CN106243390A - A kind of high intensity load silver/titanium dioxide compound glass is fine and ties up preparation method - Google Patents
A kind of high intensity load silver/titanium dioxide compound glass is fine and ties up preparation method Download PDFInfo
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- CN106243390A CN106243390A CN201610612844.0A CN201610612844A CN106243390A CN 106243390 A CN106243390 A CN 106243390A CN 201610612844 A CN201610612844 A CN 201610612844A CN 106243390 A CN106243390 A CN 106243390A
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- glass fibre
- titanium dioxide
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- glass
- glass fiber
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 36
- 229910001923 silver oxide Inorganic materials 0.000 title claims abstract description 35
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Substances [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000011521 glass Substances 0.000 title claims description 33
- -1 titanium dioxide compound Chemical class 0.000 title abstract description 6
- 239000003365 glass fiber Substances 0.000 claims abstract description 143
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 58
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 55
- 239000002131 composite material Substances 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 26
- 239000006185 dispersion Substances 0.000 claims description 49
- 238000013019 agitation Methods 0.000 claims description 43
- 239000002096 quantum dot Substances 0.000 claims description 34
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 32
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 28
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 28
- 238000002156 mixing Methods 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 18
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 18
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 18
- 229910052719 titanium Inorganic materials 0.000 claims description 18
- 239000010936 titanium Substances 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 16
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 16
- 229910052593 corundum Inorganic materials 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 238000005303 weighing Methods 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- 238000005491 wire drawing Methods 0.000 claims description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 9
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 9
- 229910006295 Si—Mo Inorganic materials 0.000 claims description 9
- 238000010306 acid treatment Methods 0.000 claims description 9
- 235000019270 ammonium chloride Nutrition 0.000 claims description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 9
- 238000000137 annealing Methods 0.000 claims description 9
- 238000005266 casting Methods 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 239000010431 corundum Substances 0.000 claims description 9
- 230000018044 dehydration Effects 0.000 claims description 9
- 238000006297 dehydration reaction Methods 0.000 claims description 9
- 238000000465 moulding Methods 0.000 claims description 9
- 238000010792 warming Methods 0.000 claims description 9
- 239000011787 zinc oxide Substances 0.000 claims description 9
- YASYEJJMZJALEJ-UHFFFAOYSA-N Citric acid monohydrate Chemical compound O.OC(=O)CC(O)(C(O)=O)CC(O)=O YASYEJJMZJALEJ-UHFFFAOYSA-N 0.000 claims description 8
- 229960002303 citric acid monohydrate Drugs 0.000 claims description 8
- 238000005304 joining Methods 0.000 claims description 7
- 229910052738 indium Inorganic materials 0.000 claims description 6
- 229950000845 politef Drugs 0.000 claims description 6
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- 239000012530 fluid Substances 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- ZHMOXORLBQHYAG-UHFFFAOYSA-N C(CC(O)(C(=O)O)CC(=O)O)(=O)O.O.[Na].[Na].[Na].C(CC(O)(C(=O)O)CC(=O)O)(=O)O Chemical compound C(CC(O)(C(=O)O)CC(=O)O)(=O)O.O.[Na].[Na].[Na].C(CC(O)(C(=O)O)CC(=O)O)(=O)O ZHMOXORLBQHYAG-UHFFFAOYSA-N 0.000 claims description 3
- NMGYKLMMQCTUGI-UHFFFAOYSA-J diazanium;titanium(4+);hexafluoride Chemical compound [NH4+].[NH4+].[F-].[F-].[F-].[F-].[F-].[F-].[Ti+4] NMGYKLMMQCTUGI-UHFFFAOYSA-J 0.000 claims description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 3
- 239000002048 multi walled nanotube Substances 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims 1
- 238000001035 drying Methods 0.000 claims 1
- 239000000155 melt Substances 0.000 claims 1
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 12
- 239000011248 coating agent Substances 0.000 abstract description 11
- 238000000576 coating method Methods 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 6
- 230000000845 anti-microbial effect Effects 0.000 abstract description 5
- 239000004332 silver Substances 0.000 abstract description 4
- 229910052709 silver Inorganic materials 0.000 abstract description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract description 3
- 238000011068 loading method Methods 0.000 description 13
- 230000000694 effects Effects 0.000 description 11
- 239000000835 fiber Substances 0.000 description 11
- 238000012360 testing method Methods 0.000 description 10
- 239000010410 layer Substances 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 230000003115 biocidal effect Effects 0.000 description 5
- 239000001509 sodium citrate Substances 0.000 description 5
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 5
- 229940038773 trisodium citrate Drugs 0.000 description 5
- 229910001845 yogo sapphire Inorganic materials 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000011152 fibreglass Substances 0.000 description 3
- 230000001954 sterilising effect Effects 0.000 description 3
- 230000001580 bacterial effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 241001466460 Alveolata Species 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000003082 abrasive agent Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000013068 control sample Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 239000007943 implant Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000009291 secondary effect Effects 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000012430 stability testing Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0806—Silver
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The invention discloses a kind of load silver/titanium dioxide compound glass fibre and dimension preparation method thereof, described preparation method comprises the following steps: (1) prepares glass fibre；(2) glass fibre pretreatment；(3) glass fibre of preparation load silver；(4) coating porous graphene；(5) glass fibre of preparation load silver/titanium dioxide.The mechanical property of this composite glass fiber is more excellent, can increase substantially intensity and the toughness of material, owing to the antibacterial characteristics of silver and titanium dioxide makes composite have excellent anti-microbial property.It addition, the method technique of the present invention is simple, with low cost, practicality is good.
Description
Technical field
The present invention relates to technical field of composite materials, particularly relate to a kind of high intensity load silver/titanium dioxide multiple
Close glass fibers and dimension preparation method thereof.
Background technology
(English original name is glass fibre: glass fiber or fiberglass) be the inorganic non-gold of a kind of excellent performance
Belonging to material, of a great variety, advantage is good insulating, thermostability is strong, corrosion resistance good, and mechanical strength is high, but shortcoming is that property is crisp, resistance to
Mill property is poor.It is usually with glass bead or discarded glass for raw material through high temperature melting, wire drawing, doff, the technique manufacture such as weave cotton cloth
Become, a diameter of several microns of its monofilament to twenties meters micron, be equivalent to the 1/20 ~ 1/5 of a hairline, often restraint fibre
Dimension precursor is all made up of hundreds of the most thousands of monofilament.
Graphene, as the allotrope of carbon, is that carbon atom has alveolate texture by what sp2 orbital hybridization was formed
Monolayer two dimensional crystal material, good mechanical performance that Graphene has, chemical stability etc. also will be in fields such as composites
Have broad application prospects.
At present, although have and Graphene is coated on fiberglass surfacing with the physical property of reinforcing glass fiber, but
It is not highly desirable for improving effect, need to further enhance.And, have been reported now by adding at fiberglass surfacing
Nanometer silver thus give glass fibre with anti-microbial property, can be applicable to filter paper and resin etc. and make it have antibacterial characteristics；But
It is that nanometer silver is in granular form, often can only be gathered in the specific part of glass fibre, it is impossible to be evenly distributed on surface, thus affect
Antibacterial effect；On the other hand, nanometer silver and glass fibre cannot be combined closely (particularly when nano-Ag particles content increases
Time, it is susceptible to agglomeration), the most easily come off, thus affect service life and antibacterial effect.
Summary of the invention
The technical problem to be solved there is provided a kind of high intensity with durable antibiotic performance and high tenacity
Load silver/titanium dioxide composite glass fiber.Present invention also offers a kind of described load silver/titanium dioxide compound glass fine
Dimension preparation method.
The technical problem to be solved is achieved by the following technical programs:
The preparation method of a kind of high intensity load silver/titanium dioxide composite glass fiber, comprises the following steps:
(1) glass fibre is prepared: by 50 ~ 55% SiO2,10 ~ 15%B2O3,5 ~ 10%Na2O, 10 ~ 15%Al2O3,15 ~ 20%CaO
After mixing with 0.1 ~ 0.5% multi-walled carbon nano-tubes (OD is 8nm) crushing, stirring, it is placed in the corundum crucible of 400mL, uses Si-Mo rod
Resistance furnace is founded, and charge temperature is 1370 DEG C, and melted clarifying temp is 1450 ± 10 DEG C, comes out of the stove in 1200 DEG C, and moulding by casting send
Enter in Muffle furnace, in 500 DEG C of annealing, prepare glass；Prepared glass is heated to the temperature 1050 DEG C of wire drawing viscosity, is drawn into
Glass fibre about diameter about 10 μm；
(2) glass fibre pretreatment: after taking 5 ~ 50 parts of glass fibre split-phases, enters in the HCl solution that 100ml concentration is 1mol/L
Row acidleach processes, and it is to carry out under the conditions of constant temperature 95 DEG C that acidleach processes, make the Na2O-B2O3 phased soln that separates in glass fibre in
Acid, in acid add 5ml concentration be the NH4Cl solution of 40% as buffer agent, the acid treatment time is 30min；Through rinse dehydration, baking
Dry, obtain pretreated glass fiber；
(3) weighing graphene quantum dot (particle diameter about 2 ~ 5nm) and be configured to the dispersion soln that concentration is 0.1 ~ 1mg/ml, solvent is
Water, acetone or dimethyl sulfoxide；Ultrasonic agitation (300 ~ 500W ultrasonic power, 200 ~ 300rpm mixing speed) 50 ~ 60ml graphite
Alkene quantum dot dispersion soln, joining concentration is 0.01 ~ 0.03mol/L silver nitrate solution, and controlling reaction temperature is 45 ~ 60 DEG C,
Dropping concentration is 0.1～0.8mol/L bis-citric acid monohydrate trisodium, continues ultrasonic agitation 60 ~ 120min；Dropping 10 ~ 20ml graphite
Alkene quantum dot dispersion soln；Being added thereto by pretreated glass fibre, ultrasonic agitation speed halves, and impregnates 30 ~ 60min,
Period avoids fibre matting, impact coating effect；Taking-up glass fibre cleans, and dries, stand-by；Graphene quantum dot dispersion,
The volume ratio of silver nitrate solution and two citric acid monohydrate trisodiums is 3 ~ 4:2 ~ 3:1 ~ 2；
(4) weigh porous graphene (2 ~ 5 layers, hole size about 3 ~ 6nm) to be configured to the Graphene that concentration is 0.2 ~ 0.8mg/ml and divide
Dissipating solution, solvent is water, acetone or dimethyl sulfoxide；(300 ~ 500W ultrasonic power, 200 ~ 300rpm stirs speed to ultrasonic agitation
Degree) 80 ~ 100ml graphene dispersion solution, add the glass fibre that step (3) prepares, ultrasonic agitation 10min, then move to gather
In the reactor of tetrafluoroethene, at 80 ~ 120 DEG C, it is incubated 15 ~ 30min；Taking-up glass fibre cleans, and dries, stand-by；
(5) weighing Zinc oxide quantum dot (particle diameter about 5 ~ 10nm) and be configured to the dispersion liquid that concentration is 0.5 ~ 1mg/ml, solvent is water；
Ultrasonic agitation (300 ~ 500W ultrasonic power, 200 ~ 300rpm mixing speed) 80 ~ 100ml zinc oxide fluid dispersion, makes step (4)
The glass fibre obtained is added thereto, and ultrasonic agitation speed halves, and impregnates 30 ~ 60min, and period avoids fibre matting, impact coating
Effect；Taking-up glass fibre cleans, and dries, stand-by；
(6) 0.1 ~ 0. 3M titanium source (titanium source is potassium fluotitanate, ammonium titanium fluoride, isopropyl titanate or titanium tetrachloride) is joined 1 M
In sulfuric acid solution, mix homogeneously；Add the glass fibre that step (5) prepares, be warming up to 110 DEG C, after reaction 3 ~ 5h, use strong aqua ammonia
Solution adjusts pH value to 7, after being aged 12 hours, cleans, is dried, and obtains loading silver/titanium dioxide composite glass fiber.
There is advantages that
Glass fibre can be coated in by the most dispersed to Graphene, silver and titanium dioxide by the method for the present invention
On, and increase glass fibre and matrix interaction area and interface binding power further, so that using this compound glass fine
The mechanical property of the composite of dimension is more excellent, increases substantially intensity and the toughness of material, due to silver and titanium dioxide
Antibacterial characteristics makes composite have excellent anti-microbial property.It addition, the method technique of the present invention is simple, with low cost, real
Good by property.Composite glass fiber can be as the implant of injected plastics material, to increase sheet material, the mechanical performance of bulk and antibacterial
Characteristic.
Detailed description of the invention
Below in conjunction with embodiment, the present invention will be described in detail, and embodiment is only the preferred embodiment of the present invention,
It it not limitation of the invention.
Embodiment 1
A kind of preparation method loading silver/titanium dioxide composite glass fiber, comprises the following steps:
(1) glass fibre is prepared: after 51% SiO2,15%B2O3,6%Na2O, 10%Al2O3 and 18%CaO crushing, stirring mixing,
Being placed in the corundum crucible of 400mL, found with Si-Mo rod resistance furnace, charge temperature is 1370 DEG C, and melted clarifying temp is 1450
± 10 DEG C, come out of the stove in 1200 DEG C, moulding by casting, send in Muffle furnace, in 500 DEG C of annealing, prepare glass；Prepared glass is added
Heat, to the temperature 1050 DEG C of wire drawing viscosity, is drawn into the glass fibre about diameter about 10 μm；
(2) glass fibre pretreatment: after taking 45 parts of glass fibre split-phases, is carried out in the HCl solution that 100ml concentration is 1mol/L
Acidleach processes, and it is to carry out under the conditions of constant temperature 95 DEG C that acidleach processes, make the Na2O-B2O3 phased soln that separates in glass fibre in
Acid, in acid add 5ml concentration be the NH4Cl solution of 40% as buffer agent, the acid treatment time is 30min；Through rinse dehydration, baking
Dry, obtain pretreated glass fiber；
(3) weigh graphene quantum dot (particle diameter about 2 ~ 5nm) and be configured to the dispersion soln that concentration is 0.1mg/ml, solvent be water,
Acetone or dimethyl sulfoxide；The dispersion of ultrasonic agitation (500W ultrasonic power, 200rpm mixing speed) 60ml graphene quantum dot is molten
Liquid, joining concentration is 0.01mol/L silver nitrate solution, and controlling reaction temperature is 45 DEG C, and dropping concentration is 0.1mol/L bis-water
Close trisodium citrate, continue ultrasonic agitation 90min；Dropping 20ml graphene quantum dot dispersion soln；By pretreated glass
Fiber is added thereto, and ultrasonic agitation speed halves, and impregnates 60min, and period avoids fibre matting, impact coating effect；Take out glass
Glass fiber, washing for several times, is dried, stand-by；Graphene quantum dot dispersion, silver nitrate solution and the body of two citric acid monohydrate trisodiums
Long-pending ratio is 3:2:2；
(4) weighing porous graphene (2 ~ 5 layers, hole size about 3 ~ 6nm), to be configured to the graphene dispersion that concentration is 0.8mg/ml molten
Liquid, solvent is water, acetone or dimethyl sulfoxide；Ultrasonic agitation (500W ultrasonic power, 200rpm mixing speed) 100ml Graphene
Dispersion soln, adds the glass fibre that step (3) prepares, ultrasonic agitation 10min, then moves to the reactor of politef
In, at 100 DEG C, it is incubated 30min；Taking-up glass fibre cleans, and dries, stand-by；
(5) 0. 1M titanium source (titanium source is potassium fluotitanate) is joined in 1 M sulfuric acid solution, mix homogeneously；Add step (4) system
The glass fibre obtained, is warming up to 110 DEG C, after reaction 4h, adjusts pH value to 7 with concentrated ammonia solution, after being aged 12 hours, cleans, dry
Dry, obtain loading silver/titanium dioxide composite glass fiber.
Embodiment 2
A kind of preparation method loading silver/titanium dioxide composite glass fiber, comprises the following steps:
(1) glass fibre is prepared: after 51% SiO2,15%B2O3,6%Na2O, 10%Al2O3 and 18%CaO crushing, stirring mixing,
Being placed in the corundum crucible of 400mL, found with Si-Mo rod resistance furnace, charge temperature is 1370 DEG C, and melted clarifying temp is 1450
± 10 DEG C, come out of the stove in 1200 DEG C, moulding by casting, send in Muffle furnace, in 500 DEG C of annealing, prepare glass；Prepared glass is added
Heat, to the temperature 1050 DEG C of wire drawing viscosity, is drawn into the glass fibre about diameter about 10 μm；
(2) glass fibre pretreatment: after taking 45 parts of glass fibre split-phases, is carried out in the HCl solution that 100ml concentration is 1mol/L
Acidleach processes, and it is to carry out under the conditions of constant temperature 95 DEG C that acidleach processes, make the Na2O-B2O3 phased soln that separates in glass fibre in
Acid, in acid add 5ml concentration be the NH4Cl solution of 40% as buffer agent, the acid treatment time is 30min；Through rinse dehydration, baking
Dry, obtain pretreated glass fiber；
(3) weigh graphene quantum dot (particle diameter about 2 ~ 5nm) and be configured to the dispersion soln that concentration is 0.3mg/ml, solvent be water,
Acetone or dimethyl sulfoxide；The dispersion of ultrasonic agitation (500W ultrasonic power, 200rpm mixing speed) 50ml graphene quantum dot is molten
Liquid, joining concentration is 0.03mol/L silver nitrate solution, and controlling reaction temperature is 45 DEG C, and dropping concentration is 0.8mol/L bis-water
Close trisodium citrate, continue ultrasonic agitation 90min；Dropping 10ml graphene quantum dot dispersion soln；By pretreated glass
Fiber is added thereto, and ultrasonic agitation speed halves, and impregnates 60min, and period avoids fibre matting, impact coating effect；Take out glass
Glass fiber cleans, and dries, stand-by；Graphene quantum dot dispersion, silver nitrate solution and the volume ratio of two citric acid monohydrate trisodiums
For 4:3:2；
(4) weighing porous graphene (2 ~ 5 layers, hole size about 3 ~ 6nm), to be configured to the graphene dispersion that concentration is 0.2mg/ml molten
Liquid, solvent is water, acetone or dimethyl sulfoxide；Ultrasonic agitation (500W ultrasonic power, 200rpm mixing speed) 100ml Graphene
Dispersion soln, adds the glass fibre that step (3) prepares, ultrasonic agitation 10min, then moves to the reactor of politef
In, at 100 DEG C, it is incubated 30min；Taking-up glass fibre cleans, and dries, stand-by；
(5) 0. 3M titanium source (titanium source is isopropyl titanate) is joined in 1 M sulfuric acid solution, mix homogeneously；Add step (4)
The glass fibre prepared, is warming up to 110 DEG C, after reaction 5h, adjusts pH value to 7 with concentrated ammonia solution, after being aged 12 hours, cleans,
It is dried, obtains loading silver/titanium dioxide composite glass fiber.
Embodiment 3
A kind of preparation method loading silver/titanium dioxide composite glass fiber, comprises the following steps:
(1) glass fibre is prepared: after 51% SiO2,15%B2O3,6%Na2O, 10%Al2O3 and 18%CaO crushing, stirring mixing,
Being placed in the corundum crucible of 400mL, found with Si-Mo rod resistance furnace, charge temperature is 1370 DEG C, and melted clarifying temp is 1450
± 10 DEG C, come out of the stove in 1200 DEG C, moulding by casting, send in Muffle furnace, in 500 DEG C of annealing, prepare glass；Prepared glass is added
Heat, to the temperature 1050 DEG C of wire drawing viscosity, is drawn into the glass fibre about diameter about 10 μm；
(2) glass fibre pretreatment: after taking 45 parts of glass fibre split-phases, is carried out in the HCl solution that 100ml concentration is 1mol/L
Acidleach processes, and it is to carry out under the conditions of constant temperature 95 DEG C that acidleach processes, make the Na2O-B2O3 phased soln that separates in glass fibre in
Acid, in acid add 5ml concentration be the NH4Cl solution of 40% as buffer agent, the acid treatment time is 30min；Through rinse dehydration, baking
Dry, obtain pretreated glass fiber；
(3) weigh graphene quantum dot (particle diameter about 2 ~ 5nm) and be configured to the dispersion soln that concentration is 0.8mg/ml, solvent be water,
Acetone or dimethyl sulfoxide；The dispersion of ultrasonic agitation (500W ultrasonic power, 200rpm mixing speed) 50ml graphene quantum dot is molten
Liquid, joining concentration is 0.03mol/L silver nitrate solution, and controlling reaction temperature is 45 DEG C, and dropping concentration is 0.5mol/L bis-water
Close trisodium citrate, continue ultrasonic agitation 90min；Dropping 20ml graphene quantum dot dispersion soln；By pretreated glass
Fiber is added thereto, and ultrasonic agitation speed halves, and impregnates 60min, and period avoids fibre matting, impact coating effect；Take out glass
Glass fiber cleans, and dries, stand-by；Graphene quantum dot dispersion, silver nitrate solution and the volume ratio of two citric acid monohydrate trisodiums
For 3:2:1；
(4) weighing porous graphene (2 ~ 5 layers, hole size about 3 ~ 6nm), to be configured to the graphene dispersion that concentration is 0.5mg/ml molten
Liquid, solvent is water, acetone or dimethyl sulfoxide；Ultrasonic agitation (500W ultrasonic power, 200rpm mixing speed) 80ml Graphene
Dispersion soln, adds the glass fibre that step (3) prepares, ultrasonic agitation 10min, then moves to the reactor of politef
In, at 100 DEG C, it is incubated 30min；Taking-up glass fibre cleans, and dries, stand-by；
(5) 0.2M titanium source (titanium source is ammonium titanium fluoride) is joined in 1 M sulfuric acid solution, mix homogeneously；Add step (4) to prepare
Glass fibre, be warming up to 110 DEG C, after reaction 3h, adjust pH value to 7 with concentrated ammonia solution, after be aged 12 hours, clean, dry,
Obtain loading silver/titanium dioxide composite glass fiber.
Embodiment 4
The preparation method of a kind of high intensity load silver/titanium dioxide composite glass fiber, comprises the following steps:
(1) glass fibre is prepared: 51% SiO2,15%B2O3,6%Na2O, 9.8%Al2O3,18%CaO and the carbon of wall more than 0.2% are received
After the mixing of mitron (OD about 8nm) crushing, stirring, it is placed in the corundum crucible of 400mL, founds with Si-Mo rod resistance furnace, charge temperature
Being 1370 DEG C, melted clarifying temp is 1450 ± 10 DEG C, comes out of the stove in 1200 DEG C, moulding by casting, sends in Muffle furnace, in 500 DEG C
Annealing, prepares glass；Prepared glass is heated to the temperature 1050 DEG C of wire drawing viscosity, is drawn into the glass about diameter about 10 μm
Glass fiber；
(2) glass fibre pretreatment: after taking 45 parts of glass fibre split-phases, is carried out in the HCl solution that 100ml concentration is 1mol/L
Acidleach processes, and it is to carry out under the conditions of constant temperature 95 DEG C that acidleach processes, make the Na2O-B2O3 phased soln that separates in glass fibre in
Acid, in acid add 5ml concentration be the NH4Cl solution of 40% as buffer agent, the acid treatment time is 30min；Through rinse dehydration, baking
Dry, obtain pretreated glass fiber；
(3) weigh graphene quantum dot (particle diameter about 2 ~ 5nm) and be configured to the dispersion soln that concentration is 0.3mg/ml, solvent be water,
Acetone or dimethyl sulfoxide；The dispersion of ultrasonic agitation (500W ultrasonic power, 200rpm mixing speed) 50ml graphene quantum dot is molten
Liquid, joining concentration is 0.03mol/L silver nitrate solution, and controlling reaction temperature is 45 DEG C, and dropping concentration is 0.8mol/L bis-water
Close trisodium citrate, continue ultrasonic agitation 90min；Dropping 10ml graphene quantum dot dispersion soln；By pretreated glass
Fiber is added thereto, and ultrasonic agitation speed halves, and impregnates 60min, and period avoids fibre matting, impact coating effect；Take out glass
Glass fiber cleans, and dries, stand-by；Graphene quantum dot dispersion, silver nitrate solution and the volume ratio of two citric acid monohydrate trisodiums
For 4:3:2；
(4) weighing porous graphene (2 ~ 5 layers, hole size about 3 ~ 6nm), to be configured to the graphene dispersion that concentration is 0.2mg/ml molten
Liquid, solvent is water, acetone or dimethyl sulfoxide；Ultrasonic agitation (500W ultrasonic power, 200rpm mixing speed) 100ml Graphene
Dispersion soln, adds the glass fibre that step (3) prepares, ultrasonic agitation 10min, then moves to the reactor of politef
In, at 100 DEG C, it is incubated 30min；Taking-up glass fibre cleans, and dries, stand-by；
(5) weighing Zinc oxide quantum dot (particle diameter about 5 ~ 10nm) and be configured to the dispersion liquid that concentration is 0.5mg/ml, solvent is water；Super
Sound stirring (500W ultrasonic power, 200rpm mixing speed) 80ml zinc oxide fluid dispersion, adds the glass fibre that step (4) prepares
Entering wherein, ultrasonic agitation speed halves, and impregnates 60min, and period avoids fibre matting, impact coating effect；Take out glass fibre
Clean, dry, stand-by；
(6) 0. 3M titanium source (titanium source is potassium fluotitanate) is joined in 1 M sulfuric acid solution, mix homogeneously；Add step (5) system
The glass fibre obtained, is warming up to 110 DEG C, after reaction 5h, adjusts pH value to 7 with concentrated ammonia solution, after being aged 12 hours, cleans, dry
Dry, obtain loading silver/titanium dioxide composite glass fiber.
Embodiment 5
The preparation method of a kind of high intensity load silver/titanium dioxide composite glass fiber, comprises the following steps:
(1) glass fibre is prepared: 51% SiO2,15%B2O3,6%Na2O, 10%Al2O3,17.5%CaO and the carbon of wall more than 0.5% are received
After the mixing of mitron (OD about 8nm) crushing, stirring, it is placed in the corundum crucible of 400mL, founds with Si-Mo rod resistance furnace, charge temperature
Being 1370 DEG C, melted clarifying temp is 1450 ± 10 DEG C, comes out of the stove in 1200 DEG C, moulding by casting, sends in Muffle furnace, in 500 DEG C
Annealing, prepares glass；Prepared glass is heated to the temperature 1050 DEG C of wire drawing viscosity, is drawn into the glass about diameter about 10 μm
Glass fiber；
(2) glass fibre pretreatment: after taking 45 parts of glass fibre split-phases, is carried out in the HCl solution that 100ml concentration is 1mol/L
Acidleach processes, and it is to carry out under the conditions of constant temperature 95 DEG C that acidleach processes, make the Na2O-B2O3 phased soln that separates in glass fibre in
Acid, in acid add 5ml concentration be the NH4Cl solution of 40% as buffer agent, the acid treatment time is 30min；Through rinse dehydration, baking
Dry, obtain pretreated glass fiber；
(3) weigh graphene quantum dot (particle diameter about 2 ~ 5nm) and be configured to the dispersion soln that concentration is 0.3mg/ml, solvent be water,
Acetone or dimethyl sulfoxide；The dispersion of ultrasonic agitation (500W ultrasonic power, 200rpm mixing speed) 50ml graphene quantum dot is molten
Liquid, joining concentration is 0.03mol/L silver nitrate solution, and controlling reaction temperature is 45 DEG C, and dropping concentration is 0.8mol/L bis-water
Close trisodium citrate, continue ultrasonic agitation 90min；Dropping 10ml graphene quantum dot dispersion soln；By pretreated glass
Fiber is added thereto, and ultrasonic agitation speed halves, and impregnates 60min, and period avoids fibre matting, impact coating effect；Take out glass
Glass fiber cleans, and dries, stand-by；Graphene quantum dot dispersion, silver nitrate solution and the volume ratio of two citric acid monohydrate trisodiums
For 4:3:2；
(4) weighing porous graphene (2 ~ 5 layers, hole size about 3 ~ 6nm), to be configured to the graphene dispersion that concentration is 0.2mg/ml molten
Liquid, solvent is water, acetone or dimethyl sulfoxide；Ultrasonic agitation (500W ultrasonic power, 200rpm mixing speed) 100ml Graphene
Dispersion soln, adds the glass fibre that step (3) prepares, ultrasonic agitation 10min, then moves to the reactor of politef
In, at 100 DEG C, it is incubated 30min；Taking-up glass fibre cleans, and dries, stand-by；
(5) weighing Zinc oxide quantum dot (particle diameter about 5 ~ 10nm) and be configured to the dispersion liquid that 100ml concentration is 1mg/ml, solvent is
Water；Ultrasonic agitation (500W ultrasonic power, 200rpm mixing speed) 100ml zinc oxide fluid dispersion, the glass that step (4) is prepared
Fiber is added thereto, and ultrasonic agitation speed halves, and impregnates 60min, and period avoids fibre matting, impact coating effect；Take out glass
Glass fiber cleans, and dries, stand-by；
(6) 0.3M titanium source (titanium source is titanium tetrachloride) is joined in 1M sulfuric acid solution, mix homogeneously；Add step (5) to prepare
Glass fibre, be warming up to 110 DEG C, after reaction 5h, adjust pH value to 7 with concentrated ammonia solution, after be aged 12 hours, clean, dry,
Obtain loading silver/titanium dioxide composite glass fiber.
Comparative example 1
A kind of preparation method loading silver/titanium dioxide composite glass fiber, comprises the following steps:
(1) glass fibre is prepared: after 51% SiO2,15%B2O3,6%Na2O, 10%Al2O3 and 18%CaO crushing, stirring mixing,
Being placed in the corundum crucible of 400mL, found with Si-Mo rod resistance furnace, charge temperature is 1370 DEG C, and melted clarifying temp is 1450
± 10 DEG C, come out of the stove in 1200 DEG C, moulding by casting, send in Muffle furnace, in 500 DEG C of annealing, prepare glass；Prepared glass is added
Heat, to the temperature 1050 DEG C of wire drawing viscosity, is drawn into the glass fibre about diameter about 10 μm；
(2) glass fibre pretreatment: after taking 45 parts of glass fibre split-phases, is carried out in the HCl solution that 100ml concentration is 1mol/L
Acidleach processes, and it is to carry out under the conditions of constant temperature 95 DEG C that acidleach processes, make the Na2O-B2O3 phased soln that separates in glass fibre in
Acid, in acid add 5ml concentration be the NH4Cl solution of 40% as buffer agent, the acid treatment time is 30min；Through rinse dehydration, baking
Dry, obtain pretreated glass fiber；
(3) 0. 3M titanium source (titanium source is isopropyl titanate) is joined in 1 M sulfuric acid solution, mix homogeneously；Add step (3)
The glass fibre prepared, is warming up to 110 DEG C, after reaction 5h, adjusts pH value to 7 with concentrated ammonia solution, after being aged 12 hours, cleans,
It is dried, obtains carried titanium dioxide composite glass fiber.
Comparative example 2
A kind of preparation method loading silver/titanium dioxide composite glass fiber, comprises the following steps:
(1) glass fibre is prepared: after 51% SiO2,15%B2O3,6%Na2O, 10%Al2O3 and 18%CaO crushing, stirring mixing,
Being placed in the corundum crucible of 400mL, found with Si-Mo rod resistance furnace, charge temperature is 1370 DEG C, and melted clarifying temp is 1450
± 10 DEG C, come out of the stove in 1200 DEG C, moulding by casting, send in Muffle furnace, in 500 DEG C of annealing, prepare glass；Prepared glass is added
Heat, to the temperature 1050 DEG C of wire drawing viscosity, is drawn into the glass fibre about diameter about 10 μm；
(2) glass fibre pretreatment: after taking 45 parts of glass fibre split-phases, is carried out in the HCl solution that 100ml concentration is 1mol/L
Acidleach processes, and it is to carry out under the conditions of constant temperature 95 DEG C that acidleach processes, make the Na2O-B2O3 phased soln that separates in glass fibre in
Acid, in acid add 5ml concentration be the NH4Cl solution of 40% as buffer agent, the acid treatment time is 30min；Through rinse dehydration, baking
Dry, obtain pretreated glass fiber；
(3) compound concentration is 0.03mol/L silver nitrate solution, ultrasonic agitation (500W ultrasonic power, 200rpm mixing speed), will
Pretreated glass fibre is added thereto, and controlling reaction temperature is 45 DEG C, and dropping concentration is 0.8mol/L bis-citric acid monohydrate
Trisodium, continues ultrasonic agitation 60min；Taking-up glass fibre cleans, and dries, stand-by；Silver nitrate solution and two citric acid monohydrate three
The volume ratio of sodium is 3:2；
(4) 0. 3M titanium source (titanium source is isopropyl titanate) is joined in 1 M sulfuric acid solution, mix homogeneously；Add step (3)
The glass fibre prepared, is warming up to 110 DEG C, after reaction 5h, adjusts pH value to 7 with concentrated ammonia solution, after being aged 12 hours, cleans,
It is dried, obtains loading silver/titanium dioxide composite glass fiber.
Make naval stores according to a conventional method by loading silver/titanium dioxide composite glass fiber above and carry out mechanical property
Test and anti-microbial property test.
Mechanics Performance Testing:
Antibiotic property is tested:
Anti-microbial property detection, with reference to state of People's Republic of China (PRC) light industry standard QB/T2591-2003, uses film applicator coating, investigates
The antibiotic rate of sample 6 ~ 48h, total plate count measures and counts with reference to GB/T4789.2-2003；Make hot-forming for naval stores
The antibacterial model of 50*50mm.The computing formula of antibiotic rate is as follows: R%=(B-C)/B*100, wherein, R be antibiotic rate (%), B be empty
The white average bacterial count recovered of control sample, cfu/ sheet, C is the average bacterial count recovered of antibacterial model, cfu/ sheet.Sterilization rate test result is such as
Following table:
It addition, antibacterial for after the wearability of test above load silver/titanium dioxide composite glass fiber and long-term practical abrasion
Effect, is simulated using wear testing by antibacterial model, the abrasive material that wear testing selects Mohs' hardness to be 3～4, friction 1000
The secondary effect imitated after using 2 years.After friction, sample clean is dried, and test antibacterial effect according to the method described above.Sterilizing
Rate test result is as follows:
Further, carry out heat stability testing, be antibacterial model is placed in 60 DEG C under the conditions of place 10h, sterilization rate test result is such as
Under:
Embodiment described above only have expressed embodiments of the present invention, therefore it describes more concrete and detailed, but can not be
And it is interpreted as the restriction to the scope of the claims of the present invention, as long as using the technical side that the form of equivalent or equivalent transformation is obtained
Case, all should fall within the scope and spirit of the invention.
Claims (7)
1. a preparation method for high intensity load silver/titanium dioxide composite glass fiber, comprises the following steps:
(1) glass fibre is prepared: by 50 ~ 55% SiO2,10 ~ 15%B2O3,5 ~ 10%Na2O, 10 ~ 15%Al2O3,15 ~ 20%CaO
After 0.1 ~ 0.5% multi-walled carbon nano-tubes crushing, stirring mixing, it is placed in the corundum crucible of 400mL, melts with Si-Mo rod resistance furnace
System, charge temperature is 1370 DEG C, and melted clarifying temp is 1450 ± 10 DEG C, comes out of the stove in 1200 DEG C, moulding by casting, sends into Muffle furnace
In, in 500 DEG C of annealing, prepare glass；Prepared glass is heated to the temperature 1050 DEG C of wire drawing viscosity, is drawn into glass fibers
Dimension；
(2) glass fibre pretreatment；
(3) weighing graphene quantum dot and be configured to the dispersion soln that concentration is 0.1 ~ 1mg/ml, solvent is water, acetone or dimethyl
Sulfoxide；Ultrasonic agitation 50 ~ 60ml graphene quantum dot dispersion soln, joining concentration is that 0.01 ~ 0.03mol/L silver nitrate is molten
Liquid, controlling reaction temperature is 45 ~ 60 DEG C, and dropping concentration is 0.1～0.8mol/L bis-citric acid monohydrate trisodium, continues ultrasonic agitation
60~120min；Dropping 10 ~ 20ml graphene quantum dot dispersion soln；Pretreated glass fibre is added thereto, ultrasonic stirs
Mix speed to halve, impregnate 30 ~ 60min；Taking-up glass fibre cleans, and dries, stand-by；Graphene quantum dot dispersion, silver nitrate
The volume ratio of solution and two citric acid monohydrate trisodiums is 3 ~ 4:2 ~ 3:1 ~ 2；
(4) weigh porous graphene and be configured to the graphene dispersion solution that concentration is 0.2 ~ 0.8mg/ml, solvent be water, acetone or
Dimethyl sulfoxide；Ultrasonic agitation 80 ~ 100ml graphene dispersion solution, adds the glass fibre that step (3) prepares, ultrasonic agitation
10min, then moves in the reactor of politef, is incubated 15 ~ 30min at 80 ~ 120 DEG C；Taking-up glass fibre cleans,
Dry, stand-by；
(5) weighing Zinc oxide quantum dot and be configured to the dispersion liquid that concentration is 0.5 ~ 1mg/ml, solvent is water；Ultrasonic agitation 80 ~
100ml zinc oxide fluid dispersion, by step (4) prepare glass fibre be added thereto, ultrasonic agitation speed halves, dipping 30 ~
60min；Taking-up glass fibre cleans, and dries, stand-by；
(6) 0.1 ~ 0. 3M titanium source is joined in 1 M sulfuric acid solution, mix homogeneously；Add the glass fibre that step (5) prepares,
It is warming up to 110 DEG C, after reaction 3 ~ 5h, adjusts pH value to 7 with concentrated ammonia solution, after being aged 12 hours, clean, be dried, loaded
Silver/titanium dioxide composite glass fiber.
The preparation method of high intensity the most according to claim 1 load silver/titanium dioxide composite glass fiber, its feature exists
In, described step (2) specifically includes following steps: after taking 5 ~ 50 parts of glass fibre split-phases, molten at the HCl that concentration is 1 ~ 2mol/L
Carrying out acidleach process in liquid, it is to carry out under the conditions of constant temperature 90 ~ 95 DEG C that acidleach processes, and makes the Na2O-separated in glass fibre
B2O3 phased soln adds NH4Cl solution that concentration is 40% as buffer agent in acid, acid, and the acid treatment time is 30 ~ 60min；Warp
Rinse dehydration, drying, obtain pretreated glass fiber.
The preparation method of high intensity the most according to claim 1 load silver/titanium dioxide composite glass fiber, its feature exists
In, the particle diameter of described graphene quantum dot is 2 ~ 10nm.
4. the preparation method of silver/titanium dioxide composite glass fiber is loaded according to the high intensity described in claim 1,2 or 3, its
Being characterised by, described porous graphene is 2 ~ 5 layers, and hole size is the porous graphene of 3 ~ 6nm.
The preparation method of high intensity the most according to claim 1 load silver/titanium dioxide composite glass fiber, its feature exists
In, described titanium source is potassium fluotitanate, ammonium titanium fluoride, isopropyl titanate or titanium tetrachloride.
The preparation method of high intensity the most according to claim 4 load silver/titanium dioxide composite glass fiber, its feature exists
In, described Zinc oxide quantum dot particle diameter is 5 ~ 10nm.
7. the high intensity load silver/titanium dioxide composite glass fiber that the method according to any one of claim 1 to 6 prepares.
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| CN114057225A (en) * | 2020-08-05 | 2022-02-18 | 黄石加柯环保科技有限公司 | Method and equipment for preparing linear titanium dioxide crystal |
| CN114249545A (en) * | 2021-12-08 | 2022-03-29 | 天津包钢稀土研究院有限责任公司 | Coated glass with ultraviolet shielding function |
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