CN1781864A - Magnetic glass fiber and its preparing method - Google Patents
Magnetic glass fiber and its preparing method Download PDFInfo
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- CN1781864A CN1781864A CN 200410096177 CN200410096177A CN1781864A CN 1781864 A CN1781864 A CN 1781864A CN 200410096177 CN200410096177 CN 200410096177 CN 200410096177 A CN200410096177 A CN 200410096177A CN 1781864 A CN1781864 A CN 1781864A
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- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
- C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
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Abstract
The magnetic glass fiber contains nanometer level magnetic ferrite powder distributed homogeneously in 2-13 wt%, and the nanometer level magnetic ferrite powder is coated in SiO2. The magnetic glass fiber is prepared through mixing nanometer level magnetic ferrite powder in 2-13 wt% and glass fiber material with SiO2 amount equal to that in conventional glass fiber material subtracting that in the magnetic ferrite powder, smelting the mixture at 1300-1400 deg.c, and drawing to obtain magnetic glass fiber. The magnetic glass fiber has obvious magnetic performance, and may be used widely in electromagnetic shielding, stealth material, structure strengthening material, etc.
Description
Invention field
The present invention relates to a kind of glass fibre and preparation method thereof, particularly a kind of magnetic glass fiber and preparation method thereof.
Background technology
Along with science and technology development, to demands for higher performance such as the mechanics of glass fibre, heat-resisting and conductions, since the sixties in 20th century many special glass fibres have appearred, as refractory glass fibre, high strength glass fiber, electroconductive glass fibre and high-modulus glass fiber etc.Special glass fibre has become the important component part of fiber glass industry.Special glass fibre is different from the alkali-free and the anacidity glass fibre of widespread production and use on the general industry, and it has special performances.And property has then determined their special purpose.Have good heat-resistance and ablation resistance as resurrection glass fibre, therefore can be used as the ablation resistant material of defence and military product.Existing and the general glass fibre production method of special glass fibre is identical, and its special producing method is arranged again.Special glass fibre is owing to have some special performances and function is subjected to people's favor very much, but is partial to improve the physics and the chemical properties such as intensity, modulus, electrical insulating property, acid and alkali-resistance, high temperature of glass.The development of new special glass fibre, except that will satisfying the fundamental characteristics energy that general glass fibre has, also require to have special performance-have certain functional, such as glass fibre etc. with conductivity.This electroconductive glass fibre has caused that people's attention is because can be used as antistatic material, electro-conductive material after this glass fibre and the resin compounded.At present the special magnetic glass fibre with specific magnetic function be yet there are no report both at home and abroad.
Summary of the invention
The objective of the invention is to: a kind of magnetic glass fiber is provided, and this magnetic glass fiber contains a certain amount of magnetic, can have electromagnetic shielding after itself and the resin compounded and absorb the hertzian wave function to have strong mechanical performance again; Can be used as electromagnetic shielding, stealth material and structural reinforcement material or the like; Be applicable to aspects such as civilian, military affairs, have bigger society and economic benefit.
Another object of the present invention is to: a kind of preparation method of magnetic glass fiber is provided, and this method technology is simple, easy to operate; The magnetic glass fiber of made can be used as electromagnetic shielding, stealth material and structural reinforcement material or the like; Be applicable to aspects such as civilian, military affairs, have bigger society and economic benefit.
Technical scheme of the present invention is as follows:
Magnetic glass fiber provided by the invention is characterized in that, this magnetic glass fiber contains the nano level CoFe of 2-13% weight uniformly
2O
4Ferrite, BaFe
12O
19Ferrite or NiFe
2O
4Ferromagnetic oxide powder;
Described nano level CoFe
2O
4Ferrite, BaFe
12O
19Ferrite or NiFe
2O
4Ferromagnetic oxide powder is coated with SiO
2, it is prepared as follows:
1) salt that will contain Co and contain Fe is that 1: 2 ratio is weighed formation mixture A in the mol ratio of Co and Fe; The salt that perhaps will contain Ba and contain Fe is that 1: 12 ratio is weighed in the mol ratio of Ba and Fe, constitutes mixture B, and the salt that perhaps will contain Ni and contain Fe is that 1: 2 ratio is weighed formation mixture C in the mol ratio of Ni and Fe;
2) said mixture material A, mixture B or mixture C are dissolved in the nitric acid acidifying deionized water, and add the mixed organic solvents of forming by methyl alcohol, methane amide and tetraethoxy, after 20-60 ℃ of gel 2-12 hour, under 20-60 ℃ of temperature ageing 24-48 hour; Gained xerogel under 40-120 ℃ vacuum dry 2-4 days then is warming up to 200-300 ℃ and be incubated 20-60 minute under this condition; Grind after taking out cooling, place again in the retort furnace, under air atmosphere, be heated to 950-1050 ℃ of calcining 2-6 hour, promptly make and be coated with SiO with the temperature rise rate of 1-5 ℃/min
2Nano level CoFe
2O
4Ferrite, BaFe
12O
19Ferrite or NiFe
2O
4Ferromagnetic oxide powder;
The weight part proportioning of methyl alcohol, methane amide and tetraethoxy is 1-9: 1-5: 5-15 in the described mixed organic solvents;
The concentration of nitric acid is 0.001-0.05mol/L in the described nitric acid acidifying deionized water;
The salt of the described Co of containing is Xiao Suangu, cobalt chloride, rose vitriol or Cobaltous diacetate; The salt of the described Ba of containing is nitrate of baryta, bariumchloride or hydrated barta; The salt of the described Ni of containing is nickelous nitrate, nickelous chloride, single nickel salt or nickel acetate; The salt of the described Fe of containing is iron nitrate, iron(ic) chloride or ferric sulfate;
Being prepared as follows of described magnetic glass fiber:
With strength blended way with the above-mentioned SiO that is coated with
2Nano level CoFe
2O
4Ferrite, BaFe
12O
19Ferrite or NiFe
2O
4Ferrite super-fine magnetic powder and glass fibre raw material mix, and the weight percent content of wherein said ferrite super-fine magnetic powder is 2-13%, SiO in the described glass fibre raw material
2Consumption equal SiO in the conventional glass fibre raw material
2The consumption SiO that deducts in the ferromagnetic oxide powder to be coated
2Amount; And mixture melted at 1300-1400 ℃, and make magnetic glass fiber through wire drawing.
The granularity of the nanometer ferrite magnetic that described magnetic glass fiber is contained is 5-100nm.The diameter of described magnetic glass fiber is 1-30 μ m.
The preparation method of magnetic glass fiber provided by the invention, its step is as follows:
1, preparation is coated with SiO
2Nano-level iron oxysome super-fine magnetic powder:
(1) salt that will contain Co and contain Fe is that 1: 2 ratio is weighed formation mixture A in the mol ratio of Co and Fe; The salt that perhaps will contain Ba and contain Fe is that 1: 12 ratio is weighed in the mol ratio of Ba and Fe, constitutes mixture B, and the salt that perhaps will contain Ni and contain Fe is that 1: 2 ratio is weighed formation mixture C in the mol ratio of Ni and Fe;
(2) said mixture material A, mixture B or mixture C are dissolved in the nitric acid acidifying deionized water, and add the mixed organic solvents of forming by methyl alcohol, methane amide and tetraethoxy, after 20-60 ℃ of gel 2-12 hour, under 20-60 ℃ of temperature ageing 24-48 hour; Gained xerogel under 40-120 ℃ vacuum dry 2-4 days then is warming up to 200-300 ℃ and be incubated 20-60 minute under this condition; Grind after taking out cooling, place again in the retort furnace, under air atmosphere, be heated to 950-1050 ℃ of calcining 2-6 hour, promptly make and be coated with SiO with the temperature rise rate of 1-5 ℃/min
2Nano level CoFe
2O
4Ferrite, BaFe
12O
19Ferrite or NiFe
2O
4Ferromagnetic oxide powder;
The weight part proportioning of methyl alcohol, methane amide and tetraethoxy is 1-9: 1-5: 5-15 in the described mixed organic solvents;
The concentration of nitric acid is 0.001-0.05mol/L in the described nitric acid acidifying deionized water;
The salt of the described Co of containing is Xiao Suangu, cobalt chloride, rose vitriol or Cobaltous diacetate; The salt of the described Ba of containing is nitrate of baryta, bariumchloride or hydrated barta; The salt of the described Ni of containing is nickelous nitrate, nickelous chloride, single nickel salt or nickel acetate; The salt of the described Fe of containing is iron nitrate, iron(ic) chloride or ferric sulfate;
2, preparation magnetic glass fiber:
With strength blended way with the above-mentioned SiO that coated
2Nano level CoFe
2O
4Ferrite, BaFe
12O
19Ferrite or NiFe
2O
4Ferromagnetic oxide powder and glass fibre raw material mix, and the weight percent content of wherein said ferromagnetic oxide powder is 213%, SiO in the described glass fibre raw material
2Consumption equal SiO in the conventional glass fibre raw material
2The consumption SiO that deducts in the ferromagnetic oxide powder to be coated
2Amount; And mixture melted at 1300-1400 ℃, and prepare magnetic glass fiber through wire drawing.
The granularity of the nanometer ferrite magnetic that described magnetic glass fiber is contained is 5-100nm.The diameter of magnetic glass fiber is 1-30 μ m.
The magnetic glass fiber of the present invention preparation contains a certain amount of magnetic, its with resin compounded after can have electromagnetic shielding and absorption hertzian wave function has strong mechanical performance again; Can be used as electromagnetic shielding, stealth material and structural reinforcement material or the like; Be applicable to aspects such as civilian, military affairs, have bigger society and economic benefit.Its method technology is simple, easy to operate.
Description of drawings
Fig. 1-1 is respectively the SiO that is coated with that contains different content to Fig. 1-6
2The bundle photo of magnetic glass fiber of nano-level iron oxysome super-fine magnetic powder;
Fig. 2 under the room temperature for the coating that contains different content SiO
2The magnetic property synoptic diagram of magnetic glass fiber of nano-level iron oxysome super-fine magnetic powder.
Embodiment
Embodiment 1, the preparation magnetic glass fiber that evenly contains 2wt% nano barium ferrite magnetic of the present invention:
1, employed magnetic is to have coated SiO
2The nano barium ferrite magnetic, it is prepared as follows;
1) is that 1: 12 ratio is weighed with nitrate of baryta (also can with bariumchloride or hydrated barta) and iron nitrate (also can with iron(ic) chloride or ferric sulfate) in the mol ratio of Ba and Fe, constitutes mixture B1;
2) said mixture material B1 is dissolved in the nitric acid acidifying deionized water, and adds the mixed organic solvents of being made up of methyl alcohol, methane amide and tetraethoxy, after 2 hours, ageing is 48 hours under 20 ℃ of temperature at 60 ℃ of gels; Gained xerogel under 40 ℃ vacuum dry 4 days, then under this condition, be warming up to 300 ℃ of insulations 60 minutes, taking out the cooling back grinds, place in the retort furnace again, under air atmosphere, temperature rise rate with 5 ℃/min is heated to 1050 ℃, and calcines 6 hours, the SiO that promptly made coating that present embodiment uses
2Nano level BaFe
12O
19Ferritic super-fine magnetic powder;
The weight part proportioning of methyl alcohol, methane amide and tetraethoxy is 1: 5: 5 in the described mixed organic solvents; The concentration of nitric acid is 0.001mol/L in the described nitric acid acidifying deionized water.
2, preparation magnetic glass fiber:
With strength blended way with the above-mentioned SiO that coated
2Nano level BaFe
12O
19Ferritic super-fine magnetic powder and glass fibre raw material uniform mixing, the weight percent content of wherein said ferromagnetic oxide powder is 2%, SiO in the described glass fibre raw material
2Consumption equal SiO in the conventional glass fibre raw material
2The consumption SiO that deducts in the ferromagnetic oxide powder to be coated
2Amount; And mixture melted at 1300 ℃, and prepare magnetic glass fiber through wire drawing.
The diameter 1-5 μ m of the magnetic glass fiber of present embodiment preparation, its water content≤0.20%, the linear density deviation is ± 7%; The granularity of wherein contained ferrite super-fine magnetic powder is 5-100nm.
Metallic compound that is added and the final weight that generates soft silica calculate the content of magnetic and silicon-dioxide, suppose that ferritic content is a% that is:, and required SiO prepares burden
2The magnetic of parcel is Ag, and then magnetic substance-ferritic weight is that (g of A * a%), the weight of silicon-dioxide is the (g of A-A * a%).The glass master composition (mass ratio) of the magnetic glass fiber of present embodiment is constant, i.e. SiO
2Be 54.1%, Al
2O
3Be 14.2%, B
2O
3Be 7.6%, CaO is 22.8%.Accurately take by weighing SiO on request
2(purity 〉=99.5%), Al
2O
3(purity 〉=99.5%), B
2O
3(purity 〉=99.5%), CaO (purity 〉=99.5%), a spot of soda ash and coated SiO
2Nano barium ferrite, place mortar to grind after 30 minutes, pour the old soldi of a good seal into, 30 minutes grey powder of continuous shaking mixing is poured clay crucible into, feeding temperature is 1380 ℃, and wire drawing behind 1400 ℃ of fusion 2h obtains magnetic glass fiber (shown in Fig. 1-2).A among magnetic property such as Fig. 2.
Embodiment 2, the preparation magnetic glass fiber that evenly contains 3.5wt% nanometer Ni ferrite magnetic of the present invention:
1, employed magnetic is to have coated SiO
2Nanometer Ni ferrite magnetic, it is prepared as follows;
1) nickelous nitrate (also can with nickelous chloride, single nickel salt or nickel acetate) and iron nitrate (can be that 1: 2 ratio is weighed in the mol ratio of Ni and Fe with iron(ic) chloride or ferric sulfate also, constitute mixture B2;
2) said mixture material B2 is dissolved in the nitric acid acidifying deionized water, and adds the mixed organic solvents of being made up of methyl alcohol, methane amide and tetraethoxy, after 12 hours, ageing is 24 hours under 60 ℃ of temperature at 20 ℃ of gels; Gained xerogel under 120 ℃ vacuum dry 2 days, then under this condition, be warming up to 200 ℃ of insulations 20 minutes, taking out the cooling back grinds, place in the retort furnace again, under air atmosphere, temperature rise rate with 5 ℃/min is heated to 950 ℃, and calcines 6 hours, the SiO that promptly made coating that present embodiment uses
2Nano level NiFe
2O
4Ferritic super-fine magnetic powder;
The weight part proportioning of methyl alcohol, methane amide and tetraethoxy is 9: 1: 15 in the described mixed organic solvents; The concentration of nitric acid is 0.05mol/L in the described nitric acid acidifying deionized water.
2, preparation magnetic glass fiber:
With strength blended way with the above-mentioned SiO that coated
2Nano level NiFe
2O
4Ferritic super-fine magnetic powder and glass fibre raw material uniform mixing, the weight percent content of wherein said ferrite super-fine magnetic powder is 3.5%, SiO in the described glass fibre raw material
2Consumption equal SiO in the conventional glass fibre raw material
2The consumption SiO that deducts in the ferromagnetic oxide powder to be coated
2Amount; And mixture melted at 1400 ℃, and prepare magnetic glass fiber through wire drawing.
The diameter 6-10 μ m of the magnetic glass fiber of present embodiment preparation, its water content≤0.20%, the linear density deviation is ± 7%; The granularity of wherein contained ferrite super-fine magnetic powder is 5-100nm.
Metallic compound that is added and the final weight that generates soft silica calculate the content of magnetic and silicon-dioxide, suppose that ferritic content is a% that is:, and required SiO prepares burden
2The magnetic of parcel is Ag, and then magnetic substance-ferritic weight is that (g of A * a%), the weight of silicon-dioxide is the (g of A-A * a%).The glass master composition (mass ratio) of the magnetic glass fiber of present embodiment is constant, i.e. SiO
2Be 54.1%, Al
2O
3Be 14.2%, B
2O
3Be 7.6%, CaO is 22.8%.Accurately take by weighing SiO on request
2(purity 〉=99.5%), Al
2O
3(purity 〉=99.5%), B
2O
3(purity 〉=99.5%), CaO (purity 〉=99.5%), a spot of soda ash and coated SiO
2The nanometer Ni ferrite, place mortar to grind after 30 minutes, pour the old soldi of a good seal into, 30 minutes grey powder of continuous shaking mixing is poured clay crucible into, feeding temperature is 1380 ℃, and wire drawing behind 1400 ℃ of fusion 2h obtains magnetic glass fiber (shown in Fig. 1-3).What table 1 showed is the composition data of the major ingredient of magnetic glass fiber, the b among magnetic property such as Fig. 2.
Embodiment 3, the preparation magnetic glass fiber that evenly contains 6wt% nanometer vectolite magnetic of the present invention:
1, employed magnetic is to have coated SiO
2The vectolite magnetic, it is prepared as follows;
1) is that 1: 2 ratio is weighed with Xiao Suangu (also can with cobalt chloride, rose vitriol or Cobaltous diacetate) and iron nitrate (also can with iron(ic) chloride or ferric sulfate) in the mol ratio of Co and Fe, constitutes mixture B3;
2) said mixture material B3 is dissolved in the nitric acid acidifying deionized water, and adds the mixed organic solvents of being made up of methyl alcohol, methane amide and tetraethoxy, after 8 hours, ageing is 30 hours under 40 ℃ of temperature at 40 ℃ of gels; Gained xerogel under 100 ℃ vacuum dry 3 days, then under this condition, be warming up to 250 ℃ of insulations 40 minutes, taking out the cooling back grinds, place in the retort furnace again, under air atmosphere, temperature rise rate with 3 ℃/min is heated to 1000 ℃, and calcines 4 hours, the SiO that promptly made coating that present embodiment uses
2Nano level CoFe
2O
4Ferritic super-fine magnetic powder;
The weight part proportioning of methyl alcohol, methane amide and tetraethoxy is 5: 3: 10 in the described mixed organic solvents; The concentration of nitric acid is 0.02mol/L in the described nitric acid acidifying deionized water.
2, preparation magnetic glass fiber:
With strength blended way with the above-mentioned SiO that coated
2Nano level CoFe
2O
4Ferritic super-fine magnetic powder and glass fibre raw material uniform mixing, the weight percent content of wherein said ferrite super-fine magnetic powder is 6%, SiO in the described glass fibre raw material
2Consumption equal SiO in the conventional glass fibre raw material
2The consumption SiO that deducts in the ferromagnetic oxide powder to be coated
2Amount; And mixture melted at 1350 ℃, and prepare magnetic glass fiber through wire drawing.
The diameter 10-15 μ m of the magnetic glass fiber of present embodiment preparation, its water content≤0.20%, the linear density deviation is ± 7%; The granularity of wherein contained ferrite super-fine magnetic powder is 5-100nm.
Metallic compound that is added and the final weight that generates soft silica calculate the content of magnetic and silicon-dioxide, suppose that ferritic content is a% that is:, and required SiO prepares burden
2The magnetic of parcel is Ag, and then magnetic substance-ferritic weight is that (g of A * a%), the weight of silicon-dioxide is the (g of A-A * a%).The glass master composition (mass ratio) of the magnetic glass fiber of present embodiment is constant, i.e. SiO
2Be 54.1%, Al
2O
3Be 14.2%, B
2O
3Be 7.6%, CaO is 22.8%.Accurately take by weighing SiO on request
2(purity 〉=99.5%), Al
2O
3(purity 〉=99.5%), B
2O
3(purity 〉=99.5%), CaO (purity 〉=99.5%), a spot of soda ash and coated SiO
2The nanometer vectolite, place mortar to grind after 30 minutes, pour the old soldi of a good seal into, 30 minutes grey powder of continuous shaking mixing is poured clay crucible into, feeding temperature is 1380 ℃, and wire drawing behind 1400 ℃ of fusion 2h obtains magnetic glass fiber (shown in Fig. 1-4).What table 1 showed is the composition data of the major ingredient of magnetic glass fiber, the c among magnetic property such as Fig. 2.
Embodiment 4, the preparation magnetic glass fiber that evenly contains 8wt% nanometer vectolite magnetic of the present invention:
1, employed magnetic is to have coated SiO
2Nanometer vectolite magnetic, it is prepared as follows;
1) is that 1: 2 ratio is weighed with cobalt chloride (also can with Xiao Suangu, rose vitriol or Cobaltous diacetate) and iron(ic) chloride (also can with iron nitrate or ferric sulfate) in the mol ratio of Co and Fe, constitutes mixture B4;
2) said mixture material B4 is dissolved in the nitric acid acidifying deionized water, and adds the mixed organic solvents of being made up of methyl alcohol, methane amide and tetraethoxy, after 10 hours, ageing is 40 hours under 30 ℃ of temperature at 30 ℃ of gels; Gained xerogel under 80 ℃ vacuum dry 4 days, then under this condition, be warming up to 200 ℃ of insulations 60 minutes, taking out the cooling back grinds, place in the retort furnace again, under air atmosphere, temperature rise rate with 2 ℃/min is heated to 980 ℃, and calcines 6 hours, the SiO that promptly made coating that present embodiment uses
2Nano level CoFe
2O
4Ferritic super-fine magnetic powder;
The weight part proportioning of methyl alcohol, methane amide and tetraethoxy is 3: 5: 9 in the described mixed organic solvents; The concentration of nitric acid is 0.01mol/L in the described nitric acid acidifying deionized water.
2, preparation magnetic glass fiber:
With strength blended way with the above-mentioned SiO that coated
2Nano level CoFe
2O
4Ferritic super-fine magnetic powder and glass fibre raw material uniform mixing, the weight percent content of wherein said ferrite super-fine magnetic powder is 8%, SiO in the described glass fibre raw material
2Consumption equal SiO in the conventional glass fibre raw material
2The consumption SiO that deducts in the ferromagnetic oxide powder to be coated
2Amount; And mixture melted at 1380 ℃, and prepare magnetic glass fiber through wire drawing.
The diameter 15-20 μ m of the magnetic glass fiber of present embodiment preparation, its water content≤0.20%, the linear density deviation is ± 7%; The granularity of wherein contained ferrite super-fine magnetic powder is 5-100nm.
Metallic compound that is added and the final weight that generates soft silica calculate the content of magnetic and silicon-dioxide, suppose that ferritic content is a% that is:, and required SiO prepares burden
2The magnetic of parcel is Ag, and then magnetic substance-ferritic weight is that (g of A * a%), the weight of silicon-dioxide is the (g of A-A * a%).The glass master composition (mass ratio) of the magnetic glass fiber of present embodiment is constant, i.e. SiO
2Be 54.1%, Al
2O
3Be 14.2%, B
2O
3Be 7.6%, CaO is 22.8%.Accurately take by weighing SiO on request
2(purity 〉=99.5%), Al
2O
3(purity 〉=99.5%), B
2O
3(purity 〉=99.5%), CaO (purity 〉=99.5%), a spot of soda ash and coated SiO
2The nanometer vectolite, place mortar to grind after 30 minutes, pour the old soldi of a good seal into, 30 minutes grey powder of continuous shaking mixing is poured clay crucible into, feeding temperature is 1380 ℃, and wire drawing behind 1400 ℃ of fusion 2h obtains magnetic glass fiber (shown in Fig. 1-5).What table 1 showed is the composition data of the major ingredient of magnetic glass fiber, the d among magnetic property such as Fig. 2.
Embodiment 5, the preparation magnetic glass fiber that evenly contains the magnetic of 13wt% nanometer vectolite of the present invention:
1, employed magnetic is to have coated SiO
2The nanometer vectolite, it is prepared as follows:
1) is that 1: 2 ratio is weighed with rose vitriol (also can with Xiao Suangu, cobalt chloride or Cobaltous diacetate) and ferric sulfate (also can with iron nitrate or iron(ic) chloride) in the mol ratio of Co and Fe, constitutes mixture B5;
2) said mixture material B5 is dissolved in the nitric acid acidifying deionized water, and adds the mixed organic solvents of being made up of methyl alcohol, methane amide and tetraethoxy, after 5 hours, ageing is 35 hours under 50 ℃ of temperature at 50 ℃ of gels; Gained xerogel under 100 ℃ vacuum dry 3 days, then under this condition, be warming up to 300 ℃ of insulations 50 minutes, taking out the cooling back grinds, place in the retort furnace again, under air atmosphere, temperature rise rate with 4 ℃/min is heated to 1000 ℃, and calcines 5 hours, the SiO that promptly made coating that present embodiment uses
2Nano level CoFe
2O
4Ferritic super-fine magnetic powder;
The weight part proportioning of methyl alcohol, methane amide and tetraethoxy is 7: 4: 8 in the described mixed organic solvents; The concentration of nitric acid is 0.05mol/L in the described nitric acid acidifying deionized water.
2, preparation magnetic glass fiber:
With strength blended way with the above-mentioned SiO that coated
2Nano level CoFe
2O
4Ferritic super-fine magnetic powder and glass fibre raw material uniform mixing, the weight percent content of wherein said ferrite super-fine magnetic powder is 13%, SiO in the described glass fibre raw material
2Consumption equal SiO in the conventional glass fibre raw material
2The consumption SiO that deducts in the ferromagnetic oxide powder to be coated
2Amount; And mixture melted at 1400 ℃, and prepare magnetic glass fiber through wire drawing.
The diameter 20-30 μ m of the magnetic glass fiber of present embodiment preparation, its water content≤0.20%, the linear density deviation is ± 7%; The granularity of wherein contained ferrite super-fine magnetic powder is 5-100nm.
Metallic compound that is added and the final weight that generates soft silica calculate the content of magnetic and silicon-dioxide, suppose that ferritic content is a% that is:, and required SiO prepares burden
2The magnetic of parcel is Ag, and then magnetic substance-ferritic weight is that (g of A * a%), the weight of silicon-dioxide is the (g of A-A * a%).The glass master composition (mass ratio) of the magnetic glass fiber of present embodiment is constant, i.e. SiO
2Be 54.1%, Al
2O
3Be 14.2%, B
2O
3Be 7.6%, CaO is 22.8%.Accurately take by weighing SiO on request
2(purity 〉=99.5%), Al
2O
3(purity 〉=99.5%), B
2O
3(purity 〉=99.5%), CaO (purity 〉=99.5%), a spot of soda ash and coated SiO
2The nanometer vectolite, place mortar to grind after 30 minutes, pour the old soldi of a good seal into, 30 minutes grey powder of continuous shaking mixing is poured clay crucible into, feeding temperature is 1380 ℃, and wire drawing behind 1400 ℃ of fusion 2h obtains magnetic glass fiber (shown in Fig. 1-6).What table 1 showed is the composition data of the major ingredient of magnetic glass fiber, the e among magnetic property such as Fig. 2.
The target of table 1 magnetic glass fiber is formed
| Embodiment | The magnetic kind | SiO 2 (％) | Al 2O 3 (％) | B 2O 3 (％) | CaO (％) | Ferrite (％) | Other (%) |
| 1 2 3 4 5 | BaFe 12O 19 NiFe 2O 4 CoFe 2O 4 CoFe 2O 4 Cofe 2O 4 | 53.0 52.2 50.9 49.8 47.1 | 13.9 13.7 13.3 13.1 12.4 | 7.4 7.3 7.1 7.0 6.6 | 22.3 22.0 21.4 21.0 19.8 | 2 3.5 6 8 13 | 1.4 1.3 1.3 1.1 1.1 |
Claims (6)
1, a kind of magnetic glass fiber is characterized in that: this magnetic glass fiber contains the nano level CoFe of 2-13% weight uniformly
2O
4Ferrite, BaFe
12O
19Ferrite or NiFe
2O
4Ferromagnetic oxide powder;
Described nano level CoFe
2O
4Ferrite, BaFe
12O
19Ferrite or NiFe
2O
4Ferromagnetic oxide powder is coated with SiO
2, it is prepared as follows:
1) salt that will contain Co and contain Fe is that 1: 2 ratio is weighed formation mixture (A) in the mol ratio of Co and Fe; The salt that perhaps will contain Ba and contain Fe is that 1: 12 ratio is weighed in the mol ratio of Ba and Fe, constitutes mixture (B), and the salt that perhaps will contain Ni and contain Fe is that 1: 2 ratio is weighed formation mixture (C) in the mol ratio of Ni and Fe;
2) (CO is dissolved in the nitric acid acidifying deionized water with said mixture material (A), mixture (B) or mixture, and add the mixed organic solvents of forming by methyl alcohol, methane amide and tetraethoxy, after 20-60 ℃ of gel 2-12 hour, under 20-60 ℃ of temperature ageing 24-48 hour; Gained xerogel under 40-120 ℃ vacuum dry 2-4 days then is warming up to 200-300 ℃ and be incubated 20-60 minute under this condition; Grind after taking out cooling, place again in the retort furnace, under air atmosphere, be heated to 950-1050 ℃ of calcining 2-6 hour, promptly make and be coated with SiO with the temperature rise rate of 1-5 ℃/min
2Nano level CoFe
2O
4Ferrite, BaFe
12O
19Ferrite or NiFe
2O
4Ferromagnetic oxide powder;
The weight part proportioning of methyl alcohol, methane amide and tetraethoxy is 1-9: 1-5: 5-15 in the described mixed organic solvents;
The concentration of nitric acid is 0.001-0.05mol/L in the described nitric acid acidifying deionized water;
The salt of the described Co of containing is Xiao Suangu, cobalt chloride, rose vitriol or Cobaltous diacetate; The salt of the described Ba of containing is nitrate of baryta, bariumchloride or hydrated barta; The salt of the described Ni of containing is nickelous nitrate, nickelous chloride, single nickel salt or nickel acetate; The salt of the described Fe of containing is iron nitrate, iron(ic) chloride or ferric sulfate;
Being prepared as follows of described magnetic glass fiber:
With strength blended way with the above-mentioned SiO that is coated with
2Nano level CoFe
2O
4Ferrite, BaFe
12O
19Ferrite or NiFe
2O
4Ferrite super-fine magnetic powder and glass fibre raw material mix, and the weight percent content of wherein said ferrite super-fine magnetic powder is 2-13%, SiO in the described glass fibre raw material
2Consumption equal SiO in the conventional glass fibre raw material
2The consumption SiO that deducts in the ferromagnetic oxide powder to be coated
2Amount; And mixture melted at 1300-1400 ℃, and make magnetic glass fiber through wire drawing.
2, by the described magnetic glass fiber of claim 1, it is characterized in that: the granularity of the nanometer ferrite magnetic that described magnetic glass fiber is contained is 5-100nm.
3, by the described magnetic glass fiber of claim 1, it is characterized in that: the diameter of described magnetic glass fiber is 1-30 μ m.
4, the preparation method of the described magnetic glass fiber of a kind of claim 1, its step is as follows:
1) preparation is coated with SiO
2Nano-level iron oxysome super-fine magnetic powder:
(1) salt that will contain Co and contain Fe is that 1: 2 ratio is weighed formation mixture (A) in the mol ratio of Co and Fe; The salt that perhaps will contain Ba and contain Fe is that 1: 12 ratio is weighed in the mol ratio of Ba and Fe, constitutes mixture (B), and the salt that perhaps will contain Ni and contain Fe is that 1: 2 ratio is weighed formation mixture (C) in the mol ratio of Ni and Fe;
(2) said mixture material (A), mixture (B) or mixture (C) are dissolved in the nitric acid acidifying deionized water, and add the mixed organic solvents of forming by methyl alcohol, methane amide and tetraethoxy, after 20-60 ℃ of gel 2-12 hour, under 20-60 ℃ of temperature ageing 24-48 hour; Gained xerogel under 40-120 ℃ vacuum dry 2-4 days then is warming up to 200-300 ℃ and be incubated 20-60 minute under this condition; Grind after taking out cooling, place again in the retort furnace, under air atmosphere, be heated to 950-1050 ℃ of calcining 2-6 hour, promptly make and be coated with SiO with the temperature rise rate of 1-5 ℃/min
2Nano level CoFe
2O
4Ferrite, BaFe
12O
19Ferrite or NiFe
2O
4Ferromagnetic oxide powder;
The weight part proportioning of methyl alcohol, methane amide and tetraethoxy is 1-9: 1-5: 5-15 in the described mixed organic solvents;
The concentration of nitric acid is 0.001-0.05mol/L in the described nitric acid acidifying deionized water;
The salt of the described Co of containing is Xiao Suangu, cobalt chloride, rose vitriol or Cobaltous diacetate; The salt of the described Ba of containing is nitrate of baryta, bariumchloride or hydrated barta; The salt of the described Ni of containing is nickelous nitrate, nickelous chloride, single nickel salt or nickel acetate; The salt of the described Fe of containing is iron nitrate, iron(ic) chloride or ferric sulfate;
2) preparation magnetic glass fiber:
With strength blended way with the above-mentioned SiO that coated
2Nano level CoFe
2O
4Ferrite, BaFe
12O
19Ferrite or NiFe
2O
4Ferromagnetic oxide powder and glass fibre raw material mix, and the weight percent content of wherein said ferromagnetic oxide powder is 2-13%, SiO in the described glass fibre raw material
2Consumption equal SiO in the conventional glass fibre raw material
2The consumption SiO that deducts in the ferromagnetic oxide powder to be coated
2Amount; And mixture melted at 1300-1400 ℃, and prepare magnetic glass fiber through wire drawing.
5, by the preparation method of the described magnetic glass fiber of claim 4, it is characterized in that the granularity of the nanometer ferrite magnetic that described magnetic glass fiber is contained is 5-100nm.
6, by the preparation method of the described magnetic glass fiber of claim 4, it is characterized in that the diameter of described magnetic glass fiber is 1-30 μ m.
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| CN1065055A (en) * | 1991-03-20 | 1992-10-07 | 张维 | Magnetothermal glass absorbing and shielding electromagnetic wave |
| CN1211306C (en) * | 1999-05-13 | 2005-07-20 | 同济大学 | Magnetic microcrystalline pyroceram |
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