CN1847463A - Chrome plating component - Google Patents
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- CN1847463A CN1847463A CN 200610071602 CN200610071602A CN1847463A CN 1847463 A CN1847463 A CN 1847463A CN 200610071602 CN200610071602 CN 200610071602 CN 200610071602 A CN200610071602 A CN 200610071602A CN 1847463 A CN1847463 A CN 1847463A
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Abstract
The invention discloses a chrome plating element, which is characterized by the following: setting chrome plating layer on the metal structure surface with even diameter of micrite at over 16.0nm in the chrome plating layer; testing the peak strength rate of {211} and {222} at over 0.10 according to X-ray diffractormetry method; preventing chrome plating layer from cracking at over 300 deg.c in the heating course.
Description
Technical field
The present invention relates to the chrome plating component that a kind of surface at metal system member is provided with electrodeposited chromium layers.
Background technology
In order to improve the wearability of metal system member, carried out metal system member is implemented the chromium plating processing, and covered the surface of metal system member by chromium coating.The little epithelium (chromium coating) of frictional coefficient because of hard in chromium plating can be obtained less expensively, so be used to the protection of metal system member more.Yet the hardization if improve the hardness of chromium coating, wearability improves, but its negative be the toughness deterioration.Therefore, be subjected to tensile stress, or stand thermal process and the chromium coating contraction, the crack then takes place owing to implemented chromed member.If have the crack to take place at chromium coating, this crack is conveyed to the surface of metal system member, and the medium that constitutes corrosion is then arranged, from the surface of chromium coating by the intrusion of crack part, corroding metal system member and have the problem of erosion resistance deterioration.
Therefore, in patent documentation 1, proposed as standing the technology that thermal process also can not make the chrome-plated part of erosion resistance deterioration.In this technology, by will handling the surface that the chromium coating of having paid compressive residual stress is arranged at member, thereby prevent the fissured generation when the thermal process that stands about 200 ℃ by plating.So in this document, if disclosing the size of the crystallite that makes chromium coating is more than the 9nm, then also not having the crack in the state after superheating process produces, and record if the size of crystallite becomes excessive, then the crystalline texture of chromium layer itself begins to change, therefore the upper limit of crystallite can be made as below the 16nm, and the crack in the chromium layer exists with ... the unrelieved stress of chromium layer and the size of crystallite.
Now the most extensive what be used is the mold (below, being called Cu is mold) of Cu or Cu alloy system as the continuous casting mold of steel so.This mold thermal conductivity height can obtain excellent cooling efficiency.
In when continuous casting, in order to prevent the oxidation of molten steel, and prevent that molten steel or strand from directly contacting with the mold inner face, also keep oilness outward in order to make between mold inner face and the solidified shell, and use fusing assistant (flux).But,, directly contact the interior surface damage of mold with the mold inner face so can not prevent molten steel or strand fully owing to be formed at fusing assistant layer in uneven thickness of the internal surface of mold.
In addition, use steel scrap (scrap) is arranged recently as the raw material of molten steel, but also confirm the melting loss of sneaking into the mold inner face that the zinc in the steel scrap causes, also become the very big reason of the mold lost of life.That is, if there is zinc to sneak in molten steel, then its condensation is in meniscus (meniscus) part of mold, because fused zinc, Cu is that the inner face of mold is etched and melting loss.
Therefore recently, by being the surface formation protection epithelium of mold at Cu, to realize alleviating of melting loss.The demand characteristics of looking for as this protection epithelium, owing to contact with molten steel, and the thermotolerance (anti-crack property) and the anti-fused zinc of the temperature of molten steel are born in requirement in the meniscus side of mold.On the other hand, the exit side at mold requires wearability owing to contacting with solidified shell.Therefore as the protection epithelium, be suitable for being provided with the chromium plating film.
But, when using continuous casting mold, because stand the abominable like this thermal cycling (thermal process) of quick cooling that produces by the heating rapidly that produces with contacting of pyritous molten steel and the water-cooled when making molten steel solidification etc., so there is very big tensile stress to act on chromium coating.Therefore,, then there is the crack to take place and produces peeling off of film, perhaps have fused zinc to invade, and produce the problem that mold is corroded etc. by this crack at chromium coating if chromium coating stands abominable thermal process.
Also having, as standing 300 ℃ of other thermal processs of level fissured chromium layer does not take place yet, is the chromium layer that obtains through spraying plating (spatter) processing.But, because the hardness of the chromium layer that is obtained by the spraying plating processing is the soft about Hv250, thus be unsuitable for the coating of the member of wearability requirement, and because form hole (space) easily, so anti-fused zinc is also poor.In addition, when carrying out spraying plating, be subjected to metal system member shape restriction and do not have versatility.In addition, if compare relative high price with the chromium coating of electroplating acquisition.
[patent documentation 1] spy opens 2000-199095 communique ([scope of claim], [0006], [0008], [0036], [0047])
Summary of the invention
The present invention carries out in view of such situation, and its purpose is, a kind of chrome plating component is provided, and it is provided with in the harsh thermal process that stands more than 300 ℃, also is difficult to the electrodeposited chromium layers that has the crack to take place.In addition, other purposes of the present invention are, provide a kind of wearability also excellent chrome plating component.
To be provided with the harsh thermal process that stands more than 300 ℃ in order providing, also to be difficult to the chrome plating component of fissured electrodeposited chromium layers takes place and to study repeatedly.Its result, if find to make the crystallite of electrodeposited chromium layers to increase, and the crystallization control orientation makes it become inconsistent, can thermal contraction even then stand harsh thermal process yet, and can prevent fissured generation, thus finished the present invention.
Promptly, described chrome plating component of the present invention, have following main points: be the chrome plating component that is provided with electrodeposited chromium layers on the surface of metal system member, the mean diameter of the crystallite in the described electrodeposited chromium layers is more than the 16.0nm, and according to X-ray diffraction method obtain { 211} is with { peak strength of 222} is more than 0.10 than ({ 211}/{ 222}).
In order to improve toughness, the hardness of described electrodeposited chromium layers is preferably below the Hv600.In order to prevent the fissured generation when the thermal process that stands 450 ℃, the thickness of described electrodeposited chromium layers is preferably more than the 5 μ m.
In order further to improve wearability, preferably on the upper strata of described electrodeposited chromium layers, be provided with and compare the hardness height, and hardness surpasses the hard layer of Hv600 with this electrodeposited chromium layers.
In the present invention, also comprise the continuous casting mold that constitutes by above-mentioned chrome plating component.
According to the present invention, a kind of chrome plating component can be provided, it is not provided with can make the wearability deterioration, stands abominable thermal process more than 300 ℃ and also is difficult to the electrodeposited chromium layers that has the crack to take place.Described electrodeposited chromium layers also is difficult to have the crack to take place because stand abominable thermal process, can not invade by the crack part from the surface of chromium coating so for example constitute the medium of corrosion, can prevent the corrosion of member.If the upper strata at above-mentioned electrodeposited chromium layers is provided with hard layer, the wearability of chrome plating component is improved.
Embodiment
In the present invention, utilize plating and form chromium coating.Adopt to electroplate, with handle by spraying plating that the chromium coating that obtains compares can high rigidityization, can guarantee wearability.Can also realize cost degradation in addition.But, because electroplate the chromium coating that obtains, compare the hardness height, so general relatively difficulty takes place in the crack that is suppressed at when standing thermal process with the chromium layer of handling acquisition by spraying plating.When standing thermal process, the fissured generation of electrodeposited chromium layers is that the lattice imperfection amount that this contraction is present in the crystal boundary of electrodeposited chromium layers influences because electrodeposited chromium layers shrinks.The lattice imperfection amount increases if crystal boundary becomes at most, and the crack becomes and takes place easily when standing thermal process.Therefore,, stand the thermal process thermal contraction and also can be suppressed,, also can prevent fissured generation even electroplate the chromium coating that obtains if reduce crystal boundary then the lattice imperfection amount reduces.In order to reduce crystal boundary, crystallite is increased.
Even yet increase crystallite and when standing abominable thermal process 300 ℃ of ranks more than, also have the crack generation.Therefore present inventors further study repeatedly in order also to prevent fissured generation under the situation that stands the harsh thermal process.Its result has distinguished and can make it in inconsistent direction by the crystal orientation of control chromium coating, specifically, recognizes exactly to make crystal orientation be distributed to { 211} direction and { 222} direction.
Therefore, chrome plating component of the present invention is the chrome plating component that is provided with electrodeposited chromium layers on the surface of metal system member, make the crystallite of electrodeposited chromium layers become big, and the crystal orientation of electrodeposited chromium layers is controlled on the inconsistent direction.
Specifically, the mean diameter of crystallite forms more than the 16.0nm.When the mean diameter of crystallite is lower than 16.0nm, many because crystal boundary becomes, so lattice imperfection increases.Its result, it is big that the contraction when standing thermal process becomes, and has the crack to take place easily at chromium coating.Therefore in the present invention, increase the diameter of crystallite.Described mean diameter is preferably more than the 16.5nm, more preferably more than the 17nm, more than the preferred especially 17.5nm.The upper limit of the mean diameter of crystallite is not done qualification, and is preferably big as much as possible.Optimal can be that chromium coating is certainly as monocrystalline.Also have, be limited to (for example 20～30 μ m) about tens of μ m on the crystallite that calculates by X-ray diffraction device (XRD).
Also have, so-called crystallite, the meaning is the crystallite that can be considered monocrystalline.Be about 5～10nm generally by the mean diameter of electroplating the crystallite in the electrodeposited chromium layers that obtains.
The diameter of above-mentioned crystallite uses the characteristic X-ray Cu-K α of X-ray diffraction device, carries out at Cr (222) diffraction surfaces, and the formula of the following Scherrer of measurement result substitution of the diffusion (integral breadth) of diffraction profile is tried to achieve.Also have, in integral breadth, used value by the correction of Cauchy function.The Alpha-ray wavelength of K is 1.54 .
D＝K·λ/βcosθ
Be expressed as respectively in the formula: D is the diameter () of crystallite; K is constant (1.05); λ is for measuring X ray wavelength (); β is according to the diffusion of the diffracted ray of the diameter of crystallite (integral breadth, unit are radian (radian)); θ is the Bragg angle of diffracted ray.
Locating of crystallite is made as the surface of electrodeposited chromium layers, and locating is 5 places, and the result calculates mean diameter by average measurement.
Increase the crystallite of electrodeposited chromium layers, take place effectively for the crack that reduces this electrodeposited chromium layers, but only this is also insufficient.Therefore in the present invention, as mentioned above, be controlled to be the crystal orientation of chromium coating inconsistent.The inconsistent degree of crystal orientation can be according to the X-ray diffraction evaluation.That is, electrodeposited chromium layers of the present invention is more than 0.10 according to the peak strength of X-ray diffraction method (XRD diffraction) than ({ 211}/{ 222}).When the peak strength ratio is lower than 0.10, because to { orientation ratio of 222} direction became strong, so if stand thermal process, then be easy to generate the crack in specific direction contraction.Particularly if thermal process becomes more than 300 ℃, then shrink change greatly, the crack becomes and is easy to generate.The peak strength ratio is preferably more than 0.2, more preferably more than 0.4.If particularly the peak strength ratio is more than 0.4, then stand the thermal process more than 400～500 ℃, the crack also is difficult to take place.The upper limit of peak strength ratio is not specially limited, but for example is about 0.5.
Also having, for by as the film forming electrodeposited chromium layers of the general employed decoration chrome plating electroplate liquid of industrial chromium plating bath, if measure above-mentioned peak strength ratio by X-ray diffraction method, then is about 0.01～0.1, to { orientation ratio of 222} direction is strong.
Above-mentioned peak strength is than ({ 211}/{ 222}), be by X-ray diffraction device service performance X ray Cu-K α (the Alpha-ray wavelength of K is 1.54 ), calculate { 211} and { peak strength of 222}, the value of trying to achieve respectively according to the X-ray diffractogram of obtaining by their ratio ({ peak strength of 211}/{ peak strength of 222}).
Locating of above-mentioned peak strength is the surface of electrodeposited chromium layers, and measuring the place is 5 places, calculates the peak strength ratio by the average measurement result.Also have, baseline is not on average to be 3 of peak value and trying to achieve.
Above-mentioned electrodeposited chromium layers can be provided with 1 layer at least on the surface of metal system member, but also the electrodeposited chromium layers that satisfies above-mentioned prerequisite can be provided with more than 2 layers.For example when being provided with 2 layers, preferably make the mean diameter of crystallite of chromium coating of the face side of the metal system of being arranged at member, identical with the mean diameter of the crystallite of second chromium coating on the surface that is arranged at this chromium coating, perhaps the mean diameter than the crystallite of second chromium coating is big.In addition, preferably make the peak strength ratio of chromium coating, with the peak strength of second chromium coating than identical, perhaps than the peak strength of the second chromium degree layer than big.Also have, when being provided with more than 3 layers, identical with 2 layers situation.
The thickness of above-mentioned electrodeposited chromium layers is not specially limited, but can be made as 1～50 μ m.When thickness was lower than 1 μ m, because have trickle crack to enter even connect coating at electrodeposited chromium layers, erosion resistance fully improved so be difficult to just.Thickness more preferably more than the 2 μ m, more preferably more than the 5 μ m, is preferably more than the 10 μ m especially.Particularly, in order to prevent the fissured generation when the thermal process that stands 450 ℃, recommending the thickness of electrodeposited chromium layers is more than the 5 μ m.But if thickness surpasses 50 μ m, then electrodeposited chromium layers becomes blocked up, has the crack that the erosion resistance deterioration takes place on the contrary easily.Thickness more preferably below the 45 μ m, more preferably below the 40 μ m, is preferably below the 35 μ m especially.
According to above-mentioned electrodeposited chromium layers, can take into account the reduction of crack generation and suitable hardness and guarantee.The hardness of above-mentioned electrodeposited chromium layers for example is more than the Hv350, to be preferably more than the Hv380, more preferably more than the Hv400.Also have, if measuring the hardness of general electrodeposited chromium layers then is more than the Hv900, but it is excessive to reach this horizontal high rigidityization, even control the mean diameter and the crystal orientation of the crystallite of electrodeposited chromium layers as described above, the crack also can become and take place easily when bearing thermal process.So the hardness of electrodeposited chromium layers, recommending for example is below the Hv600, more preferably below the Hv590.
The hardness of above-mentioned electrodeposited chromium layers can be by the section of Vickers micro Vickers hardness meter mensuration electrodeposited chromium layers.Survey periodic load and be made as 0.49N (50gf).The mensuration place of hardness is 5 places, averages and calculates hardness removing maximum value and minimum value among the measurement result 3.
In the present invention, preferably on the surface of above-mentioned electrodeposited chromium layers, the hard layer higher than this electrodeposited chromium layers hardness is set.By hard layer is set, the wearability of chrome plating component is further improved.Described hard layer, in order to ensure wearability, thus the above-mentioned electrodeposited chromium floor height of hardness ratio, and can surpass Hv600.The hardness of hard layer is more preferably more than the Hv800, more preferably more than the Hv900.The upper limit of the hardness of hard layer is not specially limited, but if hardness is too high, then toughness became low, produces peeling off of hard layer, so for example be made as below the Hv1500.
The kind of hard layer limits especially, for example can list hard chrome coating or hard Ni-P coating, CrN layer, TiN layer etc.Particularly if hard chrome coating is set, then because and the good institute of the compactness between the above-mentioned electrodeposited chromium layers think preferred.
Hard chromium layer, the mean diameter of preferred crystallite is more than the 16.0nm, and according to { the 211} and { peak strength of 222} is more than 0.10 than ({ 211}/{ 222}) of X-ray diffraction method.This is because if the mean diameter of crystallite and above-mentioned peak strength ratio satisfy this scope, even the abominable thermal process crack of then bearing more than 300 ℃ also is difficult to take place.
Hard layer can be provided with the surperficial stacked of above-mentioned electrodeposited chromium layers, also can between electrodeposited chromium layers and hard layer the middle layer be set.
The thickness of hard layer is not particularly limited, but can be made as about 10～50 μ m.When being lower than 10 μ m,, hard layer can not improve wearability fully even being set.But if surpass 50 μ m then thickness become excessive, the crack takes place easily in large quantities.
On the surface of above-mentioned electrodeposited chromium layers, during stacked above-mentioned hard chrome coating, preferably the total with the thickness of electrodeposited chromium layers and hard chrome coating is made as below the 100 μ m.
Also have, when stacked electrodeposited chromium layers and hard chromium layer,, then can confirm whether to be provided with hard chromium layer if use the microscopic examination section, as microscope, can adopt any of opticmicroscope, scanning electron microscope (SEM), transmission electron microscope (TEM).And for easy, if the hardness of measuring the lamination part at several places just can confirm whether to be provided with hard chrome coating.
Become the metal system member of the base material of above-mentioned electrodeposited chromium layers etc., be not specially limited, for example can list copper or copper alloy, iron, steel, aluminium, aluminium alloy, titanium alloy, magnesium alloy etc.Also have, when chrome plating component of the present invention is used as the former material of continuous casting mold,, preferably adopt copper or copper alloy as above-mentioned base material from improving the viewpoint of cooling efficiency.
Chrome plating component of the present invention is suitable as the former material that the meniscus side of the mold that contacts with molten steel is used.On the other hand,, be provided with the member of hard chromium layer, because wearability is also excellent, so can be preferably used as the former material that the exit side of the mold that contacts with solidified shell uses as hard layer on the upper strata of above-mentioned electrodeposited chromium layers.
Chrome plating component of the present invention satisfies above-mentioned prerequisite, and its making method is not particularly limited, but the following describes an example of making method.
Satisfy the chrome plating component of above-mentioned prerequisite, the temperature of electroplating solution during plating is made as 65～100 ℃, and current density is made as 50～500A/dm
2, obtain by plating.
Temperature of electroplating solution is made as 65～100 ℃ of surfaces at metal system member electrodeposited chromium layers is set.When temperature of electroplating solution was lower than 65 ℃, crystallite diminished, and electrodeposited chromium layers is to { it is inconsistent that the orientation ratio grow of 222} direction, crystal orientation can not become in addition.Temperature of electroplating solution is preferably more than 70 ℃, more preferably more than 75 ℃.But, when temperature of electroplating solution surpasses 100 ℃, because will need the interior pressure-controlled container of autoclave etc., thus the operation variation, cost uprises, so temperature of electroplating solution is made as below 100 ℃.Temperature of electroplating solution is preferably below 95 ℃.
When making chrome plating component of the present invention, set temperature of electroplating solution than common raising, but only improve temperature of electroplating solution, can not control the inconsistent degree of the diameter and the crystal orientation of the crystallite in the electrodeposited chromium layers fully.Therefore, except that the control of temperature of electroplating solution, the current density during with electrodeposited chromium is made as 50～500A/dm
2When current density is lower than 50A/dm
2The time, owing to think that film forming speed is little, the growth of crystallite is impaired, and crystal orientation cooperates easily when the absorption of Cr grain, so crystallite diminishes, and crystal orientation is also { consistent on the 222} direction.Think also that in addition if film forming speed is little, the hydrogen quantitative change in the film that then is ingested is many, strain produces in a large number owing to the existence of hydrogen, its result, and the hardness of electrodeposited chromium layers becomes too high.In addition, film forming speed diminishes, and cost uprises.Current density is preferably 100A/dm
2More than, 150A/dm more preferably
2More than.But current density is if surpass 500A/dm
2, then bad at the end or the protuberance generation plating of member, coating is peeled off, so current density is made as 500A/dm
2Below.Current density is preferably 450A/dm
2Below, 400A/dm more preferably
2Below, be preferably 350A/dm especially
2Below.
Above-mentioned electrodeposited chromium layers also can apply pulsed electrical chromium plating by pulsed current.If apply pulse, then when the absorption of Cr crystal grain, think hydrogen react cause before, cut off the electricity supply, the hydrogen quantitative change in the film that is ingested is few, the dependent variable in the film reduces.Fissured generation when this result can further prevent to bear thermal process.
When applying pulsed electrical chromium plating, temperature of electroplating solution is made as 65～100 ℃, and the maximum current density of pulsed current is made as 50～500A/dm
2, in addition frequency is made as 100～1000Hz.When frequency was lower than 100Hz, even suitably control temperature of electroplating solution and maximum current density, crystallite still diminished, and to { the orientation grow of 222} direction of crystal orientation.If frequency is low, then almost can't obtain to apply the effect that pulse produces in addition, only be that film forming speed reduces.Frequency is preferably more than the 150Hz, more preferably more than the 200Hz.But if frequency surpasses 1000Hz, then crystallite diminishes, and the hardness of electrodeposited chromium layers uprises.Frequency is preferably below the 900Hz, more preferably below the 800Hz.Also have, minimum electrical current density can be made as 0A/dm
2Below (comprising opposite polarity situation).
The waveform of above-mentioned pulsed current is not particularly limited, and still, with respect to the ratio of film forming time of plating in electrodeposited chromium treatment time (film forming time of plating/all plating treatment times), is preferably 0.25～0.9.When ratio is lower than 0.25, because film forming speed is low excessively, so want the overspending time in order to obtain the ideal thickness.On the other hand, if ratio surpasses 0.9, then cut off the hydrogen difficulty that becomes that reacts.
Also have, also can implement treatment condition (for example, temperature of electroplating solution and current density, frequency etc.) are changed and tilting of electrodeposited chromium to hardness.In addition, when carrying out electrodeposited chromium, preferably stir the filtration, liquid circulation etc. of (for example, pneumatic blending or vibration etc.) or impurity.
As the electrodeposited chromium electroplate liquid, can adopt the decoration chrome plating electroplate liquid.So-called decoration chrome plating electroplate liquid is to be the electroplate liquid of main component with chromic acid and sulfuric acid, if adopt this electroplate liquid, then can industrialization ground the film forming electrodeposited chromium layers of hard relatively at high speed.The decoration chrome plating electroplate liquid for plating bath, preferably contains the anhydrous chromic acid of 100～400g/L, the trivalent chromium of 1～20g/L, the sulfuric acid of 1.0～5.0g/L.
Particularly the anhydrous chromic acid in the electrodeposited chromium electroplate liquid preferably is made as 270～400g/L.By anhydrous chromic acid is brought up to more than the 270g/L, can strengthen the film forming speed of electrodeposited chromium layers, the membranous thick plating that can easily be fit to.
In the electrodeposited chromium electroplate liquid, also can add promoting agent.As promoting agent, can list for example organic sulfonic acid etc.When adding promoting agent,, can add the organic sulfonic acid about 5～10g/L for plating bath.
On the surface of above-mentioned electrodeposited chromium layers, the condition when being provided with than the high hard layer of this electrodeposited chromium layers hardness is not done special qualification, can adopt known method.As hard layer, when hard chromium layer was set, if be considered to this aspect, then preferred the employing electroplated.When electroplating, can prepare the chromium plating electroplate liquid of 2 kinds, also can adopt same chromium plating electroplate liquid, in galvanized variable process conditions midway and film forming.In order to adopt same chromium plating electroplate liquid with the electrodeposited chromium method, the hard chromium layer bigger than electrodeposited chromium layers hardness is set, as the chromium plating electroplate liquid when using the decoration chrome plating electroplate liquid, for example, can reduce the temperature of electroplating solution of electroplate liquid, the current density when perhaps reducing electrodeposited chromium.In addition, in order according to applying pulsed electrical chromium plating method hard chromium layer to be set by pulsed current, for example, can be with respect to the ratio of film forming time of plating in frequency and electrodeposited chromium treatment time (film forming time of plating/all plating treatment times), according to the composition of electroplate liquid the hardness of hard chromium layer is become and control greatly.Also have, can handle that also hard chromium layer being set with spraying plating.
When hard chromium layer is set on the surface of above-mentioned electrodeposited chromium layers, also can be in the mode that tilts to the hardness of electrodeposited chromium layers and hard chromium layer continuous film forming.
Below, further describe the present invention according to experimental example, but the unqualified character of the present invention of following experimental example also can suitably change enforcement in the scope that can be fit to the forward and backward aim of stating, these all are contained in technical scope of the present invention.
Embodiment
Experimental example 1
The surface of the pole of the φ 8 * 100mm of the Cu system that obtains in deoxidation is adopted the decoration chrome plating electroplate liquid to carry out electrodeposited chromium, thereby is formed electrodeposited chromium layers, and it is used as test film, carries out following test.
The composition of above-mentioned decoration chrome plating electroplate liquid as main component, as promoting agent wherein, has used the organic sulfonic acid that has added 8g/L for plating bath with chromic acid and sulfuric acid.Also have, the decoration chrome plating electroplate liquid contains the anhydrous chromic acid of 300g/L, the sulfuric acid of 5.0g/L, the trivalent chromium of 5g/L.
Electrodeposited chromium, the temperature of electroplating solution that makes electroplate liquid is the temperature shown in the table 1, stably carries out by the current density shown in the table 1.The thickness of resulting electrodeposited chromium layers is 30 μ m.
Use X-ray diffraction device (the X-ray diffraction device of the electric society of Rigaku system " RINTULTIMA PC (device name) "), with the diameter and peak strength ratio of the crystallite of the above-mentioned resulting electrodeposited chromium layers of step measurements.Locate, be the surface of the electrodeposited chromium layers of the central part of test film, carry out 5 places and measure and average.Its result is by the unified expression of following table 1.
Then, measure the hardness of electrodeposited chromium layers of the section of above-mentioned test film.In the mensuration of hardness, use Vickers micro Vickers hardness meter (" Hardness Tester MVK-G2 (the device name) " of akashi society of Co., Ltd. system), load is 0.49N.The measuring point of hardness is 5 places, and 3 of having removed maximum value and minimum value among the measurement result are average, calculates hardness.The result is represented by following table 1.
Then, by the fused zinc dip test, estimate having or not of the crack generation of resulting electrodeposited chromium layers when bearing thermal process.The fused zinc dip test, be that above-mentioned test film was flooded 20 minutes in 450 ℃ fused zinc, the test film behind the dipping at the lengthwise direction slit shearing, is imbedded resin, carry out mirror ultrafinish, use opticmicroscope with 400 times of interfaces of observing Cu base material (pole) and electrodeposited chromium layers.The observation place is the central part and the end of test film, calculates the length surface with respect to electrodeposited chromium layers, and Cu base material and electrodeposited chromium layers are the ratio of the length of the part be close to, and average value is perfected rate as epithelium.The test film that above-mentioned electrodeposited chromium layers is set be impregnated in 450 ℃ the fused zinc, thereby can apply thermal process to electrodeposited chromium layers, have at this moment in the electrodeposited chromium layers of crack generation, because zinc permeates from the crack part, reach the surface of Cu base material, the Cu base material is corroded thus, makes the generation of peeling off of electrodeposited chromium layers, so perfect rate and can estimate fissured occurrence degree by calculating epithelium.It is that situation more than 60% is qualified that epithelium perfects rate, and it is defective being lower than 60% situation.
[table 1]
| No. | Temperature of electroplating solution (℃) | Current density (A/dm 2) | Crystallite (nm) | The peak strength ratio | Hardness (Hv) | Epithelium perfects rate (%) |
| 1 | 70 | 50 | 16.1 | 0.15 | 600 | 75 |
| 2 | 90 | 200 | 19.4 | 0.93 | 500 | 95 |
| 3 | 80 | 100 | 16.3 | 0.61 | 570 | 95 |
| 4 | 50 | 100 | 9.3 | 0.02 | 1150 | 0 |
| 5 | 80 | 25 | 15.6 | 0.32 | 650 | 25 |
| 6 | 60 | 50 | 16.0 | 0.09 | 620 | 55 |
Can carry out following investigation by table 1.The example by the prerequisite of the present invention's regulation is satisfied in No.1～3rd, because the crystallite dimension of electrodeposited chromium layers and peak strength are than suitably being controlled, so epithelium perfects the rate height,, also can reduce fissured generation even bear abominable thermal process more than 300 ℃.On the other hand, the example by the prerequisite of the present invention's regulation is not satisfied in No.4～6th, because can not bear the thermal process more than 300 ℃, a large amount of cracks has taken place, so the Cu base material is corroded.
Experimental example 2
Be substituted in the electrodeposited chromium in the above-mentioned experimental example 1 and form electrodeposited chromium layers to apply pulsed electrical chromium plating.Apply pulsed electrical chromium plating, the temperature of electroplating solution of electroplate liquid is the temperature shown in the table 2, and the current density shown in the table 2 is a maximum current density, and minimum electrical current density is 0A/dm
2With respect to the ratio of film forming time of plating in electrodeposited chromium treatment time (film forming time of plating/all plating times) is 0.5.Frequency is certain, pays sine wave and film forming.The thickness of resulting electrodeposited chromium layers is 30 μ m.Also have, in No.15 and No.21, change the thickness of plating time with the control electrodeposited chromium layers, No.15 is 3 μ m, and No.21 is 5 μ m.
The resulting diameter that applies the crystallite of pulsed electrical chromium plating layer, peak strength perfect rate than, hardness and epithelium, with the step measurements identical with above-mentioned experimental example 1.The result is by the unified expression of following table 2.
[table 2]
| No. | Temperature of electroplating solution (℃) | Frequency (Hz) | Current density (A/dm 2) | Thickness (nm) | Crystallite (nm) | The peak strength ratio | Hardness (Hv) | Epithelium perfects rate (%) |
| 11 | 75 | 700 | 250 | 30 | 16.5 | 0.42 | 590 | 91 |
| 12 | 80 | 100 | 500 | 30 | 17.5 | 0.75 | 420 | 97 |
| 13 | 80 | 1000 | 100 | 30 | 18.1 | 0.63 | 500 | 100 |
| 14 | 80 | 700 | 100 | 30 | 17.8 | 0.71 | 400 | 100 |
| 15 | 80 | 700 | 100 | 5 | 17.8 | 0.71 | 400 | 60 |
| 16 | 60 | 700 | 100 | 30 | 10.8 | 0.07 | 950 | 12 |
| 17 | 60 | 50 | 100 | 30 | 11.1 | 0.08 | 850 | 10 |
| 18 | 80 | 1200 | 100 | 30 | 14.3 | 0.29 | 550 | 40 |
| 19 | 60 | 1000 | 25 | 30 | 16.1 | 0.09 | 630 | 57 |
| 20 | 80 | 700 | 60 | 30 | 17.5 | 0.52 | 450 | 30※ |
| 21 | 80 | 700 | 100 | 3 | 17.8 | 0.71 | 400 | 24 |
※ peels off the end
Can carry out following investigation from table 2.The example of the prerequisite of the present invention regulation is satisfied in No.11～15th, because the crystallite dimension of electrodeposited chromium layers and peak strength are than suitably being controlled, so epithelium perfects the rate height,, also can reduce fissured generation even bear abominable thermal process more than 300 ℃.On the other hand, No.16～19th, discontented unabridged version is invented the example of the prerequisite of regulation, because can not bear the thermal process more than 300 ℃, a large amount of cracks has taken place, so the Cu base material is corroded.
No.20 and No.21 are reference example.Because the current density when No.20 applies pulsed electrical chromium plating is outside the scope that the present invention recommends, so though that the epithelium of the electrodeposited chromium layers of test film central part perfects rate is good, the electrodeposited chromium layers in the end of test film has confirmed to be peeled off.No.21 is the thin excessively example of thickness of electrodeposited chromium layers, if bear 450 ℃ thermal process, then can not suppress fissured generation fully, and zinc permeates from the crack, thereby fails to improve the erosion resistance of Cu base material.
Experimental example 3
The plate-like test film of the Cu system that obtains in the deoxidation (surface of φ 44mm * 8mm), with with the same terms shown in the No.14 of the No.3 of above-mentioned experimental example 1 or above-mentioned experimental example 2, form after the electrodeposited chromium layers, do not wash and drying, in identical electroplate liquid, hard layer is set on the surface of this electrodeposited chromium layers.As hard layer, with the identical condition shown in the No.12 of the No.5 of the No.4 of above-mentioned experimental example 1, above-mentioned experimental example 1 or above-mentioned experimental example 2, electrodeposited chromium layers is set.But, when the electrodeposited chromium layers shown in the No.4 that above-mentioned experimental example 1 is set as hard layer, after forming the electrodeposited chromium layers shown in the No.14 of the No.3 of above-mentioned experimental example 1 or above-mentioned experimental example 2, temperature of electroplating solution shelved be cooled to 50 ℃ in 10 minutes, keep electroplating in this temperature.Because electroplate, so tilt to the hardness of hard layer while cooling off temperature of electroplating solution.
On the surface of electrodeposited chromium layers, carry out sliding wear testing, thereby estimate the wearability of the test film that is provided with hard layer.Sliding wear testing adopts the trier of selling dish-type (pin ondisk) as the sliding wear testing machine.The sliding test condition adopts Al as the fitting pin material
2O
3The pole of the φ 5mm of system, sliding velocity is 1m/ second, and load is 98N (10kgf), and sliding distance is 1km, carries out with dry type.Mensuration is based on the reduction of the wearing and tearing of test film, with following standard evaluation wearability.The result is represented by following table 3.Also have, why adopted Al as the fitting pin material
2O
3The pole of system is because consider continuous casting mold and the Al that solidifies in the strand
2O
3Inclusion contacts, and makes the surface abrasion of continuous casting mold.
[judgement criteria of wearability]
◎: the reduction of the test film that produces by wearing and tearing is lower than 50mg, and wearability is excellent especially.
Zero: the reduction of the test film that produces by wearing and tearing is 50～100mg, excellent in wear resistance.
*: the reduction of the test film that produces by wearing and tearing surpasses 100mg, and wearability is poor.
[table 3]
| No. | Electrodeposited chromium layers | Hard layer | Wearability | ||
| Kind | Hardness (Hv) | Kind | Hardness (Hv) | ||
| 31 | No.3 | 570 | No.4 | 1150 | ◎ |
| 32 | No.3 | 570 | No.5 | 650 | ○ |
| 33 | No.14 | 400 | No.4 | 1150 | ◎ |
| 34 | No.14 | 400 | No.5 | 650 | ○ |
| 35 | No.3 | 570 | No.12 | 420 | × |
| 36 | No.14 | 400 | No.12 | 420 | × |
Can carry out following investigation from table 3.The example of the prerequisite of the present invention regulation is satisfied in No.31～34th, because on the upper strata of electrodeposited chromium layers, be provided with than this electrodeposited chromium layers hardness height, and hardness surpasses the hard layer of Hv600, so excellent in wear resistance.On the other hand, No.35 and No.36, because the hardness of hard layer is littler than the hardness of electrodeposited chromium layers, perhaps the hardness than electrodeposited chromium layers is big, but below 600Hv, so wearability is poor.
Claims (7)
1, a kind of chrome plating component, it is characterized in that, it is the chrome plating component that is provided with electrodeposited chromium layers on the surface of metal system member, the mean diameter of the crystallite in the described electrodeposited chromium layers is more than the 16.0nm, and according to X-ray diffraction method measure { 211} is with { peak strength of 222} is than { 211}/{ 222} is more than 0.10.
2, according to the chrome plating component of claim 1 record, it is characterized in that described electrodeposited chromium layers hardness is below the Hv600.
3, according to the chrome plating component of claim 1 record, it is characterized in that the thickness of described electrodeposited chromium layers is more than the 5 μ m.
4, according to the chrome plating component of claim 2 record, it is characterized in that the thickness of described electrodeposited chromium layers is more than the 5 μ m.
5, according to the chrome plating component of each record in the claim 1～4, it is characterized in that,, be provided with, and hardness surpasses the hard layer of Hv600 than this electrodeposited chromium layers hardness height on the upper strata of described electrodeposited chromium layers.
6, a kind of continuous casting mold is characterized in that, is made of the chrome plating component of each record in the claim 1～4.
7, a kind of continuous casting mold is characterized in that, the chrome plating component of being put down in writing by claim 5 constitutes.
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| JP2005098936 | 2005-03-30 | ||
| JP2005098936 | 2005-03-30 | ||
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105506697A (en) * | 2016-02-19 | 2016-04-20 | 苏州市华婷特种电镀有限公司 | Mold piece with chromium coating on surface |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105506697A (en) * | 2016-02-19 | 2016-04-20 | 苏州市华婷特种电镀有限公司 | Mold piece with chromium coating on surface |
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