CN1285431C - Mold copper plate for continuous casting and its production method - Google Patents
Mold copper plate for continuous casting and its production method Download PDFInfo
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- CN1285431C CN1285431C CNB038029308A CN03802930A CN1285431C CN 1285431 C CN1285431 C CN 1285431C CN B038029308 A CNB038029308 A CN B038029308A CN 03802930 A CN03802930 A CN 03802930A CN 1285431 C CN1285431 C CN 1285431C
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
- B22D11/04—Continuous casting of metals, i.e. casting in indefinite lengths into open-ended moulds
- B22D11/059—Mould materials or platings
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
- B22D11/04—Continuous casting of metals, i.e. casting in indefinite lengths into open-ended moulds
- B22D11/057—Manufacturing or calibrating the moulds
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Abstract
To provide a mold copper sheet for continuous casting having a high adhesion to the mold copper sheet base even when it is actually used for continuous casting and comprising a surface coating layer excellent in wear resistance. A metal layer of one or more kinds of metals selected from Ti, Cr, Ni, B, Si, and Al is formed as the innermost layer on the surface of a mold copper sheet base. Layers of a nitride or carbide of the metals of the metal layer or of a carbonitride and layers of the metals are alternated on the metal layer. A nitride, carbide, or carbonitride layer is formed as the outermost layer. The layers are preferably formed by PVD. At least the metal layer, the innermost layer, is desirably formed by using a bias voltage of the arc cut.
Description
Technical field
The present invention relates to be suitable for the structure of mould parts that particularly use in the continuous casting of molten steel at motlten metal, particularly be suitable as the copper coin of the copper plate of crystallizer of casting molten metal.And relate to the technology that helps improving its durability for this copper plate of crystallizer and maybe can force the technology cooled off.
The present invention also relates to the manufacture method of above-mentioned mold copper plate for continuous casting in addition.Be particularly related to the tack that effective improvement covers the lip-deep wear-resisting overlay of copper plate of crystallizer, further improve the manufacturing technology of this copper plate of crystallizer durability.
Background technology
, try hard in recent years improve production capacity particularly in the continuous casting of molten steel at motlten metal by improving casting speed.Meanwhile also require more effectively to produce the strand of many kinds and many sizes.
The continuous casting of motlten metal is general to be used at the upstream of casting direction one side and the unlimited water-cooled crystallizer of downstream one side.Just adopt motlten metal is injected in this crystallizer, owing to the crystallizer heat radiation motlten metal is solidified from motlten metal, the forging type that the while is pulled out the strand downstream that is cast.Crystallizer is fixed or vibrates repeatedly along casting direction at this moment, all can produce friction under the various situations between strand and crystallizer.Because the face that crystallizer contacts with strand constantly is exposed in the high temperature, particularly big thermic load is born on its surface.
Certain insulation for the lubricated and molten metal surface between crystallizer/strand, anti-oxidation is used with the crystallizer protecting residue of oxide as main component.But particularly under the situation of high-speed casting, because the relative velocity of strand and crystallizer increases, the frictional force that crystallizer bears significantly increases.And because raising speed makes strand temperature rising in the crystallizer, the thermic load that crystallizer bears also significantly increases.Its result forms crackle easily with the increase of access times on the crystallizer surface.
During this external continuous casting of slab,, usually in casting, change the width of slab in order to cast expeditiously.Compare when being cast under this situation and the stable state, between crystallizer and strand, also usually produce obviously big frictional force.
Have under the situation of carrying out the such high-grade steel continuous casting of high stainless steel of calorific intensity and high-carbon steel, because the hardness ratio ordinary steel height of solidified shell, the wearing and tearing of crystallizer surface are remarkable again.
Therefore in order to improve the durability of existing crystallizer, various research and development have been carried out.
Continuous casting, is configured to copper coin (hereinafter referred to as copper plate of crystallizer) as component parts contacting a side with strand generally in order to improve the cooling effectiveness of strand with crystallizer.On existing copper plate of crystallizer, for life-span of prolonging copper coin with guarantee the resistant to elevated temperatures strength of materials, mainly adopt the Cu alloy material of precipitation hardening type.
General using wet type coating process and sprayed and fused deposition etc. are arranged again at such copper plate of crystallizer surface applied Ni-Cr, the alloy of Fe-Ni, Co-Ni etc.
For example on above-mentioned precipitation hardening type Cu alloy material substrate material surface, apply with above-mentioned wet type coating process and fusion spraying process etc., as copper plate of crystallizer (finish materials), in the life-span that is used under the continuous casting situation of stainless steel and high-carbon steel, also have with to be used for ordinary steel continuous casting situation identical or than the situation of its reduction.
Therefore for the life-span of the copper plate of crystallizer that will prolong continuous casting such as the high strength steel that is used for stainless steel and high-carbon steel, develop the new crystallizer surface that does not also have so far and handle material.
From such viewpoint, open the method that has proposed to cover the copper plate of crystallizer surface in the flat 9-314288 communique with the nitride of metal (Al, 4A family element (Ti, Zr etc.), 5A family element (V, Nb, Ta etc.), 6A family element (Cr, Mo, W etc.), Fe) the spy.Because such nitride has very high hardness, so can expect to improve the wearability of copper plate of crystallizer.
Such nitride cap is because bad with the tack of copper plate of crystallizer matrix material, and basalis plating Fe alloy and the alloys such as Ni alloy, Co alloy at the coating nitride are wished in recommendation in this communique.
Open above-mentioned spy and to have delivered by experiment the chamber test in the flat 9-314288 communique and obtain anti-fragility and the good result of wearability.
When the inventor finds that reality casts continuously in offering conticaster, crack in cover nitride layer, such nitride layer peels off under a lot of situations, can not long-time continuous use.The ceramic layer of worrying nitride etc. in addition utilizes the weak effect of copper coin from motlten metal heat radiation (heat extraction).
Summary of the invention
The present invention is the invention according to above-mentioned actual conditions exploitation, the purpose of this invention is to provide the copper plate of crystallizer of continuous casting usefulness of the surface coating of the good and high abrasion resistance of the tack that has in actual use with the copper coin matrix material, good heat dissipation effect, propose effective manufacture method simultaneously.
In addition, the objective of the invention is again above-mentioned technology to be improved, the tectal tack of wearability of further raising copper plate of crystallizer is provided, further improve the effective manufacture method of mold copper plate for continuous casting of the durability etc. of copper plate of crystallizer.
The inventor in order to achieve the above object, at how the carbide of the various metals of the high abrasion resistance of high rigidity and nitride being coated on the substrate of copper or copper alloy, can adhere to securely, make under the continuous casting environment of reality, to use for a long time and also do not peel off and do not crack, carried out wholwe-hearted research.
The dry type coating process is adopted in its latest find as a result, wherein adopt high and PVD (the Physical Vapor Deposition that can the high speed film forming of rate of ionization, physical vapour deposition (PVD)) method, particularly HCD (Hollow Cathode Discharge, hollow cathode discharge) method and arc discharge method
(1) metal level that the metal of selecting one or more from Ti, Cr, Ni, B, Si and Al is constituted as the innermost layer of the lip-deep wearability tunicle of copper plate of crystallizer, can be guaranteed the tack firm with copper coin,
(2) as the outermost layer of wearability tunicle, utilize to cover one or more nitride based or carbonization system of from above-mentioned metal group group (Ti, Cr, Ni, B, Si and Al) selection and (comprise carbon-nitride based, below identical) ceramic membrane, not only can guarantee high intensity, and can guarantee good wearability and hear resistance, also can guarantee radiating effect
(3) in addition, between above-mentioned innermost layer and outermost layer, the metal level that utilizes the nitride of one or more metals that alternatively laminated selects or ceramic layer that carbide is formed and from above-mentioned metal group, select one or more metal to form from above-mentioned metal group, can alleviate the inside distortion of the compound tunicle of wearability effectively, not only can further improve the tack with copper coin, also can prevent peeling off and in this compound tunicle, particularly in ceramic membrane, cracking of the compound tunicle of wearability effectively.
The present invention is the invention based on above-mentioned understanding.
Main contents just of the present invention are as follows.
1. mold copper plate for continuous casting, it is characterized by: in the mold copper plate for continuous casting of motlten metal, be provided with from metal group Ti as the copper of matrix material or the plate surface of copper alloy system, Cr, Ni, B, the metal level that the metal of one or more that select among Si and the Al is formed is as innermost layer, the layer that alternating layer is pressed with the nitride of one or more metals selected more than a group or carbide lamella from above-mentioned metal group and one or more the metal selected from above-mentioned metal group is formed on it, and then be provided with the nitride or the carbide lamella of one or more metals of from above-mentioned metal group, selecting as outermost layer.
2. above-mentioned 1 described mold copper plate for continuous casting is characterized by: the mixed layer that forms the metal of innermost layer metal and formation matrix material on the border of above-mentioned innermost layer and matrix material.
3. above-mentioned 1 or 2 described mold copper plate for continuous casting, it is characterized by: constitute the copper of above-mentioned matrix material or the sheet material of copper alloy system, implementing with one or more that select from Ni, Cr, Fe and Co on its surface in advance is the coating of main component.
4. mold copper plate for continuous casting manufacture method, it is characterized by: on the copper or the copper alloy panel surface that constitute matrix material, form from Ti with the PVD method, Cr, Ni, B, select metal level that one or more metal forms as innermost layer among Si and the Al, the metal nitride of from above-mentioned metal group selecting one or more or the carbide lamella of alternatively laminated more than one group and the metal level of selecting one or more metal to form from above-mentioned metal group on it form the nitride of selecting one or more metals from above-mentioned metal group or the outermost layer of carbide lamella then.
5. above-mentioned 4 described mold copper plate for continuous casting manufacture methods is characterized by: the method that forms above-mentioned innermost layer is a high bias voltage discharge coating process.
6. above-mentioned 4 or 5 described mold copper plate for continuous casting manufacture methods is characterized by: the copper of above-mentioned matrix material or the sheet material of copper alloy system are that coating is the sheet material of main component to select one or more from Ni, Cr, Fe and Co on its surface.
" nitride or carbide " also comprises carbon-nitride in above-mentioned.
7. on the copper or the copper alloy panel surface of matrix material, form from Ti with the PVD method, Cr, Ni, B, select the innermost layer of the metal level that one or more metal forms among Si and the Al, the metal nitride of from above-mentioned metal group selecting one or more or the carbide lamella of alternatively laminated more than one group and the metal level of from above-mentioned metal group, selecting one or more metal to form on it, form then from above-mentioned metal group in the outermost mold copper plate for continuous casting manufacture method of the metal nitride of selecting one or more or carbide lamella, it is characterized by: at least when forming the metal level of innermost layer, the bias voltage that uses electric arc to block.
8. above-mentioned 7 described mold copper plate for continuous casting manufacture methods is characterized by: the copper of above-mentioned matrix material or the sheet material of copper alloy are that coating is the sheet material of main component to select one or more from Ni, Cr, Fe and Co on its surface.
To there is no need be to be made of same metal to each metal level in above-mentioned 1～8, selects one or more from Ti, Cr, Ni, B, Si and Al, and the metal that each layer usefulness is different is also passable.Each layer that same carbide, nitride or carbon-nitride constitute also there is no need to be made of same compound.
Description of drawings
Figure 1A is the sectional schematic diagram of the copper plate of crystallizer of surface coverage of the present invention.
Figure 1B is the sectional schematic diagram of the copper plate of crystallizer of existing surface coverage.
Fig. 2 A is the diagram of the hardness contrast of the copper plate of crystallizer of expression copper plate of crystallizer of surface coverage of the present invention and existing surface coverage.
Fig. 2 B is the diagram of the adhesive force contrast of the copper plate of crystallizer of expression copper plate of crystallizer of surface coverage of the present invention and existing surface coverage.
Fig. 3 A blocks the schematic diagram of bias voltage waveform for expression electric arc.
Fig. 3 B blocks the schematic diagram of the other waveform of bias voltage for expression electric arc.
The specific embodiment
According to figure the present invention is specifically described below.
Expression alternately covers the sectional schematic diagram of the crystallizer surface processing material of 6 groups of (the adding up to 12 layers) metal levels of Ti metal film and the ceramic layer of TiN film among Figure 1A at the copper plate of crystallizer substrate material surface according to the present invention.The existing crystallizer surface that is illustrated on the copper plate of crystallizer surface 2 layers of the coverings of plating Cr behind the plating Ni on the other hand among Figure 1B is handled the sectional schematic diagram of material.
From the situation shown in Figure 1A as can be seen, the core of crystallizer surface processing material of the present invention (copper plate of crystallizer) is as follows.
1) for the copper plate of crystallizer close attachment, adopt the metal level formed by the metal of from metal group Ti, Cr, Ni, B, Si and Al, selecting one or more and one or more of the ceramic membrane of nitride, carbide or the carbon-nitride of one or more metals of selecting by above-mentioned metal group constitute the wearability tunicle layer.
2) at the above-mentioned metal level of copper plate of crystallizer substrate material surface coating, guarantee firm adhesion property as the innermost layer of anti-film tunicle.Do not produce fully between the coat of metal that one or more the metal that just will make substrate material surface and select from above-mentioned metal group is formed and peel off.
3) outermost layer that is coated with plated film to the copper plate of crystallizer matrix material will utilize the high ceramic membrane of hardness (ceramic membrane of metal nitride, carbide or carbon-nitride composition that the metal of one or more that select is formed) from above-mentioned metal group, guarantee to improve intensity, wearability, hear resistance, and thermal diffusivity.
4) the inside distortion that covers mill for the wearability of alleviating on the copper plate of crystallizer matrix material, the ceramic layer that metal nitride, carbide or carbon-nitride that the metal level that will form one or more the metal of selecting from above-mentioned metal group and one or more the metal of selecting from above-mentioned metal group are formed is formed is as one group, their coatings are organized in utilization more, prevent peeling off and prevent and cracking in the wearability tunicle of wearability tunicle.
Wherein at least when forming the metal level of innermost layer, utilize electric arc as bias voltage to block bias voltage and make above-mentioned 2) tack further improve.
Above-mentioned Ti and Cr, Ni, B, Si, Al are in order to make with in various metals, and particularly the tack of copper or copper alloy etc. is good, will use in the present invention to be clipped in conduct with respect to the innermost layer of copper plate of crystallizer matrix material and the intermediate layer between the ceramic membrane.
The ceramic membrane of the nitride of these metals, carbide or carbon-nitride composition will use as needs high strength and wearability, stable on heating outermost layer because hardness is high especially on the other hand.
And between the outermost layer of the innermost layer of above-mentioned metal and pottery, be one group with above-mentioned ceramic layer and metal level, by one group of coating at least, the tack between each tunicle is further improved, can prevent from the wearability tunicle, to crack simultaneously.
The reason that obtains above-mentioned effect it be unclear that, and inventor's view is as follows.
The general hardness height of ceramic membrane just, thermal coefficient of expansion is compared less with the coat of metal.Therefore under the situation in order to ensure high intensity, wearability, the thick ceramic membrane of hear resistance coating, with accumulation distortion easily on the interface of matrix material, its result is peeled off easily.Therefore be difficult to guarantee adhesion property.
In contrast, think under the situation of which floor metal level of alternatively laminated and ceramic layer that distortion is discharged (metal level is transferred in the distortion of ceramic layer) effectively between each metal level-ceramic layer, its as a result tack obviously improve.Think and it would be desirable metal level-ceramic layer with the atomic unit alternatively laminated, the release that is most appropriate to distort.
Even be to find to use ceramic layer of the present invention to make cover layer unexpectedly, not only heat dispersion does not worsen, difference according to circumstances can be improved significantly.Think that this is because outermost layer uses under the situation of selected components pottery of the present invention, this pottery and significantly improve as the wetability of the melting crystallizer cosolvent of lubricant, its result has filled up the reduction of the tunicle pyroconductivity that causes because of ceramic layer, and obtains unnecessary heat dispersion.
Obtain above-mentioned radiating effect and wish the scope of outermost layer ceramic surface roughness arithmetic average roughness Ra below 5 μ.Be Ti that carbide-nitride, particularly TiN are used under the situation of ceramic layer remarkable result being arranged particularly in addition, improve 10～40% than the general copper plate of crystallizer heat dissipation capacity that on copper coin, plates metal.
Wish in the present invention to comprise that each metal layer thickness of innermost layer is about 0.1～5.0 μ m that comprise that in addition each ceramic layer thickness of outermost layer is about 0.1～5.0 μ m, aggregate thickness just wearability is about 1.0～50 μ m by film thickness.
At least need two groups in the group (comprising innermost layer, outermost layer) of substrate material surface metal level and ceramic layer in the present invention in addition.Wish that above-mentioned group number more than 3 groups, more wishes more than 5 groups.
The cost that the thickness of each layer, the number of plies, gross thickness etc. can be taken into account the effect of above-mentioned tack improvement, the wearability that requires tunicle, tunicle multiple stratification-increase thickness needs waits to determine.
Further do not improve intensity, wearability, hear resistance in order not lose tack, be suitable for making the composition of metal level and ceramic layer and the thickness of their coated layers to change at thickness direction.According to making the coated layer thickness progressive additive of each layer to outermost layer, particularly be suitable for making thermal coefficient of expansion to reduce to carry out like that coating gradually specifically for ceramic layer from innermost layer.Having the thermal coefficient of expansion of ceramic layer can utilize composition, surface state to wait again controls.
As the difference of an example linear expansion coefficient, for example under 20 ℃ of conditions be according to substance classes:
The situation 9.4 * 10 of TiN
-6/ ℃
Ti 8.6×10
-6/℃
Cu 16.5×10
-6/℃
Therefore, linear expansion coefficient is compared and will be changed with the situation of pure material according to the ratio of its composition under the situation of these compound substances.So measure the relation of proportion of composing and linear expansion coefficient in advance, can control the coefficient of expansion by the proportion of composing of key-course.Certainly be not limited to above-mentioned method.
Have again from improving the viewpoint of tack, wish before coating so that the clean state of the removing surface that is coated with surfacing is carried out coating.
As follows in order to obtain such continuous casting with the core of the manufacture method of crystallizer surface processing material.
5) in order to make copper plate of crystallizer matrix material and above-mentioned metal level, above-mentioned metal level and above-mentioned ceramic layer strong bonded, and cause the variation of matrix material for fear of the heat affecting of the high temperature of handling with surperficial coating, to adopt PVD at lower temperature (below 300 ℃) coating.
6) wish especially in PVD to adopt good HCD and the arc discharge method of rate of ionization,, and avoid the variation of the matrix material that the heat affecting of high temperature causes copper plate of crystallizer matrix material and above-mentioned metal level, above-mentioned metal level and above-mentioned ceramic layer strong bonded.
7) special hope when the metal level of coating innermost layer, utilizes the electric arc as bias voltage to block the tack that bias voltage further improves coating and matrix material at least.
Additional high bias voltage when 8) wishing the metal level of coating innermost layer forms mixed layer on the border of copper plate of crystallizer matrix material and above-mentioned metal level.
During coating of the present invention is handled to adopt the PVD method.The dry plating method of HCD and arc discharge, EB (Electron beam, electron beam)+RF (Radio Frequency, radio frequency) etc. etc. is arranged in the PVD method.Special wish to adopt rate of ionization good, HCD method or arc discharge method that can fast filming.This moment also can be two kinds of method combinations.During this external coating outermost layer, be particularly suitable for using the HCD method of ceramic coating that can smooth densification.
Wherein much less the inventor studies improve durability in composite bed of the present invention, and its result recognizes when coated metal layer and ceramic layer, and utilizing electric arc as bias voltage to block bias voltage is very effective to reaching desired target.Wherein to make copper coin with respect to ground connection be the such auxiliary voltage of negative pole to bias voltage, subsequently the absolute value of the potential difference of ground connection and copper coin as bias voltage, so-called high biasing is meant that this bias voltage is big.
Just when above-mentioned metal level of coating and ceramic layer, utilize the words of the bias voltage that electric arc blocks as bias voltage, because can prevent the paradoxical discharge that causes because of foreign matter, can make Ionized particle-stabilised, offer substrate, two-layer tack is further improved, and its result reduces the generation of crackle and peeling off of coated layer, can realize improving durability.
Describe for the bias voltage that electric arc blocks at this.The waveform imagination of blocking bias voltage for electric arc has two kinds of situations shown in Fig. 3 A, Fig. 3 B, these situations all are not the sharply rising of (orthoscopic) when voltage rises, but, can effectively prevent paradoxical discharge by (radioactive ray formula or segmented) rising to a certain extent lenitively.
The electric arc of pattern shown in Fig. 3 A blocks and is also referred to as electric arc disconnection or electric arc control, the DC power supply that generally is used to have the thyristor function.Pattern is also referred to as pulse shown in Fig. 3 B on the other hand.As the pattern that electric arc blocks general use Fig. 3 A, use the pattern of Fig. 3 B according to the different situation of some effects.
As mentioned above, the bias voltage that utilizes electric arc to block provides ionized particles owing to can stablize, so further improve tack, helps avoiding peeling off of wearability tunicle.
Therefore from preventing that the whole aspect of peeling off of cover layer (wearability tunicle) from considering, recommend at least when forming the metal level of innermost layer the bias voltage that uses electric arc to block to the utmost.
Use electric arc to block bias voltage when forming whole layers certainly, help improving the tack between the cover layer, much less can obtain optimal results.
And when above-mentioned coating, block bias voltage by utilizing electric arc as bias voltage, Ionized metallic is driven in the lower floor, form the mixed layer of these dense and careful metals at the interface of the upper and lower, its result makes both combinations more firmly, much less can realize improving the purpose of tack.
Wherein utilizing above-mentioned electric arc to block the additional suitable scope of voltage of bias voltage is 10～1000V.
When coating, in order to ensure with the metal coating of matrix material firm tack, particularly innermost layer the time, wish to adopt under the situation of additional high bias voltage, carry out the high bias voltage coating method of coating.Wherein particularly suitable auxiliary voltage is 50～1000V in this high bias voltage discharge coating method.
Use such high bias voltage generating coating method, when the metal of coating innermost layer, Ionized metallic is squeezed in the matrix material deeply, form the mixed layer of these metals at the interface of copper coin matrix material and metal innermost layer, it is both strong bonded more as a result, much less have the advantage that can realize improving tack.
Wish that with the mixed layer that such method forms the ratio of the innermost layer metal in the layer is about 10～50%.
In the present invention owing to utilize above-mentioned surface coating (wearability tunicle) can obtain high intensity, wearability and hear resistance, so for there is no particular limitation as the copper coin of matrix material or the material of copper alloy plate.Just as the copper plate of crystallizer matrix material in recent years in order to improve intensity at high temperature, develop into and use the precipitation hardening type copper alloy, need not guarantee the intensity of matrix material in the present invention specially.Therefore for example use the copper coin of the various continuous casting usefulness of selling on the market and copper alloy plate all no problem.
The thickness of slab of copper coin designs according to the size of purposes and strand in addition, is generally 30～60mm under the situation of block.
In addition, on the surface of copper coin,, also can set in advance the substrate cover layer that one or more layers is made up of various metals or pottery as the substrate of (comprising innermost layer-outermost multilayer cover layer of forming by metal level and ceramic layer) of above-mentioned wearability tunicle.Particularly, cover use so be suitable as substrate because to select one or more from Ti, Cr, Ni, B, Si and Al be that the coating (the so-called coat of metal) of main component (more than the 50 quality % that substrate just covers) is good with copper coin and above-mentioned wearability cover layer tack.Wherein wish from Ni, Cr, Fe and Co, to select one or more to be main component.
These coating now the covering on the copper plate of crystallizer be with methods such as wet type coating and fusion injection attached to copper coin on, therefore generally have about 30～2000 μ m.The effect of these metallic element coating may not be necessary in the present invention, and these metallic elements are owing to good with the tack of copper coin, so also no problem even wearability film of the present invention forms on these metals.
Therefore on existing copper plate of crystallizer, implement under the situation of wearability tunicle of the present invention trouble and the cost that need not specially peel off these coats of metal.
It is all inboard that copper plate of crystallizer of the present invention also can be used for crystallizer, also can only be used for important position.For example pay attention to heat sinking function, can consider only to be used near the entrance side (from the upper end to being deep into about the about 100mm of liquid level at least) of crystallizer, be applicable to the good material of the present invention of heat sinking function (for example adopting Ti system, the particularly tectal material of TiN).Pay attention to durability on the other hand, can consider only to be used near crystallizer bottom (the latter half from the end to entering the 30mm), be applicable to the material of the present invention of (for example Si system etc.) that hardness is high.Certainly for example use the first half to adopt the tectal copper coin of the present invention of TiN, the latter half to adopt the tectal copper coin of the present invention of SiC to constitute crystallizer, become better combination.
(embodiment)
Embodiment 1
The surface arc discharge method of the matrix material that constitutes by copper plate of crystallizer (Cr:1.0 quality %, Zr:0.1 quality %, all the other be Cu), electric arc at additional initial bias: 400V blocks under the situation of bias voltage, forms Ti metal innermost layer (thickness: 3.0 μ m).Same then lamination TiN (thick: 3.0 μ m) → Ti (thick: 3.0 μ m) → TiN (thick: 3.0 μ m) → Ti (thick: 3.0 μ m) → TiN is (thick: as 3.0 μ m), to form the thick compound tunicle of about 18 μ m.And then with the HCD method at additional initial bias: 400V (general bias voltage, below identical) situation under, form Ti (thick: 2.0 μ m) → TiN (thick: film 2.0 μ m), add up to 8 layers, make and have aggregate thickness: the copper coin of the wearability tunicle of about 22 μ m (example 1).
On this external identical substrate material surface, under the situation of additional initial bias: 250V, form Ti metal innermost layer (thickness: 3.0 μ m).Same then lamination TiN (thick: 3.0 μ m) → Ti (thick: 3.0 μ m) → TiN (thick: 3.0 μ m) → Ti (thick: 3.0 μ m) → TiN is (thick: as 3.0 μ m), to form the thick compound tunicle of about 18 μ m.And then with the HCD method under the situation of additional initial bias: 400V, form Ti (thick: 2.0 μ m) → TiN (thick: film 2.0 μ m), add up to 8 layers, make and have aggregate thickness: the copper coin of the wearability tunicle of about 22 μ m (example 2).
Fig. 2 A and Fig. 2 B represent the hardness (case hardness, test load 400g) of copper plate of crystallizer of the surface coverage that obtains like this and the result of adhesive force research.The adhesive force method of scraping wherein with HRC diamond penetrator tip (tip radius 0.2mm, 120 ° of tip angle, more than the hardness Hv8000), the copper plate of crystallizer surface that contact surface covers, on this instrument, increase load on one side continuously gradually, generally scrape substrate, the critical load when strip occurring and break (tunicle is peeled off) with the scuffing end is estimated.
Plate Ni (thickness: 0.5mm), then it above again plate Cr (thickness: 30 μ ms) by existing method with wet type plating method at the substrate material surface identical for comparative example with example.The copper plate of crystallizer of the surface coverage that obtains is obtained the result with same research method be shown in Fig. 2 A and Fig. 2 B in the lump.
From Fig. 2 A and Fig. 2 B as can be seen, example 1 compares hardness with example 2 with comparative example and adhesive force all increases substantially.It is good to use example 1 that electric arc blocks bias voltage and example 2 to compare tack in addition.
When casting stainless steel slab continuously with above-mentioned each surface coverage copper plate of crystallizer in addition, all do not crack after example 1 and example 2 are cast 1000 batches, the practical operation proof has favorable durability.Be the copper plate of crystallizer (comparative example) of the existing surface coverage of representative in order to comparative example in contrast, cast 300～600 batches of rear surface cover layers and produced crackle.
Embodiment 2
As shown in table 1, the matrix material that is made of copper plate of crystallizer (No.3～14:Cr:1.5 quality %, Zr:0.15 quality %, all the other be Cu), the matrix material (No.15,16) that is made of the copper coin of surface plating Ni and sprayed by fusion on the surface on the surface of the matrix material (No.17,18) that the copper coin of Ni-Cr constitutes and use various PVD method alternatively laminated metal levels and ceramic layer are respectively made the copper plate of crystallizer of surface coverage.
Use the method identical with embodiment 1 to study to the hardness of the copper plate of crystallizer of the surface coverage that obtains and adhesive force, its result is shown in table 1 in the lump.
In the hurdle that " whether uses electric arc to block bias voltage " in table 1, with " having " is that holostrome uses electric arc to block bias voltage.Be that holostrome uses not the bias voltage (voltage strength is identical with " having ") that electric arc blocks with " nothing " in addition.
Table 1
| No. | Wearability tunicle: the kind of metal level, ceramic layer, (thickness: μ m) | The lamination number of plies (thickness: μ m) | The plating method | Whether use electric arc to block bias voltage (auxiliary voltage V) | Hardness Hv | (Mp a) for adhesive force |
| 3 | Ti-TiN-Ti-TiN-Ti-TiC-Ti-TiC (2.5)(2.5)(2.5)(2.5)(2.5)(2.5)(2.5)(2.5) | 8 (20) | The HCD method | (250) are arranged | 2500 | 150 |
| 4 | Do not have | 2300 | 125 | |||
| 5 | Cr-CrN-Cr-CrN-Cr-CrN- (3.0)(3.0)(2.0)(2.0)(2.5)(2.5) | 6 (15) | The HCD method | (150) are arranged | 1900 | 161 |
| 6 | Do not have | 1800 | 136 | |||
| 7 | Ni-NiN-Ni-NiN-Ni-NiC-Ni-NiC-Ni-NiC (3.5)(3.5)(3.5)(3.5)(3.0)(3.0)(2.5)(2.5)(2.5)(2.5) | 10 (30) | The HCD method | (100) are arranged | 1700 | 160 |
| 8 | Do not have | 1600 | 119 | |||
| 9 | B-BN-B-BN-B-BN (3.0)(3.0)(3.0)(3.0)(3.0)(3.0) | 6 (18) | Arc discharge method | (200) are arranged | 2500 | 163 |
| 10 | Do not have | 2400 | 139 | |||
| 11 | Si-SiNx-Si-SiNx-Si-SiC-Si-SiC-Si-SiC (2.0)(2.0)(2.0)(2.0)(3.0)(3.0)(3.0)(3.0)(2.5)(2.5) | 10 (25) | SiNx: magnetron sputtering method SiC: arc discharge method | (80) are arranged | 2700 | 150 |
| 12 | Do not have | 2600 | 118 | |||
| 13 | Al-AlN-Al-AlN-Al-AlC-Al-AlC (2.5)(2.5)(2.5)(2.5)(2.5)(2.5)(2.5)(2.5) | 8 (20) | AlN: arc discharge method AlC: magnetron sputtering method | (100) are arranged | 2400 | 159 |
| 14 | Do not have | 2200 | 124 | |||
| 15 | Ti-TiN-Ti-TiN-Ti-TiC-Ti-TiC (2.5)(2.5)(2.5)(2.5)(2.5)(2.5)(2.5)(2.5) | 8 (20) | The HCD method | (150) are arranged | 2500 | 170 |
| 16 | Do not have | 2300 | 115 | |||
| 17 | Ti-TiN-Ti-TiN-Ti-TiC-Ti-TiC (2.5)(2.5)(2.5)(2.5)(2.5)(2.5)(2.5)(2.5) | 8 (20) | The HCD method | (100) are arranged | 2500 | 150 |
| 18 | Do not have | 2300 | 120 |
So shown in the table, the copper plate of crystallizer of the surface coverage that obtains by the present invention not only all has high hardness as can be seen, and can obtain good tack.This external use electric arc blocks under the situation of bias voltage can obtain better tack.
Embodiment 3
Prepare the copper plate of crystallizer (example 1,2) of the surface coating shown in the embodiment 1, the 16 kinds of surface coverage copper plate of crystallizer (example 3～18) shown in the embodiment 2 as example with Ti-TiN system.
In addition, prepare to have the copper plate of crystallizer (comparative example 1) of (Ni+Cr) coating shown in the embodiment 1 as a comparative example, on the copper coin matrix material, use the copper plate of crystallizer (comparative example 2) of the TiN of arc process lamination 10 μ m, the copper plate of crystallizer (comparative example 3) of the nitride of the chromium of usefulness HCD method lamination 10 μ m on the copper coin matrix material, on the matrix material of copper coin, plate Ni-P (thickness: substrate 30 μ m) with arc process, with the nitride (thickness: copper plate of crystallizer 7 μ m) (comparative example 4) of in substrate, using HCD method lamination titanium, on the matrix material of copper coin, plate Cr (thickness: substrate 30 μ m) with wet type plating method, in substrate, use the nitride (thickness: copper plate of crystallizer 5 μ m) (comparative example 5) of HCD method lamination chromium, on the copper coin matrix material with fusion spray Ni-Cr (thickness: substrate 1mm), in substrate, plate Cr (thickness: copper plate of crystallizer 30 μ m) (comparative example 6).
The copper plate of crystallizer of these surface coverage is used in minor face one side of crystallizer, casts continuously with conticaster.
The steel grade of casting is stainless steel (SUS 430 steel, SUS 304 steel) and the high-carbon steel of stipulating in the JIS iron and steel handbook (SK 5～SK 2).Conticaster is a vertical type, and crystallizer is of a size of thick: the slab caster of 200mm, wide: 750～1240mm, length: 915mm.Stainless casting speed is that the casting speed of 0.9～1.3m/min, high-carbon steel is 0.8～1.2m/min, and the evaluation of thermal diffusivity is carried out in the situation of 1.0m/min, width of plate slab 1000～1100mm.The physical property of the crystallizer protecting residue that uses is 1100 ℃, is 2.0poise, basicity (CaO/SiO 1300 ℃ viscosity as setting temperature
2) be 1.5.
To each mould casting one stove be that 150 tons of molten steel amount to 500 stoves.Observed the situation (flawless is arranged, peel off, wear and tear) of copper plate of crystallizer surface tunicle like this behind casting 500 stoves.
What obtain the results are shown in table 2.
Table 2
| Crystallizer minor face copper coin | |||
| Flawless is arranged | Have or not and peel off | Have or not wearing and tearing | |
| Example 1 | Do not have | Do not have | Do not have |
| Example 2 | Do not have | Do not have | Do not have |
| Example 3 | Do not have | Do not have | Do not have |
| Example 4 | Do not have | Do not have | Do not have |
| Example 5 | Do not have | Do not have | Do not have |
| Example 6 | Do not have | Do not have | Do not have |
| Example 7 | Do not have | Do not have | Do not have |
| Example 8 | Do not have | Do not have | Do not have |
| Example 9 | Do not have | Do not have | Do not have |
| Example 10 | Do not have | Do not have | Do not have |
| Example 11 | Do not have | Do not have | Do not have |
| Example 12 | Do not have | Do not have | Do not have |
| Example 13 | Do not have | Do not have | Do not have |
| Example 14 | Do not have | Do not have | Do not have |
| Example 15 | Do not have | Do not have | Do not have |
| Example 16 | Do not have | Do not have | Do not have |
| Example 17 | Do not have | Do not have | Do not have |
| Example 18 | Do not have | Do not have | Do not have |
| Comparative example 1 | Do not have | Do not have | Wear and tear at lower end coating |
| Comparative example 2 | Whole face has a large amount of crackles | Whole face has in a large number to be peeled off | Peeling off position copper coin wearing and tearing |
| Comparative example 3 | Whole face has a large amount of crackles | Whole face has in a large number to be peeled off | Peeling off position copper coin wearing and tearing |
| Comparative example 4 | A large amount of crackles are arranged near the meniscus | Peel off the lower end | Peel off position copper coin wearing and tearing in the lower end |
| Comparative example 5 | A large amount of crackles are arranged near the meniscus | Peel off the lower end | Peel off position copper coin wearing and tearing in the lower end |
| Comparative example 6 | Do not have | Do not have | Peel off position copper coin wearing and tearing in the lower end |
As can be seen from Table 2, the surface coating of example does not all crack, peels off and weares and teares.
In contrast, on comparative example 1,6, observe at crystallizer minor face lower end coating and wear and tear.Observe whole and produce a large amount of crackles and peel off on comparative example 2, comparative example 3, observe on comparative example 4, comparative example 5 and produce a large amount of crackles near meniscus, this external lower end produces peels off.
Embodiment 4
Carry out the evaluation of heat dissipation capacity for each embodiment, the comparative example that in embodiment 3, adopt.Heat dissipation capacity is calculated from temperature difference, the cooling water inflow of copper coin cooling water inlet side and outlet side, uses with the ratio of comparative example 1 and represents.In addition in order to estimate the uniformity of cooling, with 1 second measuring space under minor face width central part meniscus 100mm, from the temperature of the dark 10mm in surface, obtain the standard deviation in 10 minutes.The results are shown in table 3.
Table 3
| Surface roughness Ra (μ m) | The heat dissipation capacity ratio | The copper plate temperature standard deviation (℃) | |
| Example 1 | 1.34 | 1.11～1.35 | 1.9 |
| Example 2 | 0.12 | 1.15～1.45 | 2.1 |
| Example 3 | 0.34 | 1.01～1.09 | 2.5 |
| Example 7 | 3.19 | 1.051.11 | 2.7 |
| Example 9 | 0.12 | 0.94～1.05 | 3.5 |
| Example 11 | 1.26 | 0.97～1.07 | 4.1 |
| Comparative example 1 | 0.11 | 1.0 | 5.5 |
| Comparative example 2 | 5.3 | 1.05～1.20 | 3.3 |
| Comparative example 4 | 6.5 | 1.03～1.15 | 2.8 |
| Comparative example 6 | 0.33 | 0.95～1.05 | 4.6 |
As can be seen from Table 3, example all demonstrates at least and the suitable good thermal diffusivity of existing copper sheet material (comparative example 1).Heat radiation is little because of the difference of plate face position.Particularly the heat dissipation capacity of Ti system (example 1,2,3,7) is compared with existing material and is improved, and wherein improves more than 15% in the Ti system (example 1,2).The standard deviation of copper plate temperature is little in these external these copper coin materials, has good heat radiation uniformity.General worry produces fine lobe with the increase casting billet surface of heat dissipation capacity, with not producing such crackle on the strand of mould casting of the present invention.Therefore by using such copper plate of crystallizer, can make the material of casting force cooling and cooling evenly, can realize making slab casting speed to improve.
In contrast, comparative example 2,4 roughness of using TiN on top layer are outside suitable scope, and the effect of improving thermal diffusivity is also little.
In each above-mentioned embodiment, be main being illustrated for the situation that copper plate of crystallizer of the present invention is used for the survey of crystallizer minor face.Can confirm under the situation that is used for the crystallizer long side, also can obtain identical effect.
The possibility of utilizing on the industry
Adopt the copper plate of crystallizer of such surface coverage of the present invention, even offer solidified shell hardness is high under hot state stainless steel and the continuous casting of high-carbon steel actual, also can keep good durability and thermal diffusivity, particularly when high-speed casting, can effectively produce high-quality strand, can say industrial be very effective.
Claims (8)
1. a mold copper plate for continuous casting is the copper plate of crystallizer that is suitable for casting continuously motlten metal, it is characterized in that,
Have in fact matrix material that the sheet material by copper or copper alloy system constitutes and the cover layer that is provided with at described substrate material surface,
Described cover layer is by forming as the lower part:
Innermost layer is made up of one or more metals of selecting from metal group Ti, Cr, Ni, B, Si and Al;
The intermediate layer, be formed on the described innermost layer, alternatively laminated the layer formed of the layer formed of nitride, carbide or carbon-nitride of one group of above one or more metal of from described metal group, selecting and one or more the metal from described metal group, selected; With
Outermost layer is formed on the described intermediate layer, is made up of nitride, carbide or the carbon-nitride of one or more metals of selecting from described metal group.
2. mold copper plate for continuous casting as claimed in claim 1 is characterized in that, on the border of described innermost layer and described matrix material, forms metal that constitutes innermost layer and the mixed layer that constitutes the metal of matrix material.
3. mold copper plate for continuous casting as claimed in claim 1 or 2 is characterized in that, described matrix material, and implementing with one or more that select from Ni, Cr, Fe and Co at described plate surface in advance is the coating of main component.
4. the manufacture method of a mold copper plate for continuous casting, it is characterized in that, at the copper that constitutes matrix material or the plate surface of copper alloy system, use the PVD method, form from metal group Ti as innermost layer, Cr, Ni, B, the layer that one or more metals of selecting among Si and the Al are formed, the nitride of above one or more metals from described metal group, selected of one group of alternatively laminated in the above, the layer that carbide or carbon-nitride is formed, the layer of forming with one or more the metal of from described metal group, selecting, and then form the nitride of one or more metals of from described metal group, selecting as outermost layer, the layer that carbide or carbon-nitride is formed.
5. the manufacture method of mold copper plate for continuous casting as claimed in claim 4 is characterized in that, the method that forms described innermost layer is a high bias voltage discharge coating process.
6. the manufacture method of mold copper plate for continuous casting as claimed in claim 4 is characterized in that, at least when the metal level that forms as innermost layer, and the bias voltage that uses electric arc to block.
7. the manufacture method of mold copper plate for continuous casting as claimed in claim 5 is characterized in that, at least when the metal level that forms as innermost layer, and the bias voltage that uses electric arc to block.
8. as the manufacture method of each described mold copper plate for continuous casting in the claim 4～7, it is characterized in that, constitute the copper of described matrix material or the sheet material of copper alloy system, implementing with one or more that select from Ni, Cr, Fe and Co in advance in its surface is the coating of main component.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002020002 | 2002-01-29 | ||
| JP020002/2002 | 2002-01-29 | ||
| JP087728/2002 | 2002-03-27 | ||
| JP2002087728 | 2002-03-27 |
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| CN1625450A CN1625450A (en) | 2005-06-08 |
| CN1285431C true CN1285431C (en) | 2006-11-22 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNB038029308A Expired - Fee Related CN1285431C (en) | 2002-01-29 | 2003-01-28 | Mold copper plate for continuous casting and its production method |
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| Country | Link |
|---|---|
| KR (1) | KR100623012B1 (en) |
| CN (1) | CN1285431C (en) |
| WO (1) | WO2003064077A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103436842A (en) * | 2013-08-27 | 2013-12-11 | 郑州大学 | Deposition method of SiC-Al thin-film material with Al transition layer and low-frictional coefficient |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4513058B2 (en) * | 2004-08-10 | 2010-07-28 | 日立金属株式会社 | Casting parts |
| KR100701194B1 (en) * | 2005-12-23 | 2007-03-29 | 주식회사 포스코 | A casting mold having slopped plate layer |
| CN102485950A (en) * | 2010-12-02 | 2012-06-06 | 鸿富锦精密工业（深圳）有限公司 | Film-coated part and preparation method thereof |
| KR101443788B1 (en) * | 2012-08-09 | 2014-09-23 | 주식회사 포스코 | Casting mold |
| RU2677560C2 (en) | 2014-10-28 | 2019-01-17 | ДжФЕ СТИЛ КОРПОРЕЙШН | Mold for continuous casting machine and continuous casting method for steel |
| KR101942932B1 (en) * | 2017-07-20 | 2019-04-17 | 주식회사 포스코 | Mold and method for manufacturing the same |
| DE102019113117B4 (en) * | 2019-05-17 | 2023-12-28 | voestalpine eifeler Vacotec GmbH | Method for producing a cold forming tool and cold forming tool |
| CN110125350B (en) * | 2019-06-04 | 2024-08-13 | 中国重型机械研究院股份公司 | Multilayer composite copper plate for wide surface of slab caster crystallizer and preparation method thereof |
| CN113333696B (en) * | 2021-06-01 | 2023-02-17 | 西峡龙成特种材料有限公司 | CuAlFeNi crystallizer copper plate back plate, parent metal and machining method thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5973153A (en) * | 1982-10-21 | 1984-04-25 | Mishima Kosan Co Ltd | Mold for continuous casting and its production |
| JPH0636963B2 (en) * | 1986-03-28 | 1994-05-18 | 住友金属工業株式会社 | Mold for continuous casting |
| JPS62253758A (en) * | 1986-04-24 | 1987-11-05 | Mishima Kosan Co Ltd | Formation of cermet layer by laser irradiation and casting mold for continuous casting |
| JP3896185B2 (en) * | 1996-03-29 | 2007-03-22 | 株式会社神戸製鋼所 | Durable continuous casting mold |
-
2003
- 2003-01-28 CN CNB038029308A patent/CN1285431C/en not_active Expired - Fee Related
- 2003-01-28 KR KR1020047011511A patent/KR100623012B1/en not_active IP Right Cessation
- 2003-01-28 WO PCT/JP2003/000778 patent/WO2003064077A1/en active Application Filing
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103436842A (en) * | 2013-08-27 | 2013-12-11 | 郑州大学 | Deposition method of SiC-Al thin-film material with Al transition layer and low-frictional coefficient |
| CN103436842B (en) * | 2013-08-27 | 2015-09-30 | 郑州大学 | With the deposition method of the low-friction coefficient SiC-Al thin-film material of Al transition layer |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2003064077A1 (en) | 2003-08-07 |
| CN1625450A (en) | 2005-06-08 |
| KR100623012B1 (en) | 2006-09-13 |
| KR20040073594A (en) | 2004-08-19 |
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