CN100409981C - Method for preparing superfine metal fibers through method of organogel-thermal reduction process - Google Patents
Method for preparing superfine metal fibers through method of organogel-thermal reduction process Download PDFInfo
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- CN100409981C CN100409981C CNB200510095065XA CN200510095065A CN100409981C CN 100409981 C CN100409981 C CN 100409981C CN B200510095065X A CNB200510095065X A CN B200510095065XA CN 200510095065 A CN200510095065 A CN 200510095065A CN 100409981 C CN100409981 C CN 100409981C
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Abstract
The present invention discloses a method for preparing superfine metal fibers. The method comprises the steps that citric acid or lactic acid is stirred with one of Fe, Co and Ni salts or at least two of Fe, Co, Ni, Cu and Zn salts in deionized water; the pH value of the solution is regulated between 2 to 7 by ammonia water; the solution is polymerized into sol with certain viscidity by vacuum dewatering at constant temperature of 60 to 80 DEG C after stirred for 18 to 24 hours; the solution is dried to have to viscosity of spinning at temperature range of 60 to 80 DEG C in air atmosphere and then spun; fiber precursors are placed in a tubular furnace, and are reduced for one to three hours at temperature of 600 to 900 DEG C in mixing gas atmospheres of nitrogen and hydrogen gas, so metallic fibers of which the diameter is 0.1 to 15 mu m and the length is 0.05 to 2 m are obtained.
Description
Technical field:
The present invention relates to a kind of preparation method of metallic fiber, refering in particular to at least a slaine in citric acid or lactic acid and basic nickel carbonate, ferric nitrate, cobalt nitrate, copper nitrate, the zinc nitrate is initiation material, adopts preparing superfine metal fibers through method of organogel-thermal reduction process.
Background technology:
The progress of society causes material behavior is required more and more higher, and compoundization of material, miniaturization have become the trend of new material development.Metallic fiber and goods thereof are the infant industry material that grew up in nearly 20 years and new and high technology, high value added product, are key areas of modern science.Metallic fiber not only has the intrinsic good heat conduction of metal material itself, conduction, advantage such as anti-corrosion, high temperature resistant, some properties that also have non-metallic fibers, conductive fabric, conductive plastics, electromagnetic wave shielding, antistatic carpet, alloy fiber reinforced aluminum have been widely used in, catalyst or catalyst carrier, the filtering flow of industries such as petrochemical industry, chemical fibre, metallurgy with separate, anode material in safe automobile air bag and the high-energy battery is the essential critical material of many industrial circles and national defense industry.
The fibrous refinement process can make aspects such as its institutional framework, electromagnetic performance, thermal resistance and fusing point that extraordinary effect is arranged, and the specific area of micro metal fiber and draw ratio are all bigger, with them is that the absorbing material quality of main absorber preparation is low weight, and can realize high the absorption at very wide frequency band range.Based on reflection of electromagnetic wave, absorption, repeatedly reflex mechanism and frequency electromagnetic waves can only penetrate the reason on conductor top layer, the metallic fiber diameter is more little, and draw ratio is big more, and the magnetic conductivity of fiber is just high more, intrastitial electromagnetic wave Kelvin effect is just weak more, and fiber electro-magnetic wave absorption performance is just good more.Therefore require the metallic fiber diameter in micron, sub-micron, nanometer scale.
At present, the method for preparing metallic fiber both at home and abroad mainly contains three kinds: the one, and melt spinning method; The 2nd, the machine cut method; The 3rd, the drawing deformation method.Preceding two kinds of method costs are low, but the metallic fiber that obtains is discontinuous and inhomogeneous, are mainly used in the not high field of ask for something, and the diameter of the metallic fiber that makes is generally more than 20 μ m; The monofilament hubbing adopts the multimode continuous drawing, and characteristics are that fiber is even continuously, and the filament footpath is near 20 μ m.The appearance of boundling hubbing has solved the uneven and discontinuous problem in preceding two kinds of method silks footpath, has overcome the high shortcoming of monofilament hubbing cost again, but the producible metal fiber wire of boundling hubbing footpath is usually still more than 6 μ m.These methods prepare the above metallic fiber of diameter 4 μ m, the technology comparative maturity, and it is then very difficult to prepare thinner metallic fiber.With the water-soluble reducing process of introduction by magnetic field
[1]With introduction by magnetic field hydroxyl thermal decomposition method
[2]The diameter that has prepared cobalt and iron fiber respectively is more than the 1.5 μ m, but the metallic fiber of preparation submicron order is still very difficult.Shui and Chung
[3]The application of carbon fibres galvanoplastic have been made diameter 0.4 μ m, the nickel fiber of length 100 μ m, yet because the existence in carbon hole has reduced the electric conductivity of fiber, and diameter is subjected to the restriction of carbon fiber diameter dimension.U.S. Pat 6375703B1 utilizes the hydrazine reducing process to form the nickel fiber under the effect of magnetic field or surfactant, and its diameter also reaches submicron order.Ichiki etc.
[4]Successfully prepare diameter 100 μ m with vapour deposition process, reached the nickel fiber of 3mm.Also have the scholar to prepare the plain body of submicron order Fe with the original position deformation techniques
[5]With the Nb fiber
[6]But these method complex technical process, the preparation condition harshness, fibre diameter is inhomogeneous and distribution is narrower.
[1] HUST's journal, 1998,26 (7): 74-76.
[2] Central China University of Science and Technology's journal, 2001,29 (7): 75-77.
[3]J.Mater.Sci.，2000，35(7)：1773～1785.
[4]J.Mater.Sci.Lett.，1997，16：531-533.
[5] Hebei metallurgy, 2003,6:19-21.
[6]J.Acta?Mater，1998，46(16)：5973-5984
Summary of the invention
At the shortcoming of present technology, the objective of the invention is to be to provide a kind of product purity height, technology is simple, the preparation method of the fine long metallic fiber that process temperature is low, fibre diameter is even, draw ratio is bigger.The objective of the invention is to be achieved through the following technical solutions:
A kind of preparation method of micro metal fiber, with at least a slaine in citric acid or lactic acid and basic nickel carbonate, ferric nitrate, cobalt nitrate, copper nitrate, the zinc nitrate is initiation material, adopt preparing superfine metal fibers through method of organogel-thermal reduction process, its concrete steps are as follows:
1, with citric acid and basic nickel carbonate or cobalt nitrate ratio according to the mol ratio 0.8～2: 1 of citric acid and metal ion, or with the mixture of at least two kinds of slaines in citric acid and ferric nitrate, basic nickel carbonate, cobalt nitrate, copper nitrate and the zinc nitrate, it according to the mol ratio of citric acid and metal ion 0.66～1.5: 1 ratio, or with lactic acid and ferric nitrate ratio according to the mol ratio 2～4: 1 of lactic acid and iron ion, be mixed in the deionized water, the pH value of regulator solution is between 2～7, stirs and obtains transparent colloidal sol after 18～24 hours;
2, vitreosol is dewatered in 60～80 ℃ of vacuum constant temperatures, obtain the clear gel that viscosity is 10～100Pa.s;
3, gel at room temperature leaves standstill and wears out more than 12 hours, and in 60～70 ℃ of dryings, spinning promptly obtains the fiber presoma then.
4, descend drying after 18～20 hours, at 40～50 ℃ the fiber presoma at N
2/ H
2Volume ratio is in 600～900 ℃ of reduction 1～3 hour, H in 4: 1～10: 1 the mist
2Flow velocity be 40～80mL/min, promptly obtain metallic fiber.
It is good that above-mentioned preparation process should adopt following technological parameter or method:
In step 1 with citric acid and basic nickel carbonate or cobalt nitrate ratio according to the mol ratio 0.9～1.2: 1 of citric acid and metal ion, or with citric acid and ferric nitrate, basic nickel carbonate, cobalt nitrate, the mixture of at least two kinds of slaines in copper nitrate and the zinc nitrate, it according to the mol ratio of citric acid and metal ion 0.66～1: 1 ratio, or 3～3.5: 1 ratio with lactic acid and ferric nitrate according to the mol ratio of lactic acid and iron ion, be mixed in the deionized water, the pH value of regulator solution is between 2.5～5, reduction temperature in the step 4 is got 650～850 ℃, reduces 1.5～2.5 hours.
The mixing of slaine mixes according to mol ratios such as metal ions, when for example three kinds of slaines of ferric nitrate, basic nickel carbonate, cobalt nitrate mix, and Fe
3+: Ni
2+: Co
2+=1: 1: 1.
Carry out the adjusting of solution pH value in the step 1 with ammoniacal liquor.
The optimum condition of preparation iron, cobalt or nickel fiber is: citric acid is that 1: 1 mol ratio is mixed with basic nickel carbonate or cobalt nitrate according to citric acid and metal ion in step 1, the pH value of regulator solution is 2.5, reduction temperature in the step 4 is got 650 ℃, reduces 1.5 hours; Lactic acid is that 3.025: 1 mol ratios are mixed with ferric nitrate according to lactic acid and iron ion, and the pH value of regulator solution is 5.0, and reduction temperature is 750 ℃, reductase 12 .5 hour.
The optimum condition of preparation iron nickel, iron cobalt or nickel cobalt (alloy) fiber: the mixture of citric acid and two kinds of slaines in step 1, it is the mixture of basic nickel carbonate or cobalt nitrate and ferric nitrate, according to citric acid and metal ion is that 5: 6 mol ratios are mixed, the pH value of regulator solution is 2.5, reduction temperature in the step 4 is got 700 ℃, reductase 12 hour; Citric acid is that 1: 1 mol ratio is mixed with the mixture of basic nickel carbonate and two kinds of slaines of cobalt nitrate according to citric acid and metal ion, and the pH value of regulator solution is 3.0, and reduction temperature is 700 ℃, reduces 1.5 hours.
Preparation iron nickel cobalt, the iron ambrose alloy, the optimum condition of iron nickel zinc alloy fiber: the mixture of citric acid and three kinds of slaines in step 1, it is basic nickel carbonate, ferric nitrate and cobalt nitrate, the mixture of copper nitrate or zinc nitrate, according to citric acid and metal ion is that 7: 9 mol ratios are mixed, pH value is 3.0～5.0, reduction temperature in the preparation teleoseal fiber step 4 is got 750 ℃, reductase 12 hour, reduction temperature in the preparation iron monel fiber step 4 is 850 ℃, reductase 12 hour, reduction temperature in the preparation iron nickel zinc alloy fiber step 4 is 800 ℃, reductase 12 hour.
This patent adopts preparing superfine metal fibers through method of organogel-thermal reduction process, and raw material sources are extensive, and process equipment is simple, is easy to large-scale production.The composition of target product metallic fiber is adjustable, can be at least two kinds among a kind of or Fe, Co, Ni, Cu and the Zn among Fe, Co, the Ni.By composition, the pH value size of control raw material, technological factors such as heat treatment temperature, time, atmosphere can obtain continuously the evenly micro metal fiber of heterogeneity and ratio.The diameter of metallic fiber is 0.1～15 μ m, and length can reach 0.05～2m, and draw ratio is 50～1 * 10
6The diameter of fiber, length and draw ratio are all adjustable, satisfy the requirement of metallic fiber design of absorbing material easily, and this fiber has tangible shape anisotropy, be fit to the design of absorbing material layer structure, be expected to prepare at thin thickness, light weight, bandwidth, the strong absorbing material of absorption.
Description of drawings
Fig. 1 is the process chart of preparing superfine metal fibers through method of organogel-thermal reduction process;
Fig. 2 is embodiment 1 nickel fiber stereoscan photograph and an XRD spectra thereof;
Fig. 3 is embodiment 2 single fine nickel fiber stereoscan photographs;
Fig. 4 is embodiment 3 iron fiber stereoscan photograph and XRD spectras thereof;
Fig. 5 is embodiment 4 iron-nickel alloy fiber stereoscan photograph and XRD spectras thereof;
Fig. 6 is embodiment 5 ferrocobalt fiber stereoscan photograph and XRD spectras thereof;
Fig. 7 is embodiment 6 nickel cobalt (alloy) fiber stereoscan photograph and XRD spectras thereof;
Fig. 8 is embodiment 7 iron monel fiber stereoscan photograph and XRD spectras thereof;
Fig. 9 is embodiment 8 iron nickel zinc alloy fiber stereoscan photograph and XRD spectras thereof;
Figure 10 is embodiment 9 teleoseal fiber stereoscan photograph and XRD spectras thereof;
Can find out: the fibre diameter that organogel-thermal reduction prepares that adopts this patent to provide is more even, Diameter is between 0.1～15 μ m, and the surface is more smooth, does not substantially have adhesion between the fiber and draw ratio is adjustable, fiber Composition be adjustable and very pure. Nickel fiber with organogel-thermal reduction preparation is straight as seen from Figure 3 The footpath is very even, can reach below the submicron order, and draw ratio is bigger.
Specific embodiment
Embodiment one: prepare fine nickel metallic fiber
With 84.48 gram citric acids and 26.67 gram basic nickel carbonates, be mixed in the deionized water of 200mL citric acid and Ni
2+Mol ratio is 2: 1, with the pH value of ammoniacal liquor regulator solution about 2.4, stir and obtain the citric acid nickel solution after 18 hours, this solution is placed rotary evaporator (60r/min),, obtain the vitreosol that viscosity is 100Pas 80 ℃ of following vacuum evaporation dehydrations, at room temperature left standstill 24 hours, then, in baking oven in 70 ℃ down dry, but obtain spinning behind the clear gel of spinning.The fiber presoma placed tube furnace, at N after under 40 ℃ dry 18 hours
2/ H
2Volume ratio is in 600 ℃ of reduction 1 hour, H in 10: 1 the mist
2Flow velocity be 40mL/min, obtaining diameter is 0.1～10 μ m, length can reach 0.5～2m, draw ratio is 1 * 10
3～1 * 10
6The metallic nickel fiber.Prepared fiber pattern and composition thereof are as shown in Figure 2.
Embodiment two: prepare fine nickel metallic fiber
With 42.24 gram citric acids and 26.67 gram basic nickel carbonates, be mixed in the deionized water of 200mL citric acid and Ni
2+Mol ratio is 1: 1, with the pH value of ammoniacal liquor regulator solution about 2.0, stir and obtain the citric acid nickel solution after 18 hours, this solution is placed rotary evaporator (60r/min),, obtain the vitreosol that viscosity is 80Pas 80 ℃ of following vacuum evaporation dehydrations, at room temperature left standstill 24 hours, then, in baking oven in 70 ℃ down dry, but obtain spinning behind the clear gel of spinning.The fiber presoma placed tube furnace, at N after under 40 ℃ dry 18 hours
2/ H
2Volume ratio is in 650 ℃ of reduction 1 hour, H in 8: 1 the mist
2Flow velocity be 50mL/min, obtain the metallic nickel fiber.The pattern of prepared single microfibre as shown in Figure 3.
Embodiment three: prepare fine ferrous metal fiber
The lactic acid and the 20.50 gram ferric nitrates of 15.47 grams are mixed in the deionized water of 100mL lactic acid and Fe
3+Mol ratio is 3.025: 1, with the pH value of ammoniacal liquor regulator solution about 7.0, stir and obtain ferric lactate solution after 24 hours, this solution is placed rotary evaporator (70r/min),, obtain the vitreosol that viscosity is 10Pas 60 ℃ of following vacuum evaporation dehydrations, at room temperature left standstill 30 hours, be placed on the baking oven inner drying, the control temperature is at 60 ℃, but obtains spinning behind the clear gel of spinning.The fiber presoma descended dry 20 hours at 40 ℃, placed tube furnace, at N
2/ H
2Volume ratio is reduction 1 hour in about 750 ℃ in 8: 1 the mist, H
2Flow velocity be 60mL/min, having obtained diameter is 0.5～2 μ m, length can reach 0.05～1m, draw ratio is 50～1 * 10
4The metallic iron fiber.Prepared fiber pattern and composition thereof are as shown in Figure 4.
Embodiment four: the preparation mol ratio is 1: 1 iron-nickel alloy microfibre
31.68 gram citric acids, 6.67 gram basic nickel carbonates and 20.50 gram ferric nitrates are mixed in the deionized water of 200mL citric acid and Ni
2+/ Fe
3+Mol ratio is 1.5: 1, Ni
2+: Fe
3+Mol ratio=1: 1, with the pH value of ammoniacal liquor regulator solution about 2.5, stir and obtain the ironic citrate nickel solution after 24 hours, this solution is placed rotary evaporator (65r/min), 60 ℃ of following vacuum evaporation dehydrations, obtain the vitreosol that viscosity is 30Pas, at room temperature left standstill 30 hours, then, at the baking oven inner drying, the control temperature is at 60 ℃, but obtains spinning behind the clear gel of spinning.The fiber presoma descended dry 20 hours at 45 ℃, placed tube furnace, at N
2/ H
2Volume ratio be in 5: 1 the mist in 700 ℃ of left and right sides reductase 12 .5 hours, H
2Flow velocity be 60mL/min, having obtained diameter is 0.3～5 μ m, length can reach 0.05～1.5m, draw ratio is 1 * 10
3～1 * 10
6The iron-nickel alloy fiber.Prepared fiber pattern and composition thereof are as shown in Figure 5.
Embodiment five: the preparation mol ratio is 1: 1 ferrocobalt microfibre
21.20 gram citric acids, 14.70 gram cobalt nitrates and 20.50 gram ferric nitrates are mixed in the deionized water of 200mL citric acid and Co
2+/ Fe
3+Mol ratio is 1: 1, Co
2+: Fe
3+Mol ratio=1: 1, with the pH value of ammoniacal liquor regulator solution about 2.0, stir and obtain the ironic citrate cobalt liquor after 24 hours, this solution is placed rotary evaporator (65r/min), 60 ℃ of following vacuum evaporation dehydrations, obtain the vitreosol that viscosity is 20Pas, at room temperature left standstill 30 hours, then, at the baking oven inner drying, the control temperature is at 60 ℃, but obtains spinning behind the clear gel of spinning.The fiber presoma descended dry 20 hours at 45 ℃, placed tube furnace, at N
2/ H
2Volume ratio is reduction 1.5 hours in about 700 ℃ in 4: 1 the mist, H
2Flow velocity be 80mL/min, having obtained diameter is 0.3～5 μ m, length can reach 0.05～1m, draw ratio is 1 * 10
2～1 * 10
6The ferrocobalt fiber.Prepared fiber pattern and composition thereof are as shown in Figure 6.
Experimental example six: the preparation mol ratio is 1: 1 nickel cobalt (alloy) microfibre
16.90 gram citric acids, 17.64 gram cobalt nitrates and 8.00 gram basic nickel carbonates are mixed in the deionized water of 200mL citric acid and Co
2+/ Ni
2+Mol ratio is 0.667: 1, Co
2+: Ni
2+Mol ratio=1: 1, with the pH value of ammoniacal liquor regulator solution about 3.0, stir and obtain the citric acid nickel and cobalt solution after 24 hours, this solution is placed rotary evaporator (65r/min), 60 ℃ of following vacuum evaporation dehydrations, obtaining viscosity is the 80Pas vitreosol, at room temperature left standstill 25 hours, then, at the baking oven inner drying, the control temperature is at 70 ℃, but obtains spinning behind the clear gel of spinning.The fiber presoma descended dry 20 hours at 45 ℃, placed tube furnace, at N
2/ H
2Volume ratio is reduction 1 hour in about 700 ℃ in 6: 1 the mist, H
2Flow velocity be 60mL/min, having obtained diameter is 0.5～10 μ m, length can reach 0.05～2m, draw ratio is 50～1 * 10
5The nickel cobalt (alloy) fiber.Prepared fiber pattern and composition thereof are as shown in Figure 7.
Embodiment seven: the preparation mol ratio is 1: 1: 1 iron monel microfibre
21.11 gram citric acids, 4.00 gram basic nickel carbonates, 12.30 gram ferric nitrates and 7.28 gram copper nitrates are mixed in the deionized water of 200mL citric acid and Ni
2+/ Fe
3+/ Cu
2+Mol ratio is 1.1: 1, Ni
2+: Fe
3+: Cu
2+Mol ratio=1: 1: 1, with the pH value of ammoniacal liquor regulator solution about 5.0, stir and obtain ironic citrate ambrose alloy solution after 20 hours, this solution is placed rotary evaporator (65r/min), 70 ℃ of following vacuum evaporation dehydrations, obtain the vitreosol that viscosity is 60Pas, at room temperature left standstill 40 hours, then, at the baking oven inner drying, the control temperature range between 60～70 ℃, but obtain spinning behind the clear gel of spinning.The fiber presoma descended dry 20 hours at 50 ℃, placed tube furnace, at N
2/ H
2Volume ratio is reduction 3 hours in about 900 ℃ in 8: 1 the mist, H
2Flow velocity be 70mL/min, having obtained diameter is 0.2～10 μ m, length can reach 0.05～1.5m, draw ratio is 50～1 * 10
4Iron monel fiber.Prepared fiber pattern and composition thereof are as shown in Figure 8.
Embodiment eight: the preparation mol ratio is 1: 1: 1 iron nickel zinc alloy microfibre
14.78 gram citric acids, 4.00 gram basic nickel carbonates, 12.30 gram ferric nitrates and 9.01 gram zinc nitrates are mixed in the deionized water of 200mL citric acid and Ni
2+/ Fe
3+/ Zn
2+Mol ratio is 0.778: 1, Ni
2+: Fe
3+: Zn
2+Mol ratio be 1: 1: 1, with the pH value of ammoniacal liquor regulator solution about 4.0, stir and obtain ironic citrate nickel zinc solution after 24 hours, this solution is placed rotary evaporator (60r/min), 70 ℃ of following vacuum evaporation dehydrations, obtain the vitreosol that viscosity is 60Pas, at room temperature left standstill 35 hours, then, at the baking oven inner drying, the control temperature is 65 ℃, but obtains spinning behind the clear gel of spinning.The fiber presoma descended dry 20 hours at 50 ℃, placed tube furnace, at N
2/ H
2Volume ratio be in 5: 1 the mist in 800 ℃ of left and right sides reductase 12s hour, H
2Flow velocity be 80mL/min, having obtained diameter is 0.5～5 μ m, length can reach 0.05～1m, draw ratio is 50～1 * 10
4Iron nickel zinc alloy fiber.Prepared fiber pattern and composition thereof are as shown in Figure 9.
Embodiment nine: the preparation mol ratio is 1: 1: 1 teleoseal microfibre
27.40 gram citric acids, 4.00 gram basic nickel carbonates, 12.30 gram ferric nitrates and 8.82 gram cobalt nitrates are mixed in the deionized water of 200mL citric acid and Ni
2+/ Fe
3+/ Co
2+Mol ratio is 1.4: 1, Ni
2+: Fe
3+: Co
2+Mol ratio be 1: 1: 1, with the pH value of ammoniacal liquor regulator solution about 3.0, stir and obtain the ironic citrate nickel and cobalt solution after 24 hours, this solution is placed rotary evaporator (60r/min), 70 ℃ of following vacuum evaporation dehydrations, obtain the colloidal sol that viscosity is 60Pas, at room temperature left standstill 30 hours, then, at the baking oven inner drying, the control temperature is 65 ℃, but obtains spinning behind the clear gel of spinning.The fiber presoma descended dry 20 hours at 50 ℃, placed tube furnace, at N
2/ H
2Volume ratio is reduction 1.5 hours in about 750 ℃ in 4: 1 the mist, H
2Flow velocity be 80mL/min, having obtained diameter is 1～15 μ m, length can reach 0.05～1.5m, draw ratio is 50～1 * 10
3The teleoseal fiber.Prepared fiber pattern and composition thereof are as shown in figure 10.
Claims (7)
1. preparing superfine metal fibers through method of organogel-thermal reduction process method, with at least a slaine in citric acid or lactic acid and basic nickel carbonate, ferric nitrate, cobalt nitrate, copper nitrate, the zinc nitrate is initiation material, adopt preparing superfine metal fibers through method of organogel-thermal reduction process, it is characterized in that:
(1) with citric acid and basic nickel carbonate or cobalt nitrate ratio according to the mol ratio 0.8～2: 1 of citric acid and metal ion, or with the mixture of at least two kinds of slaines in citric acid and ferric nitrate, basic nickel carbonate, cobalt nitrate, copper nitrate and the zinc nitrate, it according to the mol ratio of citric acid and metal ion 0.66～1.5: 1 ratio, or with lactic acid and ferric nitrate ratio according to the mol ratio 2～4: 1 of lactic acid and iron ion, be mixed in the deionized water, the pH value of regulator solution is between 2～7, stirs and obtains transparent colloidal sol after 18～24 hours;
(2) vitreosol is dewatered in 60～80 ℃ of vacuum constant temperatures, obtain the clear gel that viscosity is 10～100Pas;
(3) gel at room temperature leaves standstill and wears out more than 12 hours, and in 60～70 ℃ of dryings, spinning promptly obtains the fiber presoma then;
(4) descend drying after 18～20 hours, at 40～50 ℃ the fiber presoma at N
2/ H
2Volume ratio is in 600～900 ℃ of reduction 1～3 hour, H in 4: 1～10: 1 the mist
2Flow velocity be 40～80mL/min, promptly obtain metallic fiber.
2. a kind of preparing superfine metal fibers through method of organogel-thermal reduction process method according to claim 1, it is characterized in that: in step 1 with citric acid and basic nickel carbonate or cobalt nitrate ratio according to the mol ratio 0.9～1.2: 1 of citric acid and metal ion, or with citric acid and ferric nitrate, basic nickel carbonate, cobalt nitrate, the mixture of at least two kinds of slaines in copper nitrate and the zinc nitrate, it according to the mol ratio of citric acid and metal ion 0.66～1: 1 ratio, or 3～3.5: 1 ratio with lactic acid and ferric nitrate according to the mol ratio of lactic acid and iron ion, be mixed in the deionized water, the pH value of regulator solution is between 2.5～5, reduction temperature in the step 4 is got 650～850 ℃, reduces 1.5～2.5 hours.
3. a kind of preparing superfine metal fibers through method of organogel-thermal reduction process method according to claim 1, it is characterized in that: the mixing of slaine mixes according to mol ratios such as metal ions.
4. a kind of preparing superfine metal fibers through method of organogel-thermal reduction process method according to claim 1 is characterized in that: carry out the adjusting of solution pH value in the step 1 with ammoniacal liquor.
5. a kind of preparing superfine metal fibers through method of organogel-thermal reduction process method according to claim 1, it is characterized in that: the condition of preparation iron, cobalt or nickel fiber is: citric acid is that 1: 1 mol ratio is mixed with basic nickel carbonate or cobalt nitrate according to citric acid and metal ion in step 1, the pH value of regulator solution is 2.5, reduction temperature in the step 4 is got 650 ℃, reduces 1.5 hours; Lactic acid is that 3.025: 1 mol ratios are mixed with ferric nitrate according to lactic acid and iron ion in the step 1, and the pH value of regulator solution is 5.0, and reduction temperature is 750 ℃ in the step 4, reductase 12 .5 hour.
6. a kind of preparing superfine metal fibers through method of organogel-thermal reduction process method according to claim 1, it is characterized in that: the condition of preparation iron nickel, iron cobalt or nickel cobalt (alloy) fiber is: the mixture of citric acid and two kinds of slaines in step 1, it is the mixture of basic nickel carbonate or cobalt nitrate and ferric nitrate, mix according to 5: 6 mol ratio of citric acid and metal ion, the pH value of regulator solution is 2.5, reduction temperature in the step 4 is got 700 ℃, reductase 12 hour; Citric acid is that 1: 1 mol ratio is mixed with the mixture of basic nickel carbonate and two kinds of slaines of cobalt nitrate according to citric acid and metal ion in the step 1, and the pH value of regulator solution is 3.0, and the reduction temperature in the step 4 is got 700 ℃, reduces 1.5 hours.
7. a kind of preparing superfine metal fibers through method of organogel-thermal reduction process method according to claim 1, it is characterized in that: the condition of preparation iron nickel cobalt, iron ambrose alloy, iron nickel zinc alloy fiber is: the mixture of citric acid and three kinds of slaines in step 1, it is the mixture of basic nickel carbonate, ferric nitrate and cobalt nitrate, copper nitrate or zinc nitrate, according to citric acid and metal ion is that 7: 9 mol ratios are mixed, pH value is 3.0～5.0; Reduction temperature in the preparation teleoseal fiber step 4 is got 750 ℃, reductase 12 hour, the reduction temperature in the preparation iron monel fiber step 4 is got 850 ℃, reductase 12 hour, reduction temperature in the preparation iron nickel zinc alloy fiber step 4 is got 800 ℃, reductase 12 hour.
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| EP0299618A2 (en) * | 1987-06-12 | 1989-01-18 | Minnesota Mining And Manufacturing Company | Preparation process for ferromagnetic metal fibers |
| WO2001062434A1 (en) * | 2000-02-22 | 2001-08-30 | Park Yang Za | Apparatus and method for producing metal fiber |
| CN1346722A (en) * | 2000-10-19 | 2002-05-01 | 未来金属株式会社 | Method for producing metal fibre |
| CN1529777A (en) * | 2001-07-18 | 2004-09-15 | ������������ʽ���� | Metallic fiber nonwoven fabric manufacturing apparatus, its manufacturing method and laminated aluminium material manufacturing method |
| CN1569368A (en) * | 2004-05-10 | 2005-01-26 | 西安交通大学 | Method for preparing nm-class composite rare earth molybdenum material by sol-gal process |
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