
WO2008093466A1 (ja) * | 2007-01-31 | 2008-08-07 | Nippon Steel Corporation | 捻回特性に優れるpws用めっき鋼線及びその製造方法 |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2017073579A1 (ja) * | 2015-10-26 | 2017-05-04 | 新日鐵住金株式会社 | めっき鋼板 |
JP6160793B1 (ja) * | 2015-10-26 | 2017-07-12 | 新日鐵住金株式会社 | めっき鋼板 |
TWI601853B (zh) * | 2015-10-26 | 2017-10-11 | Nippon Steel & Sumitomo Metal Corp | 鍍敷鋼板 |
US10655203B2 (en) | 2015-10-26 | 2020-05-19 | Nippon Steel Corporation | Plated steel sheet |
WO2018012625A1 (ja) * | 2016-07-14 | 2018-01-18 | 新日鐵住金株式会社 | 鋼線 |
CN107587071A (zh) * | 2017-08-30 | 2018-01-16 | 武汉钢铁有限公司 | 一种抗拉强度≥2100MPa桥梁缆索用钢及生产方法 |
JP2020059888A (ja) * | 2018-10-10 | 2020-04-16 | 日本製鉄株式会社 | 溶融めっき線およびその製造方法 |
JP7059885B2 (ja) | 2018-10-10 | 2022-04-26 | 日本製鉄株式会社 | 溶融めっき線およびその製造方法 |
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US9243315B2 (en) | 2016-01-26 |
JP4782246B2 (ja) | 2011-09-28 |
JPWO2010150537A1 (ja) | 2012-12-06 |
KR101302291B1 (ko) | 2013-09-03 |
US20120070687A1 (en) | 2012-03-22 |
CN102137949B (zh) | 2013-09-11 |
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