CN106243390B - A kind of high-intensitive load silver/titanium dioxide compound glass is fine and its ties up preparation method - Google Patents
A kind of high-intensitive load silver/titanium dioxide compound glass is fine and its ties up preparation method Download PDFInfo
- Publication number
- CN106243390B CN106243390B CN201610612844.0A CN201610612844A CN106243390B CN 106243390 B CN106243390 B CN 106243390B CN 201610612844 A CN201610612844 A CN 201610612844A CN 106243390 B CN106243390 B CN 106243390B
- Authority
- CN
- China
- Prior art keywords
- glass fibre
- solution
- glass
- added
- concentration
- 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
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 34
- 229910001923 silver oxide Inorganic materials 0.000 title claims abstract description 33
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Substances [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- -1 titanium dioxide compound Chemical class 0.000 title claims abstract description 11
- 239000011521 glass Substances 0.000 title claims description 38
- 239000003365 glass fiber Substances 0.000 claims abstract description 141
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 53
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 49
- 239000002131 composite material Substances 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 18
- 230000008569 process Effects 0.000 claims abstract description 12
- 239000002096 quantum dot Substances 0.000 claims description 32
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 32
- 239000006185 dispersion Substances 0.000 claims description 30
- 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
- 239000002253 acid Substances 0.000 claims description 28
- 238000012545 processing Methods 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 19
- 229910052719 titanium Inorganic materials 0.000 claims description 19
- 239000010936 titanium Substances 0.000 claims description 19
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [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
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 18
- 238000004140 cleaning Methods 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 18
- 238000013019 agitation Methods 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 17
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 229910052593 corundum Inorganic materials 0.000 claims description 14
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 14
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 11
- 238000002844 melting Methods 0.000 claims description 10
- 230000008018 melting Effects 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
- 235000019270 ammonium chloride Nutrition 0.000 claims description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 9
- 239000010431 corundum Substances 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
- 229910006295 Si—Mo Inorganic materials 0.000 claims description 8
- 230000032683 aging Effects 0.000 claims description 8
- 229960002303 citric acid monohydrate Drugs 0.000 claims description 8
- 230000018044 dehydration Effects 0.000 claims description 8
- 238000006297 dehydration reaction Methods 0.000 claims description 8
- 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 6
- 239000007788 liquid Substances 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
- 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
- 238000007598 dipping method Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000002048 multi walled nanotube Substances 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract description 27
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 12
- 230000000845 anti-microbial effect Effects 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 5
- 239000004332 silver Substances 0.000 abstract 1
- 229910052709 silver Inorganic materials 0.000 abstract 1
- 238000002156 mixing Methods 0.000 description 16
- 239000000835 fiber Substances 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- 238000005266 casting Methods 0.000 description 8
- 150000001336 alkenes Chemical class 0.000 description 7
- 239000010410 layer Substances 0.000 description 6
- 239000004575 stone 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
- 238000011068 loading method Methods 0.000 description 5
- 229910001845 yogo sapphire Inorganic materials 0.000 description 5
- 239000011152 fibreglass Substances 0.000 description 3
- 230000001954 sterilising effect Effects 0.000 description 3
- 238000004659 sterilization and disinfection Methods 0.000 description 3
- 235000005979 Citrus limon Nutrition 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 230000001580 bacterial effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 235000013399 edible fruits Nutrition 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 244000248349 Citrus limon Species 0.000 description 1
- 244000131522 Citrus pyriformis Species 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
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 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
- 238000010828 elution Methods 0.000 description 1
- 239000000945 filler 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
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 230000006872 improvement Effects 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
- 239000004579 marble Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- GALOTNBSUVEISR-UHFFFAOYSA-N molybdenum;silicon Chemical compound [Mo]#[Si] GALOTNBSUVEISR-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 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
- 238000004088 simulation Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- 238000012430 stability testing Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
- 229940038773 trisodium citrate Drugs 0.000 description 1
- SOBHUZYZLFQYFK-UHFFFAOYSA-K trisodium;hydroxy-[[phosphonatomethyl(phosphonomethyl)amino]methyl]phosphinate Chemical compound [Na+].[Na+].[Na+].OP(O)(=O)CN(CP(O)([O-])=O)CP([O-])([O-])=O SOBHUZYZLFQYFK-UHFFFAOYSA-K 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002759 woven fabric Substances 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a kind of load silver/titanium dioxide compound glass fibre and its dimension preparation methods, and the preparation method comprises the following steps: (1) preparing glass fibre；(2) glass fibre pre-processes；(3) glass fibre of preparation load silver；(4) porous graphene is coated；(5) glass fibre of preparation load silver/titanium dioxide.The mechanical property of the composite glass fiber is more excellent, can increase substantially the intensity and toughness of material, since the antibacterial characteristics of silver and titanium dioxide make composite material possess excellent anti-microbial property.In addition, method and process of the invention is simple, low in cost, practicability is good.
Description
Technical field
The present invention relates to technical field of composite materials, multiple more particularly to a kind of high-intensitive load silver/titanium dioxide
Close glass fibers and its dimension preparation method.
Background technique
Glass fibre (English original name are as follows: glass fiber or fiberglass) is a kind of inorganic non-gold haveing excellent performance
Belong to material, many kinds of, advantage is good insulating, heat resistance is strong, corrosion resistance is good, high mechanical strength, but the disadvantage is that property is crisp, resistance to
Mill property is poor.It is usually to manufacture using glass marble or post-consumer glass as raw material through techniques such as high temperature melting, wire drawing, doff, woven fabrics
At, the diameter of monofilament is several microns to twenties meters microns, is equivalent to the 1/20 ~ 1/5 of a hairline, every beam is fine
Dimension precursor is all made of hundreds of even thousands of monofilament.
Allotrope of the graphene as carbon, which is carbon atom, has honeycomb structure by what sp2 orbital hybridization was formed
Single layer two dimensional crystal material, good mechanical performance, chemical stability that graphene has etc. also will be in fields such as composite materials
It has broad application prospects.
Although graphene is coated on fiberglass surfacing with the physical property of reinforcing glass fiber currently, having,
Improvement be not it is highly desirable, need to be further enhanced.Moreover, being had been reported now by being added in fiberglass surfacing
Nano silver can be applied to filter paper and resin etc. and make it have antibacterial characteristics to assign glass fibre with anti-microbial property；But
It is that nano silver is in granular form, can only be often gathered in the privileged site of glass fibre, surface can not be evenly distributed on, to influences
Antibacterial effect；On the other hand, nano silver and glass fibre can not combine closely (especially when nano-Ag particles content increases
When, it is easy to happen agglomeration), it is easy to fall off in use, to influence service life and antibacterial effect.
Summary of the invention
Technical problem to be solved by the invention is to provide a kind of high intensity and high tenacity with durable antibiotic performance
Load silver/titanium dioxide composite glass fiber.The present invention also provides a kind of load silver/titanium dioxide compound glass is fine
Tie up preparation method.
The technical problems to be solved by the invention are achieved by the following technical programs:
A kind of preparation method of high-intensitive load silver/titanium dioxide composite glass fiber, comprising the following steps:
(1) glass fibre is prepared: by 50 ~ 55% SiO2,10 ~ 15%B2O3,5 ~ 10%Na2O, 10 ~ 15%Al2O3,15 ~ 20%
After CaO and 0.1 ~ 0.5% multi-walled carbon nanotube (OD 8nm) crushing, stirring mix, it is placed in the corundum crucible of 400mL, with silicon molybdenum
Stick resistance furnace is melted, and charge temperature is 1370 DEG C, and melting clarifying temp is 1450 ± 10 DEG C, comes out of the stove in 1200 DEG C, moulding by casting,
It is sent into Muffle furnace, anneals in 500 DEG C, glass is made；Glass obtained is heated to 1050 DEG C of temperature of wire drawing viscosity, is drawn
At about 10 μm of diameter or so of glass fibre；
(2) glass fibre pre-processes: after taking 5 ~ 50 parts of glass fibre split-phases, in the HCl solution that 100ml concentration is 1mol/L
Middle progress acidleach processing, acidleach processing is carried out under the conditions of 95 DEG C of constant temperature, and the Na2O-B2O3 separated in glass fibre is made to mix
The solution NH4Cl solution that addition 5ml concentration is 40% in acid, acid is 30min as buffer, acid processing time；Through water elution
Water, drying obtain pretreated glass fiber；
(3) it weighs graphene quantum dot (partial size about 2 ~ 5nm) and is configured to the dispersion solution that concentration is 0.1 ~ 1mg/ml, solvent
For water, acetone or dimethyl sulfoxide；(300 ~ 500W ultrasonic power, 200 ~ 300rpm mixing speed) 50 ~ 60ml stone is stirred by ultrasonic
Black alkene quantum dot disperses solution, and being added to concentration is 0.01 ~ 0.03mol/L silver nitrate solution, and control reaction temperature is 45 ~ 60
DEG C, dropwise addition concentration is 0.1~0.8mol/L two citric acid monohydrate trisodiums, continues 60 ~ 120min of ultrasonic agitation；10 ~ 20ml is added dropwise
Graphene quantum dot disperses solution；Pretreated glass fibre is added thereto, ultrasonic agitation speed halves, dipping 30 ~
During which 60min avoids fibre matting, influence to coat effect；Glass fibre cleaning is taken out, is dried, for use；Graphene quantum dot point
The volume ratio of dispersion liquid, silver nitrate solution and two citric acid monohydrate trisodiums is 3 ~ 4:2 ~ 3:1 ~ 2；
(4) it weighs porous graphene (2 ~ 5 layers, hole size about 3 ~ 6nm) and is configured to the graphite that concentration is 0.2 ~ 0.8mg/ml
Alkene disperses solution, and solvent is water, acetone or dimethyl sulfoxide；Ultrasonic agitation (300 ~ 500W ultrasonic power, 200 ~ 300rpm stirring
Speed) 80 ~ 100ml graphene dispersion solution, glass fibre made from step (3) is added, 10min is stirred by ultrasonic, then moves to
In the reaction kettle of polytetrafluoroethylene (PTFE), 15 ~ 30min is kept the temperature at 80 ~ 120 DEG C；Glass fibre cleaning is taken out, is dried, for use；
(5) it weighs Zinc oxide quantum dot (partial size about 5 ~ 10nm) and is configured to the dispersion liquid that concentration is 0.5 ~ 1mg/ml, solvent
For water；(300 ~ 500W ultrasonic power, 200 ~ 300rpm mixing speed) 80 ~ 100ml zinc oxide fluid dispersion is stirred by ultrasonic, by step
(4) glass fibre made from is added thereto, and ultrasonic agitation speed halves, and impregnates 30 ~ 60min, during which avoids fibre matting, is influenced
Coat effect；Glass fibre cleaning is taken out, is dried, for use；
(6) 0.1 ~ 0. 3M titanium source (titanium source is potassium fluotitanate, ammonium titanium fluoride, isopropyl titanate or titanium tetrachloride) is added
Into 1 M sulfuric acid solution, it is uniformly mixed；Glass fibre made from step (5) is added, is warming up to 110 DEG C, after reacting 3 ~ 5h, uses
Concentrated ammonia solution tune pH value after being aged 12 hours, cleans, drying to 7, obtains load silver/titanium dioxide composite glass fiber.
The invention has the following beneficial effects:
It by means of the present invention can be more effectively evenly dispersed coated in glass by graphene, silver and titanium dioxide
On fiber, and glass fibre and matrix interaction area and interface binding power are further increased, so that using the compound glass
The mechanical property of the composite material of glass fiber is more excellent, increases substantially the intensity and toughness of material, due to silver and titanium dioxide
The antibacterial characteristics of titanium make composite material possess excellent anti-microbial property.In addition, method and process of the invention is simple, it is at low cost
Honest and clean, practicability is good.Composite glass fiber can be used as the filler of injected plastics material, to increase the mechanically performance of plate, bulk
And antibacterial characteristics.
Specific embodiment
The present invention will now be described in detail with reference to examples, and the examples are only preferred embodiments of the present invention,
It is not limitation of the invention.
Embodiment 1
A kind of preparation method loading silver/titanium dioxide composite glass fiber, comprising the following steps:
(1) it prepares glass fibre: 51% SiO2,15%B2O3,6%Na2O, 10%Al2O3 and 18%CaO crushing, stirring is mixed
It after conjunction, is placed in the corundum crucible of 400mL, is melted with Si-Mo rod resistance furnace, charge temperature is 1370 DEG C, and melting clarifying temp is
It 1450 ± 10 DEG C, comes out of the stove in 1200 DEG C, moulding by casting is sent into Muffle furnace, is annealed in 500 DEG C, and glass is made；By glass obtained
Glass is heated to 1050 DEG C of temperature of wire drawing viscosity, is drawn into about 10 μm of diameter or so of glass fibre；
(2) glass fibre pre-processes: after taking 45 parts of glass fibre split-phases, in the HCl solution that 100ml concentration is 1mol/L
Acidleach processing is carried out, acidleach processing is carried out under the conditions of 95 DEG C of constant temperature, and the Na2O-B2O3 phased soln separated in glass fibre is made
It is 40% NH4Cl solution as buffer that 5ml concentration is added in acid, acid, and the acid processing time is 30min；Through rinse dehydration,
Drying, obtains pretreated glass fiber；
(3) it weighs graphene quantum dot (partial size about 2 ~ 5nm) and is configured to the dispersion solution that concentration is 0.1mg/ml, solvent is
Water, acetone or dimethyl sulfoxide；The dispersion of (500W ultrasonic power, 200rpm mixing speed) 60ml graphene quantum dot is stirred by ultrasonic
Solution, being added to concentration is 0.01mol/L silver nitrate solution, and control reaction temperature is 45 DEG C, and dropwise addition concentration is 0.1mol/L bis-
Citric acid monohydrate trisodium continues that 90min is stirred by ultrasonic；20ml graphene quantum dot is added dropwise and disperses solution；By pretreated glass
Glass fiber is added thereto, and ultrasonic agitation speed halves, and impregnates 60min, during which avoids fibre matting, influences to coat effect；It takes out
Glass fibre, washing for several times, are dried, for use；Graphene quantum dot dispersion, silver nitrate solution and two citric acid monohydrate trisodiums
Volume ratio is 3:2:2；
(4) it weighs porous graphene (2 ~ 5 layers, hole size about 3 ~ 6nm) and is configured to the graphene point that concentration is 0.8mg/ml
Solution is dissipated, solvent is water, acetone or dimethyl sulfoxide；(500W ultrasonic power, 200rpm mixing speed) 100ml stone is stirred by ultrasonic
Black alkene disperses solution, and glass fibre made from step (3) is added, and 10min is stirred by ultrasonic, then moves to the reaction of polytetrafluoroethylene (PTFE)
In kettle, 30min is kept the temperature at 100 DEG C；Glass fibre cleaning is taken out, is dried, for use；
(5) 0. 1M titanium source (titanium source is potassium fluotitanate) is added in 1 M sulfuric acid solution, is uniformly mixed；Step is added
(4) glass fibre made from, is warming up to 110 DEG C, after reacting 4h, with concentrated ammonia solution tune pH value to 7, after ageing 12 hours, clearly
It washes, it is dry, obtain load silver/titanium dioxide composite glass fiber.
Embodiment 2
A kind of preparation method loading silver/titanium dioxide composite glass fiber, comprising the following steps:
(1) it prepares glass fibre: 51% SiO2,15%B2O3,6%Na2O, 10%Al2O3 and 18%CaO crushing, stirring is mixed
It after conjunction, is placed in the corundum crucible of 400mL, is melted with Si-Mo rod resistance furnace, charge temperature is 1370 DEG C, and melting clarifying temp is
It 1450 ± 10 DEG C, comes out of the stove in 1200 DEG C, moulding by casting is sent into Muffle furnace, is annealed in 500 DEG C, and glass is made；By glass obtained
Glass is heated to 1050 DEG C of temperature of wire drawing viscosity, is drawn into about 10 μm of diameter or so of glass fibre；
(2) glass fibre pre-processes: after taking 45 parts of glass fibre split-phases, in the HCl solution that 100ml concentration is 1mol/L
Acidleach processing is carried out, acidleach processing is carried out under the conditions of 95 DEG C of constant temperature, and the Na2O-B2O3 phased soln separated in glass fibre is made
It is 40% NH4Cl solution as buffer that 5ml concentration is added in acid, acid, and the acid processing time is 30min；Through rinse dehydration,
Drying, obtains pretreated glass fiber；
(3) it weighs graphene quantum dot (partial size about 2 ~ 5nm) and is configured to the dispersion solution that concentration is 0.3mg/ml, solvent is
Water, acetone or dimethyl sulfoxide；The dispersion of (500W ultrasonic power, 200rpm mixing speed) 50ml graphene quantum dot is stirred by ultrasonic
Solution, being added to concentration is 0.03mol/L silver nitrate solution, and control reaction temperature is 45 DEG C, and dropwise addition concentration is 0.8mol/L bis-
Citric acid monohydrate trisodium continues that 90min is stirred by ultrasonic；10ml graphene quantum dot is added dropwise and disperses solution；By pretreated glass
Glass fiber is added thereto, and ultrasonic agitation speed halves, and impregnates 60min, during which avoids fibre matting, influences to coat effect；It takes out
Glass fibre cleaning, drying, for use；The volume of graphene quantum dot dispersion, silver nitrate solution and two citric acid monohydrate trisodiums
Than for 4:3:2；
(4) it weighs porous graphene (2 ~ 5 layers, hole size about 3 ~ 6nm) and is configured to the graphene point that concentration is 0.2mg/ml
Solution is dissipated, solvent is water, acetone or dimethyl sulfoxide；(500W ultrasonic power, 200rpm mixing speed) 100ml stone is stirred by ultrasonic
Black alkene disperses solution, and glass fibre made from step (3) is added, and 10min is stirred by ultrasonic, then moves to the reaction of polytetrafluoroethylene (PTFE)
In kettle, 30min is kept the temperature at 100 DEG C；Glass fibre cleaning is taken out, is dried, for use；
(5) 0. 3M titanium source (titanium source is isopropyl titanate) is added in 1 M sulfuric acid solution, is uniformly mixed；Step is added
(4) glass fibre made from, is warming up to 110 DEG C, after reacting 5h, with concentrated ammonia solution tune pH value to 7, after ageing 12 hours, clearly
It washes, it is dry, obtain load silver/titanium dioxide composite glass fiber.
Embodiment 3
A kind of preparation method loading silver/titanium dioxide composite glass fiber, comprising the following steps:
(1) it prepares glass fibre: 51% SiO2,15%B2O3,6%Na2O, 10%Al2O3 and 18%CaO crushing, stirring is mixed
It after conjunction, is placed in the corundum crucible of 400mL, is melted with Si-Mo rod resistance furnace, charge temperature is 1370 DEG C, and melting clarifying temp is
It 1450 ± 10 DEG C, comes out of the stove in 1200 DEG C, moulding by casting is sent into Muffle furnace, is annealed in 500 DEG C, and glass is made；By glass obtained
Glass is heated to 1050 DEG C of temperature of wire drawing viscosity, is drawn into about 10 μm of diameter or so of glass fibre；
(2) glass fibre pre-processes: after taking 45 parts of glass fibre split-phases, in the HCl solution that 100ml concentration is 1mol/L
Acidleach processing is carried out, acidleach processing is carried out under the conditions of 95 DEG C of constant temperature, and the Na2O-B2O3 phased soln separated in glass fibre is made
It is 40% NH4Cl solution as buffer that 5ml concentration is added in acid, acid, and the acid processing time is 30min；Through rinse dehydration,
Drying, obtains pretreated glass fiber；
(3) it weighs graphene quantum dot (partial size about 2 ~ 5nm) and is configured to the dispersion solution that concentration is 0.8mg/ml, solvent is
Water, acetone or dimethyl sulfoxide；The dispersion of (500W ultrasonic power, 200rpm mixing speed) 50ml graphene quantum dot is stirred by ultrasonic
Solution, being added to concentration is 0.03mol/L silver nitrate solution, and control reaction temperature is 45 DEG C, and dropwise addition concentration is 0.5mol/L bis-
Citric acid monohydrate trisodium continues that 90min is stirred by ultrasonic；20ml graphene quantum dot is added dropwise and disperses solution；By pretreated glass
Glass fiber is added thereto, and ultrasonic agitation speed halves, and impregnates 60min, during which avoids fibre matting, influences to coat effect；It takes out
Glass fibre cleaning, drying, for use；The volume of graphene quantum dot dispersion, silver nitrate solution and two citric acid monohydrate trisodiums
Than for 3:2:1；
(4) it weighs porous graphene (2 ~ 5 layers, hole size about 3 ~ 6nm) and is configured to the graphene point that concentration is 0.5mg/ml
Solution is dissipated, solvent is water, acetone or dimethyl sulfoxide；(500W ultrasonic power, 200rpm mixing speed) 80ml stone is stirred by ultrasonic
Black alkene disperses solution, and glass fibre made from step (3) is added, and 10min is stirred by ultrasonic, then moves to the reaction of polytetrafluoroethylene (PTFE)
In kettle, 30min is kept the temperature at 100 DEG C；Glass fibre cleaning is taken out, is dried, for use；
(5) 0.2M titanium source (titanium source is ammonium titanium fluoride) is added in 1 M sulfuric acid solution, is uniformly mixed；It is added step (4)
Glass fibre obtained is warming up to 110 DEG C, after reacting 3h, is cleaned after ageing 12 hours with concentrated ammonia solution tune pH value to 7,
It is dry, obtain load silver/titanium dioxide composite glass fiber.
Embodiment 4
A kind of preparation method of high-intensitive load silver/titanium dioxide composite glass fiber, comprising the following steps:
(1) glass fibre is prepared: by 51% SiO2,15%B2O3,6%Na2O, 9.8%Al2O3,18%CaO and 0.2% multi wall
It after the mixing of carbon nanotube (OD about 8nm) crushing, stirring, is placed in the corundum crucible of 400mL, is melted with Si-Mo rod resistance furnace, charging
Temperature is 1370 DEG C, and melting clarifying temp is 1450 ± 10 DEG C, is come out of the stove in 1200 DEG C, and moulding by casting is sent into Muffle furnace, in
500 DEG C of annealing, are made glass；Glass obtained is heated to 1050 DEG C of temperature of wire drawing viscosity, is drawn into about 10 μm of left sides of diameter
Right glass fibre；
(2) glass fibre pre-processes: after taking 45 parts of glass fibre split-phases, in the HCl solution that 100ml concentration is 1mol/L
Acidleach processing is carried out, acidleach processing is carried out under the conditions of 95 DEG C of constant temperature, and the Na2O-B2O3 phased soln separated in glass fibre is made
It is 40% NH4Cl solution as buffer that 5ml concentration is added in acid, acid, and the acid processing time is 30min；Through rinse dehydration,
Drying, obtains pretreated glass fiber；
(3) it weighs graphene quantum dot (partial size about 2 ~ 5nm) and is configured to the dispersion solution that concentration is 0.3mg/ml, solvent is
Water, acetone or dimethyl sulfoxide；The dispersion of (500W ultrasonic power, 200rpm mixing speed) 50ml graphene quantum dot is stirred by ultrasonic
Solution, being added to concentration is 0.03mol/L silver nitrate solution, and control reaction temperature is 45 DEG C, and dropwise addition concentration is 0.8mol/L bis-
Citric acid monohydrate trisodium continues that 90min is stirred by ultrasonic；10ml graphene quantum dot is added dropwise and disperses solution；By pretreated glass
Glass fiber is added thereto, and ultrasonic agitation speed halves, and impregnates 60min, during which avoids fibre matting, influences to coat effect；It takes out
Glass fibre cleaning, drying, for use；The volume of graphene quantum dot dispersion, silver nitrate solution and two citric acid monohydrate trisodiums
Than for 4:3:2；
(4) it weighs porous graphene (2 ~ 5 layers, hole size about 3 ~ 6nm) and is configured to the graphene point that concentration is 0.2mg/ml
Solution is dissipated, solvent is water, acetone or dimethyl sulfoxide；(500W ultrasonic power, 200rpm mixing speed) 100ml stone is stirred by ultrasonic
Black alkene disperses solution, and glass fibre made from step (3) is added, and 10min is stirred by ultrasonic, then moves to the reaction of polytetrafluoroethylene (PTFE)
In kettle, 30min is kept the temperature at 100 DEG C；Glass fibre cleaning is taken out, is dried, for use；
(5) it weighs Zinc oxide quantum dot (partial size about 5 ~ 10nm) and is configured to the dispersion liquid that concentration is 0.5mg/ml, solvent is
Water；(500W ultrasonic power, 200rpm mixing speed) 80ml zinc oxide fluid dispersion is stirred by ultrasonic, by glass made from step (4)
Fiber is added thereto, and ultrasonic agitation speed halves, and impregnates 60min, during which avoids fibre matting, influences to coat effect；Take out glass
The cleaning of glass fiber, drying, for use；
(6) 0. 3M titanium source (titanium source is potassium fluotitanate) is added in 1 M sulfuric acid solution, is uniformly mixed；Step is added
(5) glass fibre made from, is warming up to 110 DEG C, after reacting 5h, with concentrated ammonia solution tune pH value to 7, after ageing 12 hours, clearly
It washes, it is dry, obtain load silver/titanium dioxide composite glass fiber.
Embodiment 5
A kind of preparation method of high-intensitive load silver/titanium dioxide composite glass fiber, comprising the following steps:
(1) glass fibre is prepared: by 51% SiO2,15%B2O3,6%Na2O, 10%Al2O3,17.5%CaO and 0.5% multi wall
It after the mixing of carbon nanotube (OD about 8nm) crushing, stirring, is placed in the corundum crucible of 400mL, is melted with Si-Mo rod resistance furnace, charging
Temperature is 1370 DEG C, and melting clarifying temp is 1450 ± 10 DEG C, is come out of the stove in 1200 DEG C, and moulding by casting is sent into Muffle furnace, in
500 DEG C of annealing, are made glass；Glass obtained is heated to 1050 DEG C of temperature of wire drawing viscosity, is drawn into about 10 μm of left sides of diameter
Right glass fibre；
(2) glass fibre pre-processes: after taking 45 parts of glass fibre split-phases, in the HCl solution that 100ml concentration is 1mol/L
Acidleach processing is carried out, acidleach processing is carried out under the conditions of 95 DEG C of constant temperature, and the Na2O-B2O3 phased soln separated in glass fibre is made
It is 40% NH4Cl solution as buffer that 5ml concentration is added in acid, acid, and the acid processing time is 30min；Through rinse dehydration,
Drying, obtains pretreated glass fiber；
(3) it weighs graphene quantum dot (partial size about 2 ~ 5nm) and is configured to the dispersion solution that concentration is 0.3mg/ml, solvent is
Water, acetone or dimethyl sulfoxide；The dispersion of (500W ultrasonic power, 200rpm mixing speed) 50ml graphene quantum dot is stirred by ultrasonic
Solution, being added to concentration is 0.03mol/L silver nitrate solution, and control reaction temperature is 45 DEG C, and dropwise addition concentration is 0.8mol/L bis-
Citric acid monohydrate trisodium continues that 90min is stirred by ultrasonic；10ml graphene quantum dot is added dropwise and disperses solution；By pretreated glass
Glass fiber is added thereto, and ultrasonic agitation speed halves, and impregnates 60min, during which avoids fibre matting, influences to coat effect；It takes out
Glass fibre cleaning, drying, for use；The volume of graphene quantum dot dispersion, silver nitrate solution and two citric acid monohydrate trisodiums
Than for 4:3:2；
(4) it weighs porous graphene (2 ~ 5 layers, hole size about 3 ~ 6nm) and is configured to the graphene point that concentration is 0.2mg/ml
Solution is dissipated, solvent is water, acetone or dimethyl sulfoxide；(500W ultrasonic power, 200rpm mixing speed) 100ml stone is stirred by ultrasonic
Black alkene disperses solution, and glass fibre made from step (3) is added, and 10min is stirred by ultrasonic, then moves to the reaction of polytetrafluoroethylene (PTFE)
In kettle, 30min is kept the temperature at 100 DEG C；Glass fibre cleaning is taken out, is dried, for use；
(5) it weighs Zinc oxide quantum dot (partial size about 5 ~ 10nm) and is configured to the dispersion liquid that 100ml concentration is 1mg/ml, solvent
For water；(500W ultrasonic power, 200rpm mixing speed) 100ml zinc oxide fluid dispersion is stirred by ultrasonic, by glass made from step (4)
Glass fiber is added thereto, and ultrasonic agitation speed halves, and impregnates 60min, during which avoids fibre matting, influences to coat effect；It takes out
Glass fibre cleaning, drying, for use；
(6) 0.3M titanium source (titanium source is titanium tetrachloride) is added in 1M sulfuric acid solution, is uniformly mixed；It is added step (5)
Glass fibre obtained is warming up to 110 DEG C, after reacting 5h, is cleaned after ageing 12 hours with concentrated ammonia solution tune pH value to 7,
It is dry, obtain load silver/titanium dioxide composite glass fiber.
Comparative example 1
A kind of preparation method loading silver/titanium dioxide composite glass fiber, comprising the following steps:
(1) it prepares glass fibre: 51% SiO2,15%B2O3,6%Na2O, 10%Al2O3 and 18%CaO crushing, stirring is mixed
It after conjunction, is placed in the corundum crucible of 400mL, is melted with Si-Mo rod resistance furnace, charge temperature is 1370 DEG C, and melting clarifying temp is
It 1450 ± 10 DEG C, comes out of the stove in 1200 DEG C, moulding by casting is sent into Muffle furnace, is annealed in 500 DEG C, and glass is made；By glass obtained
Glass is heated to 1050 DEG C of temperature of wire drawing viscosity, is drawn into about 10 μm of diameter or so of glass fibre；
(2) glass fibre pre-processes: after taking 45 parts of glass fibre split-phases, in the HCl solution that 100ml concentration is 1mol/L
Acidleach processing is carried out, acidleach processing is carried out under the conditions of 95 DEG C of constant temperature, and the Na2O-B2O3 phased soln separated in glass fibre is made
It is 40% NH4Cl solution as buffer that 5ml concentration is added in acid, acid, and the acid processing time is 30min；Through rinse dehydration,
Drying, obtains pretreated glass fiber；
(3) 0. 3M titanium source (titanium source is isopropyl titanate) is added in 1 M sulfuric acid solution, is uniformly mixed；Step is added
(3) glass fibre made from, is warming up to 110 DEG C, after reacting 5h, with concentrated ammonia solution tune pH value to 7, after ageing 12 hours, clearly
It washes, it is dry, obtain carried titanium dioxide composite glass fiber.
Comparative example 2
A kind of preparation method loading silver/titanium dioxide composite glass fiber, comprising the following steps:
(1) it prepares glass fibre: 51% SiO2,15%B2O3,6%Na2O, 10%Al2O3 and 18%CaO crushing, stirring is mixed
It after conjunction, is placed in the corundum crucible of 400mL, is melted with Si-Mo rod resistance furnace, charge temperature is 1370 DEG C, and melting clarifying temp is
It 1450 ± 10 DEG C, comes out of the stove in 1200 DEG C, moulding by casting is sent into Muffle furnace, is annealed in 500 DEG C, and glass is made；By glass obtained
Glass is heated to 1050 DEG C of temperature of wire drawing viscosity, is drawn into about 10 μm of diameter or so of glass fibre；
(2) glass fibre pre-processes: after taking 45 parts of glass fibre split-phases, in the HCl solution that 100ml concentration is 1mol/L
Acidleach processing is carried out, acidleach processing is carried out under the conditions of 95 DEG C of constant temperature, and the Na2O-B2O3 phased soln separated in glass fibre is made
It is 40% NH4Cl solution as buffer that 5ml concentration is added in acid, acid, and the acid processing time is 30min；Through rinse dehydration,
Drying, obtains pretreated glass fiber；
(3) compound concentration is 0.03mol/L silver nitrate solution, ultrasonic agitation (500W ultrasonic power, 200rpm stirring speed
Degree), pretreated glass fibre is added thereto, control reaction temperature is 45 DEG C, and concentration is added dropwise as the hydration of 0.8mol/L bis-
Trisodium citrate continues that 60min is stirred by ultrasonic；Glass fibre cleaning is taken out, is dried, for use；Silver nitrate solution and two hydration lemons
The volume ratio of lemon acid trisodium is 3:2；
(4) 0. 3M titanium source (titanium source is isopropyl titanate) is added in 1 M sulfuric acid solution, is uniformly mixed；Step is added
(3) glass fibre made from, is warming up to 110 DEG C, after reacting 5h, with concentrated ammonia solution tune pH value to 7, after ageing 12 hours, clearly
It washes, it is dry, obtain load silver/titanium dioxide composite glass fiber.
Naval stores is made in the above load silver/titanium dioxide composite glass fiber according to a conventional method and carries out mechanical property
Test and anti-microbial property test.
Mechanics Performance Testing:
Antibiotic property test:
Anti-microbial property detection is referring to state of People's Republic of China (PRC) light industry standard QB/T2591-2003, using film applicator coating,
The antibiotic rate of 6 ~ 48h of sample is investigated, total plate count measurement is counted referring to GB/T4789.2-2003；Naval stores is hot-forming
The antibacterial template of 50*50mm is made.The calculation formula of antibiotic rate is as follows: R%=(B-C)/B*100, wherein R is antibiotic rate (%), B
It is averaged bacterial count recovered for blank control sample, cfu/ piece, C is that antibacterial template is averaged bacterial count recovered, cfu/ piece.Sterilization rate test knot
Fruit is as follows:
In addition, after for the wearability and long-term practical abrasion of the above load silver/titanium dioxide composite glass fiber of test
Antibacterial template is carried out simulation using wear testing by antibacterial effect, and it is 3~4 abrasive material, friction that wear testing, which selects Mohs' hardness,
It imitates using the effect after 2 years for 1000 times.Sample clean is dried after friction, and tests antibacterial effect according to the method described above.
Test result is as follows for sterilization rate:
It is that antibacterial template is placed under the conditions of 60 DEG C to place 10h in addition, carrying out heat stability testing, sterilization rate test knot
Fruit is as follows:
Embodiments of the present invention above described embodiment only expresses, the description thereof is more specific and detailed, but can not
Therefore limitations on the scope of the patent of the present invention are interpreted as, as long as skill obtained in the form of equivalent substitutions or equivalent transformations
Art scheme should all be fallen within the scope and spirit of the invention.
Claims (5)
1. a kind of preparation method of high-intensitive load silver/titanium dioxide composite glass fiber, comprising the following steps:
(1) glass fibre is prepared: by weight percentage, by 50 ~ 55% SiO2,10 ~ 15%B2O3,5 ~ 10%Na2O, 10 ~ 15%
It after Al2O3,15 ~ 20%CaO and 0.1 ~ 0.5% multi-walled carbon nanotube crushing, stirring mix, is placed in the corundum crucible of 400mL, uses
Si-Mo rod resistance furnace is melted, and charge temperature is 1370 DEG C, and melting clarifying temp is 1450 ± 10 DEG C, is come out of the stove in 1200 DEG C, is poured
Molding is sent into Muffle furnace, is annealed in 500 DEG C, and glass is made；Glass obtained is heated to the temperature 1050 of wire drawing viscosity
DEG C, it is drawn into glass fibre；
(2) glass fibre pre-processes: after taking 5 ~ 50 parts of glass fibre split-phases, carrying out in the HCl solution that concentration is 1 ~ 2mol/L
Acidleach processing, acidleach processing is carried out under the conditions of 90 ~ 95 DEG C of constant temperature, makes the Na2O-B2O3 phased soln separated in glass fibre
It is 40% NH4Cl solution as buffer that concentration is added in acid, acid, and the acid processing time is 30 ~ 60min；Through rinse dehydration,
Drying, obtains pretreated glass fiber；
(3) weighing partial size is the dispersion solution that 2 ~ 10nm graphene quantum dot is configured to that concentration is 0.1 ~ 1mg/ml, solvent be water,
Acetone or dimethyl sulfoxide；Be stirred by ultrasonic 50 ~ 60ml graphene quantum dot disperse solution, be added to concentration be 0.01 ~
0.03mol/L silver nitrate solution, control reaction temperature are 45 ~ 60 DEG C, and dropwise addition concentration is 0.1~0.8mol/L, bis- citric acid monohydrate
Trisodium continues 60 ~ 120min of ultrasonic agitation；10 ~ 20ml graphene quantum dot is added dropwise and disperses solution；By pretreated glass fibers
Dimension is added thereto, and ultrasonic agitation speed halves, and impregnates 30 ~ 60min；Glass fibre cleaning is taken out, is dried, for use；Graphene amount
The volume ratio of son point dispersion liquid, silver nitrate solution and two citric acid monohydrate trisodiums is 3 ~ 4:2 ~ 3:1 ~ 2；
(4) weigh porous graphene be configured to concentration be 0.2 ~ 0.8mg/ml graphene dispersion solution, solvent be water, acetone or
Dimethyl sulfoxide；80 ~ 100ml graphene dispersion solution is stirred by ultrasonic, glass fibre made from step (3), ultrasonic agitation is added
Then 10min is moved in the reaction kettle of polytetrafluoroethylene (PTFE), 15 ~ 30min is kept the temperature at 80 ~ 120 DEG C；Glass fibre cleaning is taken out,
Drying, for use；
(5) it weighs Zinc oxide quantum dot and is configured to the dispersion liquid that concentration is 0.5 ~ 1mg/ml, solvent is water；Ultrasonic agitation 80 ~
Glass fibre made from step (4) is added thereto by 100ml zinc oxide fluid dispersion, and ultrasonic agitation speed halves, and dipping 30 ~
60min；Glass fibre cleaning is taken out, is dried, for use；
(6) 0.1 ~ 0. 3M titanium source is added in 1 M sulfuric acid solution, is uniformly mixed；Glass fibre made from step (5) is added,
110 DEG C are warming up to, after reacting 3 ~ 5h, is cleaned after ageing 12 hours with concentrated ammonia solution tune pH value to 7, it is dry, it is loaded
Silver/titanium dioxide composite glass fiber.
2. the preparation method of high-intensitive load silver/titanium dioxide composite glass fiber according to claim 1, feature exist
In the porous graphene is 2 ~ 5 layers, and hole size is the porous graphene of 3 ~ 6nm.
3. the preparation method of high-intensitive load silver/titanium dioxide composite glass fiber according to claim 1, feature exist
In the titanium source is potassium fluotitanate, ammonium titanium fluoride, isopropyl titanate or titanium tetrachloride.
4. the preparation method of high-intensitive load silver/titanium dioxide composite glass fiber according to claim 3, feature exist
In the Zinc oxide quantum dot partial size is 5 ~ 10nm.
5. high intensity made from method described in any one of Claims 1-4 loads silver/titanium dioxide composite glass fiber.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610612844.0A CN106243390B (en) | 2016-07-29 | 2016-07-29 | A kind of high-intensitive load silver/titanium dioxide compound glass is fine and its ties up preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610612844.0A CN106243390B (en) | 2016-07-29 | 2016-07-29 | A kind of high-intensitive load silver/titanium dioxide compound glass is fine and its ties up preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106243390A CN106243390A (en) | 2016-12-21 |
| CN106243390B true CN106243390B (en) | 2018-12-11 |
Family
ID=57606029
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610612844.0A Active CN106243390B (en) | 2016-07-29 | 2016-07-29 | A kind of high-intensitive load silver/titanium dioxide compound glass is fine and its ties up preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106243390B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107583642A (en) * | 2017-09-15 | 2018-01-16 | 合肥师范学院 | Graphene quantum dot loaded Ag TiO2The preparation method of nano-array |
| 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 |
| CN114249545B (en) * | 2021-12-08 | 2023-12-12 | 天津包钢稀土研究院有限责任公司 | Coated glass with ultraviolet shielding function |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102719067A (en) * | 2012-06-28 | 2012-10-10 | 广州高金技术产业集团有限公司 | High-performance fiberglass reinforced plastic composite material and preparation method thereof |
| CN103469543A (en) * | 2013-08-06 | 2013-12-25 | 苏州三和开泰花线织造有限公司 | Anti-ultraviolet ray silk fabric production method |
| CN103599800A (en) * | 2013-11-22 | 2014-02-26 | 中国科学院新疆理化技术研究所 | Preparation method of glass fiber loaded silver-silver bromide-titanium oxide composite material |
| CN104163578A (en) * | 2014-07-22 | 2014-11-26 | 杭州杭复新材料科技有限公司 | Preparation method of graphene coated composite glass fiber |
| CN104710107A (en) * | 2015-02-10 | 2015-06-17 | 安徽丹凤集团桐城玻璃纤维有限公司 | Preparation method of porous glass fiber for water purification treatment |
-
2016
- 2016-07-29 CN CN201610612844.0A patent/CN106243390B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102719067A (en) * | 2012-06-28 | 2012-10-10 | 广州高金技术产业集团有限公司 | High-performance fiberglass reinforced plastic composite material and preparation method thereof |
| CN103469543A (en) * | 2013-08-06 | 2013-12-25 | 苏州三和开泰花线织造有限公司 | Anti-ultraviolet ray silk fabric production method |
| CN103599800A (en) * | 2013-11-22 | 2014-02-26 | 中国科学院新疆理化技术研究所 | Preparation method of glass fiber loaded silver-silver bromide-titanium oxide composite material |
| CN104163578A (en) * | 2014-07-22 | 2014-11-26 | 杭州杭复新材料科技有限公司 | Preparation method of graphene coated composite glass fiber |
| CN104710107A (en) * | 2015-02-10 | 2015-06-17 | 安徽丹凤集团桐城玻璃纤维有限公司 | Preparation method of porous glass fiber for water purification treatment |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106243390A (en) | 2016-12-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106243696B (en) | A kind of high-performance composite glass fiber reinforced resin material and preparation method thereof | |
| CN106147210B (en) | A kind of composite glass fiber reinforced resin material and preparation method thereof | |
| CN106243390B (en) | A kind of high-intensitive load silver/titanium dioxide compound glass is fine and its ties up preparation method | |
| Chen et al. | Ultra high performance cement-based composites incorporating low dosage of plasma synthesized carbon nanotubes | |
| CN106243658B (en) | A kind of high-performance polyester glass-reinforced plastic material of durable antibiotic and preparation method thereof | |
| CN106118003B (en) | A kind of modified reinforced polyester glass-reinforced plastic material and preparation method thereof | |
| CN106189151B (en) | A kind of composite glass fiber reinforced polyester glass-reinforced plastic material and preparation method thereof | |
| CN106219989B (en) | A kind of graphene is modified the preparation method of composite glass fiber | |
| CN106752119A (en) | A kind of preparation method of carbon black nano material | |
| CN106189220B (en) | A kind of graphene modified glass-fiber reinforced resin composite material and preparation method | |
| Wu et al. | Improving electrical, mechanical, thermal and hydrophobic properties of waterborne acrylic resin-glycidyl methacrylate (GMA) by adding multi-walled carbon nanotubes | |
| CN106277747B (en) | A kind of load silver/titanium dioxide compound glass is fine and its ties up preparation method | |
| CN109864042A (en) | A kind of nano-graphene preparing high thermal conductivity silk freshens food and educates silkworm method and its product | |
| CN110093680A (en) | A kind of graphene/cage modle polysilsesquioxane modified polyester fiber and preparation method | |
| CN107663328A (en) | The preparation method of carbon fiber and the ultrahigh molecular weight polyethylene abrasion-proof material of silica nanosphere collaboration filling | |
| CN106223121B (en) | A kind of durable antibiotic glass fibre air filter paper and preparation method thereof | |
| CN110184667A (en) | A kind of modified white graphite allyl synthetic fibre composite fibre and preparation method thereof | |
| CN110205809A (en) | A kind of method for sizing of carbon fiber and its application | |
| CN106220118B (en) | A kind of composite glass fiber reinforced plasterboard and its manufacturing method | |
| CN105461975B (en) | A kind of preparation method of natural rubber/palygorskite nano composite material | |
| CN106220831A (en) | A kind of preparation method of poly-lactic acid material | |
| CN106277748B (en) | A kind of antibacterial glass fibre reinforced plasterboard and its manufacturing method | |
| JPH04222866A (en) | Production of thermoplastic mixture suitable for using with reinforcing glass material used for the production of thermoplastic composite material | |
| CN105461974B (en) | A kind of preparation method of modified attapulgite used for rubber reinforcement | |
| Han et al. | Nano-TiO 2-engineered cementitious composites |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into 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: 20191115 Address after: 233010 No.2, third floor, No.319, zhanggongshan Road, zhanggongshan street, Yuhui District, Bengbu City, Anhui Province Patentee after: Bengbu aochuang Intellectual Property Operation Co.,Ltd. Address before: Foshan City, Guangdong province 528500 city streets Gaoming District (Xi'an) Guang'an River Road Development Zone No. 4 5 first floor of the garage Patentee before: FOSHAN GAOMING DISTRICT CHENGRUIJI TECHNOLOGY Co.,Ltd. |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20240110 Address after: 036002 Xinxing Industrial Park, Development Zone, Shuozhou City, Shanxi Province, North South Avenue West (Aluminum Factory East) Patentee after: Shuozhou Runyu Industry and Trade Co.,Ltd. Address before: 233010 No.2, 3rd floor, No.319, zhanggongshan Road, Yuhui District, Bengbu City, Anhui Province Patentee before: Bengbu aochuang Intellectual Property Operation Co.,Ltd. |
|
| TR01 | Transfer of patent right |