CN102634824A - Foam iron and manufacturing method thereof - Google Patents
Foam iron and manufacturing method thereof Download PDFInfo
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- CN102634824A CN102634824A CN2011100362210A CN201110036221A CN102634824A CN 102634824 A CN102634824 A CN 102634824A CN 2011100362210 A CN2011100362210 A CN 2011100362210A CN 201110036221 A CN201110036221 A CN 201110036221A CN 102634824 A CN102634824 A CN 102634824A
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Abstract
The invention relates to a manufacturing method of foam iron, and particularly relates to a method for plating iron on a conductive porous body surface by electroplating and producing foam iron through heat treatment. The manufacturing method of foam iron comprises the following steps: i) preparing an organic porous body; ii) depositing metal selected from nickel (Ni) or copper (Cu) on the organic porous body surface, then depositing titanium (Ti) to prepare a conductive porous body; iii) injecting an iron electroplating solution into the conductive porous body to electroplate iron on the conductive porous body surface, wherein the electroplating solution contains ferrous chloride (FeCl3.4H2O), is added with at least one of malonic acid, ammonium chloride (NH4Cl), and vanadium trichloride (VCl3), and has a pH of 0.5-2.5; iv) putting the conductive porous body electroplated with iron in a heat treatment furnace, performing heat treatment to remove components of the organic porous body.
Description
Technical field
The present invention relates to a kind of foam iron and method of manufacture thereof, particularly a kind ofly make the method for the foam iron that ductility is outstanding, tensile strength is higher and the foam iron of making by this method continuously through plating mode.
Background technology
Foamed metal (metal foam) is meant that metallic substance inside has the porous of a lot of bubbles (porous) metal.
This foamed metal is divided into perforating (open cell type) or closed pore formula (closed cell type) according to the bubble shape of inside.With regard to perforate, a plurality of bubbles exist with the state of interconnecting, and gas or fluid pass through with these bubbles easily.On the contrary, in closed pore, each other not connect between the bubble, and independent the existence, thus gas or fluid be not easy through.
With regard to the foamed metal with perforate, its structure and human body bone are similar, thus Stability Analysis of Structures, and the surface area ratio of unit volume is very big, simultaneously because lightweight physical property can be applied to various technical fields.
This foamed metal is applied to the component, waste gas filter of battery electrode, fuel cell with various industrial fields such as strainer, pollution control device, catalyst support, sound equipment component.
It is the foamed metal of matrix metal that known so far foamed metal mainly contains with nickel, copper, aluminium or silver, but the foam iron of iron as matrix metal is not had by extensively not known.
Summary of the invention
The present invention provides a kind of pin-and-hole (pin-hole) that suppresses the surface to greatest extent to generate, and ductility and the outstanding foam iron of tensile strength.
And it is a kind of in the process of making foam iron that the present invention also provides, and the big ferroelectric plating bath of corrodibility had the metal deposition of strong corrosion stability.
The present invention provides also that a kind of divalent iron is oxidized to 3 valency iron on the ferroelectric plating operation in the process of making foam iron, makes the particulate deposits thing that produces when generating 3 valency ironic hydroxides not be blended into the method for plating iron layer.
In addition, the present invention also provides a kind of can carry out electroplating work procedure and heat treatment step continuously in the process of making foam iron, to reduce the method for manufacturing cost.
The foam iron that one embodiment of the invention relate to is the reticulated structure with perforate; Said structure is a benchmark with weight %, and the content of titanium accounts for 0.01% to 1%, and the content of carbon (carbon) accounts for 0.001% to 0.5%; Rest parts is made up of iron, and contains inevitable impurity.
The structure of said foam iron can further comprise a kind of metal in the copper that is selected from 0.01% to 1% nickel or 0.01% to 1%.
When containing titanium (Ti) and nickel (Ni) in the said structure, wherein titanium (Ti) accounts for 20-50%, nickel (Ni) accounts for 50-80%, and when containing titanium (Ti) and copper (Cu), wherein titanium (Ti) accounts for 20-50%, copper (Cu) accounts for 50-80%.
The method of manufacture of the foam iron that one embodiment of the invention relates to may further comprise the steps: ⅰ) prepare organic porous body; ⅱ) surface deposition at organic porous body is selected from a kind of metal in nickel (Ni) or the copper (Cu), and titanium deposition (Ti) is prepared the electroconductibility porous insert with this then; ⅲ) with the electroconductibility porous insert through ferroelectric plating bath, with at said electroconductibility porous insert surface electric plating iron, said electroplate liquid contains iron protochloride (FeCl
24H
2And be added with propanedioic acid (malonic acid), ammonium chloride (NH O),
4Cl), vanadium trichloride (VCl
3) at least a material, and the pH value is 0.5 to 2.5; The electroconductibility porous insert that and ⅳ) will be coated with iron is put into heat treatment furnace, removes the composition of organic porous body through thermal treatment.
The method of manufacture of said foam iron further comprises the process of cleaning the said electroconductibility porous insert that is coated with iron.
The step that said cleaning is coated with the electroconductibility porous insert of iron comprises: under 50 ℃ ~ 70 ℃ temperature, using the pH value is that 1～1.5 hydrochloric acid solution carries out pickling, removes Acidwash solution with air afterwards; After cleaning the removed electroconductibility porous insert of said Acidwash solution with 50 ℃ ~ 70 ℃ water, remove water with air again; And after cleaning the removed electroconductibility porous insert of said water with 50 ℃ ~ 70 ℃, the water-soluble rut preventives of 0.5 ~ 5g/L, remove rut preventives with air again.
In the preparation step of said electroconductibility porous insert, again during titanium deposition (Ti), wherein nickel (Ni) accounts for 50-80% to nickel deposited (Ni), titanium (Ti) accounts for 20-50% afterwards in the ban; Again during titanium deposition (Ti), wherein copper (Cu) accounts for 50-80% to deposited copper (Cu), titanium (Ti) accounts for 20-50% afterwards in the ban.
The preparation step of electroconductibility porous insert can deposit through PVD (Physical vapor deposition) method in volume to volume equipment.
At the thickness of said organic porous body surface deposition 0.02 μ m to 0.3 μ m preferably.
The organic porous body that uses in one embodiment of the invention is selected from a kind of in polymer foaming body, nonwoven fabric, the organic fabric, preferably uses foamed polyurethane.
Ferroelectric plating bath can further comprise ferrous sulfate (FeSO
47H
2O).
And, preferably 75 ℃-95 ℃ of the temperature of ferroelectric plating bath, the apparent cathode current density of plating tank is 100 A/m preferably
2-2500A/m
2
Heat treatment process comprises: the step of the inner organic composition of iron that ⅰ) defoams; ⅱ) the defoam step of the inner residual carbon of iron; ⅲ) reduction heat treatment step; And ⅳ) annealing steps of removal stress from the foam iron of having made.
Above-mentioned heat treatment step preferably carries out in continuous tunnel furnace according to the order of sequence and continuously.
With regard to regard to the foam iron of one embodiment of the invention manufacturing; Because crystal grain is fine, ductility is outstanding, tensile strength is higher, so the component, waste gas filter that can be applied to battery electrode, fuel cell are with various industrial fields such as strainer, pollution control device, catalyst support, sound equipment component.
The method of manufacture of the foam iron that one embodiment of the invention relate to can prevent the oxidation in the plating iron process, thus in winding process, can not rupture yet, thus can make foam iron continuously.
The method of manufacture of the foam iron that one embodiment of the invention relate to provides oxidizing atmosphere in heat treatment step, thereby can prevent that foam iron from damaging because of the tension force of roller (roll).
The method of manufacture of the foam iron that one embodiment of the invention relate to can be removed organic composition and residual carbon continuously in heat treatment step, generate pin-and-hole on the foam iron surface with the inhibition manufacturing, thereby ganoid foam iron can be provided.
The method of manufacture of the foam iron that one embodiment of the invention relate to can make deposition, electroplating work procedure and the heat treatment step of conductive metal carry out continuously.
Description of drawings
Fig. 1 is the SEM photo to the foam iron after heat-treating according to the galvanized electroconductibility porous insert of embodiment of the invention manufacturing.
Fig. 2 is the SEM photo that the surface of the foam iron of Fig. 1 is amplified.
Fig. 3 heat-treats SEM photo before to the galvanized electroconductibility porous insert that the comparative example B1 according to the present invention makes.
Embodiment
Specify embodiments of the invention with reference to the accompanying drawings, so that person of ordinary skill in the field of the present invention implements easily.But the present invention can use multiple mode to implement, and is not limited in this illustrated example.
For making foam iron, prepare to be formed at the organic porous body that foam iron is inner and have the bubble syndeton.Organic porous body can use inside to have the various polymer foaming bodies, nonwoven fabric, organic fabric etc. that connect shape like bubble.One embodiment of the invention are given an example foamed polyurethane (PU) or the organic fabric as above-mentioned organic porous body have been described.
To cut into thin slice (sheet) shape as the employed organic porous body of the substrate of foam iron, the thin slice of cutting can be processed circle with the bubble section through chemistry or heat treatment process.And the organic porous body thin slice successfully carried out in order to make plating before carrying out electroplating processes, can optionally carry out galvanized preceding continuous treatment process, i.e. clean, s.t., coating catalyst, drying etc.These processes belong to the step of preparing organic porous body.
Ready organic porous body has electroconductibility hardly, so in organic porous body surface plating iron, should give electric conductivity (electrical conductivity) to organic porous body.Said process belongs to the preparation step of electroconductibility porous insert.
The preparation step of electroconductibility porous insert is accomplished through the method for coating electrically conductive property metal on laminar organic porous body.
Operation in the surface applied conductive metal of organic porous body is carried out through volume to volume (the Roll to Roll) equipment that PVD (Physical vapor deposition) device is installed.
In volume to volume equipment to the two sides metal refining of organic porous body.At this moment, be after deposition is selected from a kind of metal in nickel (Ni) or the copper (Cu) earlier in the process of organic porous body surface deposition metal, the process of titanium deposition (Ti) again.
Using titanium or titanium alloy as the PVD deposition source is in order to give stronger solidity to corrosion to porous insert.And, organic porous body surface applied titanium be because, since the back described ferroelectric plating bath have stronger acidity, so its corrodibility is stronger.That is, titanium has stronger solidity to corrosion to highly acid electroplate liquid.
When the metal that is deposited on the organic porous body surface was titanium (Ti) and nickel (Ni), its ratio preferably was controlled at nickel (Ni) and accounts for 50-80%, and titanium (Ti) accounts for 20-50%.And when titanium deposition (Ti) and copper (Cu), its ratio preferably is controlled at copper (Cu) and accounts for 50-80%, and titanium (Ti) accounts for 20-50%.So, when depositing behind other metal of mixing in the titanium,, thereby be difficult to obtain uniform coating if the content of nickel (Ni) and copper (Cu) greater than 80%, then in the described electroplating work procedure in back corrosion phenomenon will take place.And, if the content of nickel (Ni) and copper (Cu) less than 50%, then because electroconductibility is improved effect decline, thereby is difficult to obtain homogeneous coating.
When mixed with titanium (Ti) and nickel (Ni) or titanium (Ti) and copper (Cu) are when depositing afterwards on organic porous body surface, sedimentary metal layer thickness is preferably 0.02-0.3 μ m.Less than 0.02 μ m, then electroplating can be inhomogeneous as if the sedimentary metal thickness of institute, and if thickness greater than 0.3 μ m, then owing to the internal heat of depositing device, can make the porous insert distortion.
Below, in containing the plating tank of iron to carrying out electroplating processes with the porous insert of mode coating electrically conductive property metal as stated.
For the employed electroplate liquid of acierage comprises iron protochloride (FeCl
24H
2O), and with the pH value be transferred to 0.5-2.5.At this moment, preferably add the iron protochloride of 30-450g/L in the electroplate liquid, and optionally comprise the ferrous sulfate (FeSO of 50-350g/L
47H
2O).
For improving the oxidation-resistance of above-mentioned electroplate liquid, at least a material in the vanadium trichloride (VCl3) of the propanedioic acid (malonic acid) of all right further interpolation 1-10g/L, the ammonium chloride (NH4Cl) of 30-150g/L, 0.1-2g/L.Oxidation-resistance is to suppress the physical properties that divalent iron is oxidized to 3 valency iron, and said propanedioic acid and ammonium chloride have this effect, if add vanadium trichloride, then its oxidation-resistance can further improve.And ammonium chloride not only has oxidation-resistance, and has the effect of the foam of increasing iron ductile.
As previously mentioned, the pH value of electroplate liquid preferably is transferred to 0.5-2.5.If the pH value of electroplate liquid is less than 0.5, then the solubleness as the soft steel of anode material can improve, if the pH value of electroplate liquid is greater than 2.5, and the generation of then very difficult inhibition 3 valency iron.If generate 3 valency iron, the ductility variation of foam iron then, thus can not reel.
When the electroconductibility porous insert being carried out plating iron, will electroplate object through electroplating device---the electroconductibility porous insert will be electroplated the source as negative electrode---iron (Fe) is as anode.At this moment, as on the surface of the porous insert of cathode material earlier deposition be selected from behind a kind of metal in nickel (Ni) or the copper (Cu) titanium deposition (Ti) again.And it is the soft steel below 0.1% that anode material preferably uses carbon content.
On the electroconductibility porous insert during acierage, the current density of apparent negative electrode is 100-2500A/m2 in the electrolytic condition of plating tank through above-mentioned condition, and the temperature of electroplate liquid is 75-95 ℃.At this moment, when the temperature of electroplate liquid was lower than 75 ℃, the surface of galvanized electroconductibility porous insert showed black, and ductility variation and pulverizing easily.And if the temperature of electroplate liquid is higher than 95 ℃, then energy expenditure increases, and too much electroplate liquid is evaporated.
On electroconductibility porous insert surface after the acierage, in order to remove organic substance, and give ductility and tensile strength for established foam iron with above-mentioned condition, the electroconductibility porous insert of acierage is carried out following thermal treatment.
Specify heat treatment step below:
At first, remove organic porous body from the porous insert that is coated with iron, and then after aforementioned hot is handled, remain in the carbon (carbon) in the foam iron through the thermal treatment removal through heat treatment process.And, continue under reducing atmosphere, to heat-treat, with reduced iron, and be the ductility and the tensile strength of the foam iron guaranteeing to have made, be used to remove the anneal of stress continuously.
Aforesaid heat treatment step preferably carries out according to the order of sequence through continuous layout continuous tunnel furnace.And the atmosphere of the continuous tunnel furnace that be used to heat-treat this moment keeps inert condition, and employed rare gas element can be nitrogen (N
2) or argon gas (Ar).Specify this heat treatment step below:
At first, for organic compositions such as removal urethane from the electroconductibility porous insert that is coated with iron, the electroconductibility porous insert that is coated with iron is put into tunnel furnace.At this moment, the atmosphere of continuous tunnel furnace is inert atmosphere or with the hydrogen atmosphere of inert gas dilution, with regard to temperature condition, begins heating from room temperature and makes temperature remain on 500 ℃-650 ℃.In the continuous tunnel furnace that keeps above-mentioned atmosphere and temperature condition, after the electroconductibility porous insert maintenance that is coated with iron 10-60 minute, iron inner organic composition again defoams.If passing through as stated, mode then will have the shape of foam iron from electroconductibility porous insert removal organic composition.
The foam iron of removing organic composition is put into the tunnel like oxidized still continuously, with carbon residual in the iron that defoams (carbon).At this moment, the atmosphere of tunnel like oxidized still remains on the state of dilution oxygen in the rare gas element (O2).
At this moment, the content of oxygen preferably keeps being less than or equal to 3%.And the tunnel like oxidized still that foam iron is housed remains on 500 ℃ of-650 ℃ of TRs through heating.In continuous tunnel furnace, kept 10-30 minute with this state.
Heat-treat by this way is in order to prevent that foam iron oxidized in the series-operation of oxidizing thermal treatment from damaging because of the tension force of roller.And, when under oxidizing atmosphere, removing organic composition, can suppress to greatest extent to generate pin-and-hole (pin-hole) on the foam iron, thereby can make the surface of foam iron keep smooth, make its ductility and tensile strength keep outstanding simultaneously.
And, to put into after the said tunnel like oxidized still, the operation of residual carbon (carbon) is for reducing the necessary operation of carbon (carbon) content in the final foam iron product in the iron that defoams.This operation can be reduced to carbon (carbon) content below 0.05%.At this moment, can increase the tensile strength and the unit elongation of final foam iron product.
So, after the electroconductibility porous insert is removed the aforesaid thermal treatment end of organic composition and carbon component, proceed the reduction heat treatment process.It is in rare gas element, to dilute hydrogen (H that reduction heat is handled
2) continuous tunnel furnace in carry out.At this moment, in temperature rises under 950 ℃-1150 ℃ the state tunnel like reduction furnace that already oxidised foam iron packed into, and kept 10-60 minute, under reducing atmosphere, to carry out high-temperature heat treatment.Then,, be cooled to keep 10-60 minute in this temperature after 400 ℃-600 ℃ the TR, be cooled to again below 100 ℃ in order to remove the internal stress that in process of cooling, might produce.
As stated, through a plurality of operations the operation that organic porous body manufactures final foam iron is preferably carried out with the thin slice state in the equipment of arranging continuously continuously.For this reason, the manufacturing process of electroconductibility porous insert utilizes volume to volume equipment, and plating and heat treatment step preferably use can be continuously electroplating device and continuous tunnel furnace through the thin slice of reeling on the roller.
As shown in Figure 1, have the reticulated structure of perforate through the foam iron of operation manufacturing as stated.
Structure according to the foam iron of one embodiment of the invention manufacturing is a benchmark with weight %, and the content of titanium accounts for 0.01% to 1%, and the content of carbon accounts for 0.001% to 0.5%, and rest parts is made up of iron, and contains other inevitable impurity.
And, not only contain titanium and carbon according to the structure of the foam iron of one embodiment of the invention manufacturing, can also further comprise a kind of metal in the copper that is selected from 0.01% to 1% nickel or 0.01% to 1%.
And in this foam iron, when while titanium deposition and nickel, wherein titanium accounts for 20-50%, and nickel accounts for 50-80%; And when while titanium deposition and copper, wherein titanium accounts for 20-50%, and copper accounts for 50-80%.
Below by following examples further explain the present invention.These embodiment just are used to the explanation the present invention that gives an example, and the present invention is not limited thereto.
Embodiment
At first, foamed polyurethane is used as the starting material that is used to make foam iron.The thickness of employed foamed polyurethane is 1.7mm, and the mean diameter in hole is 575 μ m.
Ready foamed polyurethane is the state that had carried out basic pre-treatment, and deposit Ni-Ti (Ni-Ti), copper-titanium (Cu-Ti) through the PVD device that is provided with in the volume to volume equipment this moment.
Therefore, below according to Ni-Ti (Ni-Ti), copper-titanium (the order explanation embodiments of the invention of Cu-Ti).
One, the embodiment of deposition Ni-Ti (Ni-Ti)
Embodiment A 1
Titanium deposition again after the first nickel deposited on ready foamed polyurethane.
In embodiment A 1, be that 5:5 deposits with the blending ratio of nickel and titanium, the mixolimnion thickness of sedimentary nickel and titanium is 0.17 μ m.
In plating tank, the electroconductibility porous insert that deposits above-mentioned nickel and titanium is carried out acierage with component shown in the table 1.
When acierage, the electrolytic condition of plating tank is that the current density of apparent negative electrode is 700A/m
2, the temperature of electroplate liquid and pH value are as shown in table 1.The surface density of galvanized electroconductibility porous insert all is 420g/m
2
It is said through galvanized electroconductibility porous insert to use 60 ℃, pH value to be that 1 ~ 1.5 hydrochloric acid solution sprays pickling, and then injection air, to remove said Acidwash solution.Clean through the water that sprays 60 ℃ afterwards, making a return journey through injection air dewaters again.Then, clean through spraying 60 ℃, inhibitor (water-soluble rut preventives) solution of 0.5～5g/L, injection air again is to remove said inhibitor.
Galvanized electroconductibility porous insert like this is put into tunnel furnace, with the nitrogen (N that is injected with 97%
2) and 3% hydrogen (H
2) the temperature of tunnel furnace of mixed gas rise to 520 ℃ from room temperature, and under this temperature, kept 30 minutes.
So, after the inner organic compositions such as urethane of the iron that defoams, the foam iron of removing organic composition put into be injected with 97% nitrogen (N
2) and 3% oxygen (O
2) the tunnel like oxidized still of mixed gas in.At this moment, the temperature of tunnel like oxidized still rises to 550 ℃, and under this temperature, keeps 20 minutes, removes residual carbon (carbon) then.
Then, already oxidised foam iron is packed in the tunnel like reduction furnace, and said furnace atmosphere keeps injecting 97% nitrogen (N
2) and 3% hydrogen (H
2) mixed gas.At this moment, the temperature of tunnel like oxidized still rises to 1000 ℃, and keeps 30 minutes in this temperature.
As stated, in order to remove contingent internal stress in process of cooling, the heat treated foam iron that will under reducing atmosphere, reduce is cooled to 500 ℃, and after under this temperature, keeping 30 minutes, is cooled to 100 ℃ again.
Embodiment A 2
In embodiment A 2, be that 7:3 deposits with the blending ratio of nickel and titanium, the mixolimnion thickness of sedimentary nickel and titanium is 0.2 μ m.
In plating tank, above-mentioned electroconductibility porous insert is carried out acierage with component shown in the table 1.
When acierage, the electrolytic condition of plating tank is that the current density of apparent negative electrode is 500A/m
2, the temperature of electroplate liquid and pH value are as shown in table 1.The surface density of galvanized electroconductibility porous insert all is 418g/m
2
It is said through galvanized electroconductibility porous insert to use 60 ℃, pH value to be that 1 ~ 1.5 hydrochloric acid solution sprays pickling, and injection air then is to remove said Acidwash solution.Clean through the water that sprays 60 ℃ afterwards, making a return journey through injection air dewaters again.Then, clean through spraying 60 ℃, inhibitor (water-soluble rut preventives) solution of 0.5～5g/L, injection air again is to remove said inhibitor.
Galvanized electroconductibility porous insert like this is put into tunnel furnace, will be injected with nitrogen (N
2) inert atmosphere under rise to 600 ℃ from room temperature, and under this temperature, kept 10 minutes, and then cool off, made the removed foam iron of urethane composition with this.
So, after the inner organic compositions such as urethane of the iron that defoams, the foam iron of removing organic composition put into be injected with 97% nitrogen (N
2) and 3% oxygen (O
2) the tunnel like oxidized still of mixed gas in.At this moment, the temperature of tunnel like oxidized still rises to 600 ℃, and under this temperature, keeps 10 minutes, removes residual carbon (carbon) then.
Then, foam iron is packed in the tunnel like reduction furnace, and temperature is risen to after 1050 ℃, under this temperature, kept 20 minutes, under reducing atmosphere, foam iron has been carried out high-temperature heat treatment.At this moment, reducing atmosphere remains on and injects 97% nitrogen (N
2) and 3% hydrogen (H
2) mixed gas.
As stated, in order to remove contingent internal stress in process of cooling, the heat treated foam iron that will under reducing atmosphere, reduce is cooled to 600 ℃ from 1050 ℃, and after 600 ℃ keep 20 minutes down, is cooled to room temperature again.
Comparative example B1
In comparative example B1, be that 4:6 deposits with the blending ratio of nickel and titanium, the mixolimnion thickness of sedimentary nickel and titanium is 0.17 μ m.
In plating tank, above-mentioned electroconductibility porous insert is carried out acierage with component shown in the table 1.
When acierage, the electrolytic condition of plating tank is that the current density of apparent negative electrode is 800A/m
2, the temperature of electroplate liquid and pH value are as shown in table 1.The surface density of galvanized electroconductibility porous insert all is 418g/m
2
The matting of then carrying out and heat treatment step are to carry out with embodiment A 2 identical methods.
Comparative example B2
In comparative example B2, be that 9:1 deposits with the blending ratio of nickel and titanium, the mixolimnion thickness of sedimentary nickel and titanium is 0.2 μ m.
In plating tank, above-mentioned electroconductibility porous insert is carried out acierage with component shown in the table 1.
When acierage, the electrolytic condition of plating tank is that the current density of apparent negative electrode is 700A/m
2, the temperature of electroplate liquid and pH value are as shown in table 1.The surface density of galvanized electroconductibility porous insert all is 420g/m
2
The matting of then carrying out and heat treatment step are to carry out with embodiment A 1 identical method.
Following table 1 shows the experiment condition of the foregoing description and comparative example.
[table 1]
| ? | Iron protochloride (g/L) | Ferrous sulfate (g/L) | Ammonium chloride (g/L) | Propanedioic acid (g/L) | Vanadium trichloride (g/L) | Electroplating temperature (℃) | pH |
| Embodiment A 1 | 420 | 65 | - | 2.0 | - | 85℃ | 2.3 |
| Embodiment A 2 | 50 | 280 | 36 | 6.0 | - | 93℃ | 0.7 |
| Comparative example B1 | 430 | - | - | 2.8 | 0.3 | 93℃ | 1.5 |
| Comparative example B2 | 420 | 65 | - | 2.0 | - | 85℃ | 2.3 |
So utilize the physical property and the winding diameter of the foam iron that the Ni-Ti settled layer makes as shown in table 2.
[table 2]
| ? | Unit elongation (%) | Tensile strength (N/) | Minimum winding diameter (mm) after the plating | Minimum winding diameter (mm) after the thermal treatment | Remarks |
| Embodiment A 1 | 12.9 | 36.2 | Φ50 | Φ30 | - |
| Embodiment A 2 | 13.1 | 35.8 | Φ50 | Φ30 | - |
| Comparative example B1 | - | - | Can't reel | Can't reel | Electroplate inhomogeneous |
| Comparative example B2 | - | - | Can't reel | Can't reel | Electroplate inhomogeneous |
As represent to show in present embodiment result's the table 2 that all embodiment all demonstrate outstanding unit elongation and higher tensile strength, and electroplate or thermal treatment after when reeling the foam iron of thin slice state, do not produce fracture and coiling easily.
But, shown in comparative example, when depositing after mixed Ni and the titanium, even the physical properties of the foam iron of manufacturing is poor, or its physical properties good, but can take place unusually when reeling foam iron after electroplating or after the thermal treatment.
This is because with regard to comparative example B1, the ratio of nickel so electroconductibility is improved weak effect, is not easy to obtain the uniformly-coating layer, thereby can not reels greater than 5 in the blending ratio of nickel and titanium.
And with regard to comparative example B2, the ratio of titanium is lower than 2 in the blending ratio of nickel and titanium, so nickel is corroded when electroplating, cause electroplating inhomogeneous, thereby can not reel.
Two, the embodiment of deposited copper-titanium (Cu-Ti)
Embodiment C 1
Titanium deposition again after the first deposited copper on ready foamed polyurethane.
Embodiment C 1 is that 5:5 deposits with the blending ratio of copper and titanium, and the mixolimnion thickness of wherein sedimentary copper and titanium is 0.17 μ m.
And other experiment condition is identical with embodiment A 1.
Embodiment C 2
Embodiment C 2 is that 7:3 deposits with the blending ratio of copper and titanium, and the mixolimnion thickness of wherein sedimentary copper and titanium is 0.2 μ m.
And other experiment condition is identical with embodiment A 2.
Comparative Example D 1
In addition, Comparative Example D 1 is that 4:6 deposits with the blending ratio of copper and titanium, and the mixolimnion thickness of wherein sedimentary copper and titanium is 0.17 μ m.
And other experiment condition is identical with embodiment A 2.
Comparative Example D 2
In addition, Comparative Example D 2 is that 9:1 deposits with the blending ratio of copper and titanium, and the mixolimnion thickness of wherein sedimentary copper and titanium is 0.2 μ m.
And other experiment condition is identical with embodiment A 1.
Following table 3 shows the experiment condition of embodiment and comparative example.
[table 3]
| ? | Iron protochloride (g/L) | Ferrous sulfate (g/L) | Ammonium chloride (g/L) | Propanedioic acid (g/L) | Vanadium trichloride (g/L) | Electroplating temperature (℃) | pH |
| Embodiment C 1 | 420 | 65 | - | 2.0 | - | 85℃ | 2.3 |
| Embodiment C 2 | 50 | 280 | 36 | 6.0 | - | 93℃ | 0.7 |
| Comparative Example D 1 | 430 | - | - | 2.8 | 0.3 | 93℃ | 1.5 |
| Comparative Example D 2 | 420 | 65 | - | 2.0 | - | 85℃ | 2.3 |
Physical property and the winding diameter of foam iron of settled layer manufacturing that so utilizes copper-titanium is shown in following table 4.
[table 4]
| ? | Unit elongation (%) | Tensile strength (N/) | Minimum winding diameter (mm) after the plating | Minimum winding diameter (mm) after the thermal treatment | Remarks |
| Embodiment C 1 | 12.7 | 35.8 | Φ50 | Φ30 | - |
| Embodiment C 2 | 12.8 | 36.2 | Φ50 | Φ30 | - |
| Comparative Example D 1 | - | - | Can't reel | Can't reel | Electroplate inhomogeneous |
| Comparative Example D 2 | - | - | Can't reel | Can't reel | Electroplate inhomogeneous |
As represent to show in present embodiment result's the table 4 that all embodiment all demonstrate outstanding unit elongation and higher tensile strength, and electroplate or thermal treatment after when reeling the foam iron of thin slice state, do not produce fracture and coiling easily.
But, with regard to comparative example, when depositing after mixed copper and the titanium, even the physical properties of the foam iron of manufacturing is poor, or its physical properties good, but can take place unusually when reeling foam iron after electroplating or after the thermal treatment.
This is because the ratio of copper descends so electroconductibility is improved effect greater than 5 in the copper in Comparative Example D 1 and the blending ratio of titanium, is difficult to obtain uniform coating, thereby can not reels.
And, with regard to Comparative Example D 2 because the ratio of titanium is lower than 2 in the blending ratio of copper and titanium, so when plating copper be corroded, cause electroplating inhomogeneous, thereby can not reel.
Above preferred embodiments of the present invention have been disclosed for illustrative, but the present invention is not limited at the embodiment shown in this.Within the spirit and scope of the present invention all, the various modifications of being done, be equal to replacement and all should belong within protection scope of the present invention.
Claims (22)
1. foam iron with perforate is characterized in that:
Said foam iron is the reticulated structure with perforate, and said structure is a benchmark with weight %, and the content of titanium accounts for 0.01% to 1%, and the content of carbon (carbon) accounts for 0.001% to 0.5%, and rest parts is made up of iron, and contains inevitable impurity.
2. according to the described foam iron of claim 1, it is characterized in that with perforate:
Said structure further comprises a kind of metal that is selected from 0.01% to 1% nickel, 0.01% to 1% the copper.
3. according to the described foam iron of claim 2, it is characterized in that with perforate:
When containing titanium (Ti) and nickel (Ni) in the said structure, wherein titanium (Ti) accounts for 20-50%, nickel (Ni) accounts for 50-80%, and when containing titanium (Ti) and copper (Cu), wherein titanium (Ti) accounts for 20-50%, copper (Cu) accounts for 50-80%.
4. the method for manufacture of a foam iron is characterized in that, may further comprise the steps:
Prepare organic porous body;
Surface deposition at said organic porous body is selected from a kind of metal in nickel (Ni) or the copper (Cu), and titanium deposition (Ti) is prepared the electroconductibility porous insert with this then;
Through ferroelectric plating bath, with at said electroconductibility porous insert surface electric plating iron, said electroplate liquid contains iron protochloride (FeCl with said electroconductibility porous insert
24H
2And be added with propanedioic acid (malonic acid), ammonium chloride (NH O),
4Cl), vanadium trichloride (VCl
3) at least a material, and the pH value is 0.5 to 2.5; And
The said electroconductibility porous insert that is coated with iron is put into heat treatment furnace, thereby remove said organic porous body composition through thermal treatment.
5. according to the method for manufacture of the described foam iron of claim 4, it is characterized in that, further comprise the step of cleaning the said electroconductibility porous insert that is coated with iron.
6. according to the method for manufacture of the described foam iron of claim 5, it is characterized in that the step that said cleaning is coated with the said electroconductibility porous insert of iron comprises:
Under 50 ℃ ~ 70 ℃ temperature condition, using the pH value is that 1～1.5 hydrochloric acid solution carries out pickling, removes Acidwash solution with air afterwards;
After cleaning the electroconductibility porous insert that said Acidwash solution removed with 50 ℃ ~ 70 ℃ water, remove water with air again; And
After cleaning the removed electroconductibility porous insert of said water with 50 ℃ ~ 70 ℃, the water-soluble rut preventives of 0.5 ~ 5g/L, remove rut preventives with air again.
7. according to the method for manufacture of the described foam iron of claim 4, it is characterized in that:
In the preparation step of said electroconductibility porous insert, again during titanium deposition (Ti), wherein nickel (Ni) accounts for 50-80% to nickel deposited (Ni), titanium (Ti) accounts for 20-50% afterwards in the ban; Again during titanium deposition (Ti), wherein copper (Cu) accounts for 50-80% to deposited copper (Cu), titanium (Ti) accounts for 20-50% afterwards in the ban.
8. according to the method for manufacture of the described foam iron of claim 4, it is characterized in that:
The preparation step of said electroconductibility porous insert deposits with the PVD method in volume to volume equipment.
9. the method for manufacture of described according to Claim 8 foam iron is characterized in that:
Sedimentary thickness is 0.02 μ m to 0.3 μ m on the said porous insert.
10. according to the method for manufacture of the described foam iron of claim 4, it is characterized in that:
Said organic porous body is selected from a kind of material in polymer foaming body, nonwoven fabric, the organic fabric.
11. the method for manufacture according to the described foam iron of claim 10 is characterized in that:
Said organic porous body is a kind of material that is selected from foamed polyurethane and the porousness organic fabric.
12. the method for manufacture according to any one described foam iron in the claim 4 to 11 is characterized in that:
Said ferroelectric plating bath further comprises ferrous sulfate (FeSO
47H
2O).
13. the method for manufacture according to the described foam iron of claim 12 is characterized in that:
The iron protochloride that adds in the said ferroelectric plating bath is 30-450g/L, ferrous sulfate (FeSO
47H
2O) be 50-350g/L.
14. the method for manufacture according to any one described foam iron in the claim 4 to 11 is characterized in that:
The propanedioic acid that adds in the said ferroelectric plating bath is 1-10g/L, ammonium chloride (NH
4Cl) be 30-150g/L, vanadium trichloride (VCl
3) be 0.1-2g/L.
15. the method for manufacture according to the described foam iron of claim 13 is characterized in that:
The propanedioic acid that adds in the said ferroelectric plating bath is 1-10g/L, ammonium chloride (NH
4Cl) be 30-150g/L, vanadium trichloride (VCl
3) be 0.1-2g/L.
16. the method for manufacture according to any one described foam iron in the claim 4 to 11 is characterized in that:
The temperature of said ferroelectric plating bath is 75 ℃-95 ℃.
17. the method for manufacture according to the described foam iron of claim 12 is characterized in that:
The temperature of said ferroelectric plating bath is 75 ℃-95 ℃.
18. the method for manufacture according to any one described foam iron in the claim 4 to 11 is characterized in that:
In said plating step, the apparent cathode current density of plating tank is 100 A/m
2-2500A/m
2
19. the method for manufacture according to any one described foam iron in the claim 4 to 11 is characterized in that:
In said heat treatment step; Said galvanized electroconductibility porous insert is put into tunnel furnace; And the rare gas element of hydrogen arranged to said tunnel furnace injecting inert gas or dilution; Temperature is risen to after 500 ℃-600 ℃ from room temperature, kept 10-60 minute, and then the inner organic composition of iron that defoams.
20. the method for manufacture according to the described foam iron of claim 19 is characterized in that:
Said heat treatment step further comprises; The said foam iron of removing organic composition is put into the tunnel like oxidized still; And inject the rare gas element that dilution has oxygen to said tunnel like oxidized still; Temperature is risen to after 500 ℃-600 ℃, kept 10-30 minute, and then remove the process of residual carbon (carbon).
21. the method for manufacture according to the described foam iron of claim 20 is characterized in that:
Said heat treatment step comprises, the foam iron of removing said residual carbon is put into the tunnel like reduction furnace, and injects the hydrogen (H with inert gas dilution to said tunnel like reduction furnace
2), temperature is risen to after 950 ℃-1150 ℃, kept 10-60 minute, and under reducing atmosphere, carry out high-temperature heat treatment, be cooled to 400 ℃-600 ℃ then, and in this TR, kept 10-60 minute, be cooled to again below 100 ℃ afterwards.
22. the method for manufacture according to any one described foam iron in the claim 4 to 11 is characterized in that:
The method of manufacture of said foam iron is carried out continuously.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100362210A CN102634824A (en) | 2011-02-11 | 2011-02-11 | Foam iron and manufacturing method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100362210A CN102634824A (en) | 2011-02-11 | 2011-02-11 | Foam iron and manufacturing method thereof |
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|---|---|
| CN102634824A true CN102634824A (en) | 2012-08-15 |
Family
ID=46619397
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011100362210A Pending CN102634824A (en) | 2011-02-11 | 2011-02-11 | Foam iron and manufacturing method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105018971A (en) * | 2015-07-20 | 2015-11-04 | 哈尔滨工业大学 | Method for preparing functional micro-nano structure dendritic alpha-Fe-based material through iron |
| CN109321955A (en) * | 2018-12-14 | 2019-02-12 | 大连理工大学 | A kind of electrodeposition of Fe-Zn alloy electroplating bath |
| CN111850625A (en) * | 2020-07-16 | 2020-10-30 | 暨南大学 | Electroplating liquid for direct electrodeposition of iron on magnesium alloy surface and electroplating process thereof |
| CN114870503A (en) * | 2022-05-13 | 2022-08-09 | 益阳市菲美特新材料有限公司 | Porous oil fume filtering material and manufacturing method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20100097575A (en) * | 2009-02-26 | 2010-09-03 | 고려아연 주식회사 | Iron foam and manufacturing method thereof |
-
2011
- 2011-02-11 CN CN2011100362210A patent/CN102634824A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20100097575A (en) * | 2009-02-26 | 2010-09-03 | 고려아연 주식회사 | Iron foam and manufacturing method thereof |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105018971A (en) * | 2015-07-20 | 2015-11-04 | 哈尔滨工业大学 | Method for preparing functional micro-nano structure dendritic alpha-Fe-based material through iron |
| CN105018971B (en) * | 2015-07-20 | 2017-09-12 | 哈尔滨工业大学 | A kind of method by the dendritic α Fe sills of iron standby functional micro-nano structure |
| CN109321955A (en) * | 2018-12-14 | 2019-02-12 | 大连理工大学 | A kind of electrodeposition of Fe-Zn alloy electroplating bath |
| CN109321955B (en) * | 2018-12-14 | 2020-01-24 | 大连理工大学 | Electroplating solution for electrodepositing Fe-Zn alloy |
| CN111850625A (en) * | 2020-07-16 | 2020-10-30 | 暨南大学 | Electroplating liquid for direct electrodeposition of iron on magnesium alloy surface and electroplating process thereof |
| CN114870503A (en) * | 2022-05-13 | 2022-08-09 | 益阳市菲美特新材料有限公司 | Porous oil fume filtering material and manufacturing method thereof |
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Application publication date: 20120815 |