CN106637936B - A kind of graphene-iron composite fibre and preparation method thereof - Google Patents
A kind of graphene-iron composite fibre and preparation method thereof Download PDFInfo
- Publication number
- CN106637936B CN106637936B CN201611219108.5A CN201611219108A CN106637936B CN 106637936 B CN106637936 B CN 106637936B CN 201611219108 A CN201611219108 A CN 201611219108A CN 106637936 B CN106637936 B CN 106637936B
- Authority
- CN
- China
- Prior art keywords
- graphene
- fiber
- iron
- microns
- composite fibre
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/83—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with metals; with metal-generating compounds, e.g. metal carbonyls; Reduction of metal compounds on textiles
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/20—Electroplating: Baths therefor from solutions of iron
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/06—Wires; Strips; Foils
- C25D7/0607—Wires
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/40—Fibres of carbon
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Textile Engineering (AREA)
- Inorganic Fibers (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The present invention illustrates a kind of graphene-iron composite fibre and preparation method thereof, the graphene oxide fiber that diameter is 1-50 microns is prepared first with the method for wet spinning, again graphene oxide fiber is placed on to heat in high temperature furnace and be restored, obtain continuous pure graphene fiber, since special processing mode makes fiber surface have multistage fold, after the cathode that pure graphene fiber is fixed on electroplating bath is electroplated, so that iron layer has the extended structure for being embedded in fold.Graphene is combined closely with iron crystal, and hole defect is not present, substantially increases the electric property of material.Fibre structure is stablized, and 100 conductivities of bending are constant.
Description
Technical field
The present invention relates to a kind of novel graphene metallic composite, especially a kind of graphene-iron composite fibre and its
Preparation method.
Background technique
For metallic iron in metal alloy, the fields such as building trade and mold molding, which have, is widely applied potentiality, relative to
Other metal materials show superior ductility, but mechanical strength is not high.In order to improve practicability and the reduction of iron
Cost, the method generallyd use at present are that it is made into composite material, carbon materials with carbon material more tough and with good conductivity
Expect that such as graphite and carbon nanotube have preferable flexibility, so the composite material being made into while cost is reduced will not be bright
Develop and rings its processing performance and service performance.
Relative to graphite and carbon nanotube, graphene has more excellent electric conductivity and more preferably flexibility, therefore more
It is suitble to be made into composite material with iron.Plating iron mainly has two kinds of paths of chemical plating and plating to be electroplated more environmentally-friendly relative to chemical plating
It cleans and easy to operate, therefore realizes that iron plating is a kind of ideal method on graphene in a manner of plating.
However, being different from other carbon materials, there is super lubricating action, adhesive force between the two between graphene and metal
Very weak, this brings huge challenge to grapheme material directly electroplating on surface iron.
Summary of the invention
In view of the above problems, the present invention provides a kind of economical and effective, and a kind of graphene-iron of energy large-scale application is multiple
Condensating fiber and preparation method thereof, composite fibre stability made from this method is good, and density is low, and conductivity is high, and flexibility is good.
The purpose of the present invention is what is be achieved through the following technical solutions: a kind of graphene-iron composite fibre, the compound fibre
Dimension is made of the iron layer of pure graphene fiber and the pure graphene fiber of cladding；The pure graphene fiber surface has fold,
Iron layer has the extended structure for being embedded in fold.
Further, the width of the fold is 20 nanometers to 5 microns.
A kind of preparation method of graphene-iron composite fibre, its preparation step are as follows:
(1) prepare graphene oxide fiber using the method for wet spinning (diameter is 1-50 microns)；
(2) again graphene oxide fiber is placed on to heat in high temperature furnace and is restored, temperature is 800-3000 DEG C, and the recovery time is
1-24 hours, obtain pure graphene fiber.
(3) cathode that pure graphene fiber is fixed on electroplating bath is electroplated, electroplating bath just extremely iron staff applies with electricity
Pressure value is the DC voltage of 0.1-20V, after being electroplated 2-120 seconds in electroplate liquid, takes out fiber, fiber table is washed with deionized water
The electroplate liquid in face, it is dry in vacuum drying oven, obtain graphene-iron composite fibre.The group of the electroplate liquid becomes, ferric sulfate
Concentration is 300-550g/L, and the volumetric concentration of the concentrated sulfuric acid of 98wt% is 3-10mL/L, and the concentration of potassium sulfate is 100-200g/L.
Further, in the step 1, the spinning solution of wet spinning are as follows: the oxidation stone that piece diameter is 1-50 microns
Dispersion liquid of the black alkene in dimethylformamide, the concentration of graphene oxide are 1~10mg/mL；The internal diameter of spinning pipeline is 60-
500 microns；Coagulating bath is the mixed solution (the two volume ratio is 1:1-50:1) of ethyl acetate and methylene chloride, outer when receiving silk
Boundary's heating temperature is 80-200 DEG C.
Further, in the step 3, when voltage is 20V, required electroplating time is 2s.
Further, in the step 3, when voltage is 1V, required electroplating time is 10s.
The beneficial effects of the present invention are: preparation process of the present invention is simple and safe controllable, and time consumption and energy consumption is few, raw material sources
Extensively.Since graphene surface has many folds, metallic iron layer and graphene fiber surface can be made closely compound, obtained
Complex structure of filament is fine and close, functional.
Detailed description of the invention
Fig. 1 is graphene-iron composite fibre structural schematic diagram；
Fig. 2 is the graphene surface multistage pleated structure figure under different multiplying；
The distribution of iron particle and growth conditions when Fig. 3 is graphene-iron composite fibre plating；
Fig. 4 is graphene-iron composite fibre XRD diagram；
Fig. 5 a, b, c are respectively the state of smooth graphene surface plating metal.
Specific embodiment
As shown in Figure 1, a kind of graphene-iron composite fibre, the pure graphite that the composite fibre is 1-50 microns by diameter
The iron layer composition of alkene fiber and the pure graphene fiber of cladding；The pure graphene fiber surface has fold, and iron layer has embedding
Enter the extended structure of fold.The good physical property of fiber is combined closely from iron layer and graphene fiber surface, solution
It has determined and has been difficult to the problem of modification is electroplated between graphene and metallic particles.On the one hand obtained fibre structure is stablized, such as can be with
It is constant to be bent 100 conductivities；On the other hand, two kinds of material tights combine, and there is no hole defects, substantially increase material
The electric property of material.
As shown in Fig. 2, the width of the fold is 20 nanometers to 5 microns.After tested, plating iron graphene fiber stone obtained
Black alkene bulk density is 1.8-5.3g/cm3, graphene mass fraction is 20-80%, and the mass fraction of iron is 20-80%, fiber
Conductivity be 1.1 × 105S/m–3.6×106S/m, thickness of coating are 1-18 microns.
As shown in figure 3, due to graphene fiber surface irregularity, electronics is in radius of curvature ratio in the plating initial stage
Biggish plication region aggregation, the crystal grain of iron is preferentially nucleated here and apposition growth, and with the progress of plating, particle is gradually given birth to
Long, particle becomes larger, and the crack being crimped is fixed, and further, iron crystal grain is along fold homoepitaxial and mutually fusion is until paving
Full entire fiber surface, growth course is as shown, this growth pattern from inside to outside ensures that final coating can be uniformly
It is covered on fiber surface and stablizes attachment.On the one hand the fibre structure obtained is stablized, for example can be bent 100 conductivities not
Become；On the other hand, two kinds of material tights combine, and there is no hole defects, substantially increase the electric property of material.It ties below
Closing embodiment, the invention will be further described.
Embodiment 1
A kind of method that galvanoplastic prepare graphene and iron composite fibre, including following procedure:
(1) the graphene oxide fiber that diameter is 4 microns is prepared using the method for wet spinning, specifically: wet spinning
Spinning solution are as follows: piece diameter is the dispersion liquid of 5 microns of graphene oxide (carbon Gu Shangxi) in dimethylformamide, oxygen
The concentration of graphite alkene is 8mg/mL；The internal diameter of spinneret is 100 microns；Coagulating bath is the mixing of ethyl acetate and methylene chloride
Solution (the two volume ratio is 1:1), extraneous heating temperature when receiving silk is 200 DEG C.
(2) graphene oxide fiber is placed on to heat in high temperature furnace and is restored, temperature is 1000 DEG C, after heating 1.5 hours, is obtained
The graphene fiber for being 4 microns to diameter.
(3) cathode that graphene fiber is fixed on electroplating bath is electroplated, electroplating bath just extremely high purity iron stick, apply with
Voltage value is the DC voltage of 0.1V, and electroplate liquid is ferrous sulfate (300g/L), the dense sulphur of potassium sulfate (100g/L) and 98wt%
The electroplate liquid of fiber surface is washed off with water after plating 8 seconds in the mixed aqueous solution of sour (3mL/L), and dry 1 is small in vacuum drying oven
When.Since voltage is lower, the time is shorter, and obtaining coating is about 3 microns.As shown in figure 4, XRD final compound fibre as the result is shown
There is the peak of apparent iron crystal in dimension table face.After tested, conductivity is 7.3 × 105S/m。
Embodiment 2
A kind of method that galvanoplastic prepare graphene and iron composite fibre, including following procedure,
(1) the graphene oxide fiber that diameter is 10 microns is prepared using the method for wet spinning, specifically: wet spinning
Spinning solution are as follows: piece diameter is the dispersion liquid of 5 microns of graphene oxide (carbon Gu Shangxi) in dimethylformamide, oxygen
The concentration of graphite alkene is 8mg/mL；The internal diameter of spinneret is 250 microns；Coagulating bath is the mixing of ethyl acetate and methylene chloride
Solution (the two volume ratio is 10:1), extraneous heating temperature when receiving silk is 80 DEG C.
(2) again graphene oxide fiber is placed on to heat in high temperature furnace and is restored, temperature is 2200 DEG C, after heating 3 hours, is obtained
The graphene fiber for being 10 microns to diameter；
(3) cathode that graphene fiber is fixed on electroplating bath is electroplated, electroplating bath just extremely high purity iron stick, apply with
Voltage value is the DC voltage of 1.3V, and electroplate liquid is ferrous sulfate (450g/L), the dense sulphur of potassium sulfate (130g/L) and 98wt%
The electroplate liquid of fiber surface is washed off with water after plating 120 seconds in the mixed aqueous solution of sour (3.5mL/L), dry in vacuum drying oven
9 hours.Obtaining coating is about 5 microns.After tested, conductivity is 1.5 × 106S/m。
Embodiment 3
A kind of method that galvanoplastic prepare graphene and iron composite fibre, including following procedure:
(1) the graphene oxide fiber that diameter is 30 microns is prepared using the method for wet spinning, specifically: wet spinning
Spinning solution are as follows: piece diameter is the dispersion liquid of 50 microns of graphene oxide (carbon Gu Shangxi) in dimethylformamide,
The concentration of graphene oxide is 11mg/mL；The internal diameter of spinneret is 500 microns；Coagulating bath is ethyl acetate and methylene chloride
Mixed solution (the two volume ratio is 200:1), extraneous heating temperature when receiving silk is 100 DEG C.
(2) again graphene oxide fiber is placed on to heat in high temperature furnace and is restored, temperature is 2700 DEG C, after heating 1 hour, is obtained
The graphene fiber for being 30 microns to diameter.
(3) cathode that graphene fiber is fixed on electroplating bath is electroplated, the just extremely pure iron staff of electroplating bath, apply with
Voltage value is the DC voltage of 20V, and electroplate liquid is ferrous sulfate (500g/L), the concentrated sulfuric acid (10mL/L) and potassium sulfate of 98wt%
The electroplate liquid of fiber surface is washed off with water after plating 2 seconds in the mixed aqueous solution of (200g/L), and dry 5 is small in vacuum drying oven
When.After improving supply voltage, the potential of fiber is increased, and obtaining coating is about 10 microns.After tested, conductivity be 2.8 ×
106S/m。
Embodiment 4
Importance of the fold for metal plating of graphene surface is verified using smooth graphene surface, including following
Process:
(1) as shown in Figure 5 a, smooth graphene film is taken, is conventionally electroplated, obtained metal is multiple
It is as shown in Figure 5 b to close film, coating is relatively thin and very uneven.
(2) metallic graphite carbon alkene composite membrane is slightly rinsed in water, obtained result is as shown in Figure 5 c, and coating is shelled completely
It falls, shows very poor binding force and stability.
Claims (4)
1. a kind of graphene-iron composite fibre preparation method, the composite fibre is by pure graphene fiber and the pure stone of cladding
The iron layer of black alkene fiber forms；The pure graphene fiber surface has fold, and iron layer has the extended structure for being embedded in fold,
It is characterized in that, its preparation step is as follows:
(1) the graphene oxide fiber that diameter is 1-50 microns is prepared using the method for wet spinning；
(2) again graphene oxide fiber is placed on to heat in high temperature furnace and is restored, obtain pure graphene fiber；
(3) cathode that pure graphene fiber is fixed on electroplating bath is electroplated, electroplating bath just extremely iron staff applies with voltage value
For the DC voltage of 0.1-20V, after being electroplated 2-120 seconds in electroplate liquid, fiber is taken out, fiber surface is washed with deionized water
Electroplate liquid, it is dry in vacuum drying oven, obtain graphene-iron composite fibre；
The group of the electroplate liquid becomes, and the concentration of ferric sulfate is 300-550 g/L, and the volumetric concentration of the concentrated sulfuric acid of 98wt% is 3-
10 mL/L, the concentration of potassium sulfate are 100-200g/L.
2. the method according to claim 1, wherein in the step 1, the spinning solution of wet spinning are as follows: piece is straight
Dispersion liquid of the graphene oxide that diameter size is 1-50 microns in dimethylformamide, the concentration of graphene oxide are 1 ~ 10
mg/mL；The internal diameter of spinning pipeline is 60-500 microns；Coagulating bath is ethyl acetate and methylene chloride according to volume ratio 1:1-50:1
The mixed solution of composition, extraneous heating temperature when receiving silk are 80-200 DEG C.
3. the method according to claim 1, wherein in the step 3, when voltage is 20V, required electroplating time
For 2s.
4. the method according to claim 1, wherein in the step 3, when voltage is 1V, required electroplating time
For 10s.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611219108.5A CN106637936B (en) | 2016-12-26 | 2016-12-26 | A kind of graphene-iron composite fibre and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611219108.5A CN106637936B (en) | 2016-12-26 | 2016-12-26 | A kind of graphene-iron composite fibre and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106637936A CN106637936A (en) | 2017-05-10 |
| CN106637936B true CN106637936B (en) | 2019-04-30 |
Family
ID=58827321
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611219108.5A Active CN106637936B (en) | 2016-12-26 | 2016-12-26 | A kind of graphene-iron composite fibre and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106637936B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108411350B (en) * | 2018-04-08 | 2020-04-14 | 武汉大学苏州研究院 | Preparation method of graphene reinforced iron-based composite material |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104790067A (en) * | 2015-04-17 | 2015-07-22 | 东华大学 | Nano conductive polymer/graphene composite fiber, and preparation method and application thereof |
| CN105562636A (en) * | 2015-12-31 | 2016-05-11 | 张颖 | Preparation method for crystallizer copper plate coated with nickel-cobalt-iron alloy layer |
| CN105648579A (en) * | 2016-03-31 | 2016-06-08 | 浙江大学 | Superfine graphene fibers and method for preparing same |
| CN105845218A (en) * | 2016-05-18 | 2016-08-10 | 中天科技装备电缆有限公司 | Light total carbon cable and preparation method |
-
2016
- 2016-12-26 CN CN201611219108.5A patent/CN106637936B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104790067A (en) * | 2015-04-17 | 2015-07-22 | 东华大学 | Nano conductive polymer/graphene composite fiber, and preparation method and application thereof |
| CN105562636A (en) * | 2015-12-31 | 2016-05-11 | 张颖 | Preparation method for crystallizer copper plate coated with nickel-cobalt-iron alloy layer |
| CN105648579A (en) * | 2016-03-31 | 2016-06-08 | 浙江大学 | Superfine graphene fibers and method for preparing same |
| CN105845218A (en) * | 2016-05-18 | 2016-08-10 | 中天科技装备电缆有限公司 | Light total carbon cable and preparation method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106637936A (en) | 2017-05-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106702732B (en) | A kind of graphene-copper composite fibre and preparation method thereof | |
| CN106702731B (en) | A kind of graphene-silver composite fibre and preparation method thereof | |
| Chen et al. | One-step electrodeposition process to fabricate cathodic superhydrophobic surface | |
| Yao et al. | Fracture investigation of functionalized carbon nanotubes-grown carbon fiber fabrics/epoxy composites | |
| Pei et al. | The fabrication of a carbon nanotube transparent conductive film by electrophoretic deposition and hot-pressing transfer | |
| Eyckens et al. | Improving the effects of plasma polymerization on carbon fiber using a surface modification pretreatment | |
| CN101976594A (en) | Composite conductor application of carbon nano tube fiber and preparation method thereof | |
| Feng et al. | Fabrication of copper/carbon nanotube composite thin films by periodic pulse reverse electroplating using nanodiamond as a dispersing agent | |
| Huang et al. | Preparing a high-particle-content Ni/diamond composite coating with strong abrasive ability | |
| Wang et al. | Preparation of a multifunctional material with superhydrophobicity, superparamagnetism, mechanical stability and acids–bases resistance by electrospinning | |
| CN106637937B (en) | A kind of graphene-cobalt composite fibre and preparation method thereof | |
| Dan et al. | Preparation and characterization of wear-resistant superhydrophobic cotton fabrics | |
| CN106676878B (en) | A kind of graphene-zinc composite fibre and preparation method thereof | |
| CN106637936B (en) | A kind of graphene-iron composite fibre and preparation method thereof | |
| Li et al. | Study of deposition patterns of plating layers in SiC/Cu composites by electro-brush plating | |
| Sun et al. | A two-step method for high efficient and continuous carbon fiber treatment with enhanced fiber strength and interfacial adhesion | |
| Chen et al. | Graphene quantum dots derived from carbon fibers for oxidation of dopamine | |
| CN107354500B (en) | A kind of nanoscale Fe3O4The glass fiber compound material and preparation method thereof of grapheme modified cladding | |
| Qi et al. | Superhydrophobic brocades modified with aligned ZnO nanorods | |
| CN106676875B (en) | A kind of graphene-nickel composite fibre and preparation method thereof | |
| Xu et al. | Copper thin coating deposition on natural pollen particles | |
| An et al. | Electrodeposition in the Ni-plating bath containing multi-walled carbon nanotubes | |
| CN106676877B (en) | A kind of graphene-manganese composite fibre and preparation method thereof | |
| Wright et al. | Nanomagnetic domains of chromium deposited on vertically-aligned carbon nanotubes | |
| CN106637935B (en) | A kind of graphene-gold composite fibre and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20190903 Address after: 313100 Room 830, 8th Floor, Changxing World Trade Building, 1278 Mingzhu Road, Changxing Economic Development Zone, Huzhou City, Zhejiang Province Patentee after: Changxin de Technology Co., Ltd. Address before: 310058 Xihu District, Zhejiang, Yuhang Tong Road, No. 866, No. Patentee before: Zhejiang University |
|
| TR01 | Transfer of patent right |