CN106243696B - A kind of high-performance composite glass fiber reinforced resin material and preparation method thereof - Google Patents
A kind of high-performance composite glass fiber reinforced resin material and preparation method thereof Download PDFInfo
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- 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
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
- C08J5/08—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials glass fibres
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- C08K9/00—Use of pretreated ingredients
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- C08K2003/0806—Silver
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- 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
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Abstract
The invention discloses a kind of composite glass fiber reinforced resin materials and preparation method thereof, and the preparation method comprises the following steps：（1）Prepare glass fibre；（2）Glass fibre pre-processes；（3）Prepare the glass fibre of load silver；（4）Coat porous graphene；（5）Prepare the glass fibre of load silver/titanium dioxide；（6）It prepares graphene modified glass-fiber reinforcement and is modified by silane coupling agent, it is compound with resin-based materials.The mechanical property of the composite glass fiber reinforced resin material is more excellent, can increase substantially the intensity and toughness of material, simultaneously because the antibacterial characteristics of silver and titanium dioxide make composite material possess excellent anti-microbial property.In addition, the method and process of the present invention is simple, of low cost, practicability is good.
Description
Technical field
The present invention relates to technical field of composite materials, enhance more particularly to a kind of high-performance composite glass fiber and set
Fat material and preparation method thereof.
Background technology
Glass fibre（English original name is：Glass fiber or fiberglass）It is a kind of inorganic non-gold haveing excellent performance
Belong to material, type is various, and 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 be manufactured through techniques such as high temperature melting, wire drawing, doff, woven fabrics as raw material using glass marble or discarded glass
At, a diameter of several microns of monofilament are equivalent to the 1/20 ~ 1/5 of a hairline to twenties meters microns, fine per beam
Dimension precursor is all made of hundreds of even thousands of monofilament.
Allotrope of the graphene as carbon is carbon atom has honeycomb structure by what sp2 orbital hybridizations were 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 reinforced resin sill currently, having,
It is highly desirable to be that improvement is not, need to be further enhanced.Moreover, being had been reported now by adding in fiberglass surfacing
Plus 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 nano silver is in granular form, and can only often be gathered in the privileged site of glass fibre, can not be evenly distributed on surface, to shadow
Loud antibacterial effect；On the other hand, nano silver can not combine closely with glass fibre（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.
Invention content
Technical problem to be solved by the invention is to provide a kind of high intensity and high tenacity with durable antibiotic performance
Composite glass fiber reinforced resin material.The present invention also provides a kind of high-performance composite glass fiber reinforced resin material systems
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-performance composite glass fiber reinforced resin material, includes the following steps：
（1）Prepare glass fibre：By 50 ~ 55% SiO2,10 ~ 15%B2O3,5 ~ 10%Na2O, 10 ~ 15%Al2O3,15 ~ 20%
CaO and 0.1 ~ 0.5% multi-walled carbon nanotube（OD is 8nm）After crushing, stirring mixing, 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, is come out of the stove in 1200 DEG C, moulding by casting,
It is sent into Muffle furnace, in 500 DEG C of annealing, glass is made；Glass obtained is heated to 1050 DEG C of the temperature of wire drawing viscosity, is drawn
At about 10 μm or so of glass fibre of diameter；
（2）Glass fibre pre-processes：After taking 5 ~ 50 parts of glass fibre split-phases, in the HCl solution of a concentration of 1mol/L of 100ml
Middle progress acidleach processing, acidleach processing are 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 NH4Cl solution of 5ml a concentration of 40% is added as buffer in solution in acid, acid, and sour processing time is 30min；Through water elution
Water, drying obtain pretreated glass fiber；
（3）Weigh graphene quantum dot（Grain size about 2 ~ 5nm）It is configured to the dispersion solution of a concentration of 0.1 ~ 1mg/ml, solvent
For water, acetone or dimethyl sulfoxide (DMSO)；Ultrasonic agitation（300 ~ 500W ultrasonic powers, 200 ~ 300rpm mixing speeds）50 ~ 60ml stones
Black alkene quantum dot disperses solution, is added to a concentration of 0.01 ~ 0.03mol/L silver nitrate solutions, and controlling reaction temperature is 45 ~ 60
DEG C, a concentration of 0.1~0.8mol/L two citric acid monohydrate trisodiums are added dropwise, continue 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）Weigh porous graphene（2 ~ 5 layers, hole size about 3 ~ 6nm）It is configured to the graphite of a concentration of 0.2 ~ 0.8mg/ml
Alkene disperses solution, and solvent is water, acetone or dimethyl sulfoxide (DMSO)；Ultrasonic agitation（300 ~ 500W ultrasonic powers, 200 ~ 300rpm stirrings
Speed）Step is added in 80 ~ 100ml graphene dispersion solution（3）Glass fibre obtained is stirred by ultrasonic 10min, 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）Weigh Zinc oxide quantum dot（Grain size about 5 ~ 10nm）It is configured to the dispersion liquid of a concentration of 0.5 ~ 1mg/ml, solvent
For water；Ultrasonic agitation（300 ~ 500W ultrasonic powers, 200 ~ 300rpm mixing speeds）80 ~ 100ml zinc oxide fluid dispersions, by step
（4）Glass fibre obtained is added thereto, and ultrasonic agitation speed halves, and impregnates 30 ~ 60min, during which avoids fibre matting, influences
Coat effect；Glass fibre cleaning is taken out, is dried, for use；
（6）By 0.1 ~ 0. 3M titanium sources（Titanium source is potassium fluotitanate, ammonium titanium fluoride, isopropyl titanate or titanium tetrachloride）It is added
Into 1 M sulfuric acid solutions, it is uniformly mixed；Step is added（5）Glass fibre obtained is warming up to 110 DEG C, after reacting 3 ~ 5h, uses
Concentrated ammonia solution tune pH value is to 7, after being aged 12 hours, cleans, dry, obtains load silver/titanium dioxide composite glass fiber；
（7）By step（6）Load silver/titanium dioxide composite glass fiber obtained is with silane coupling agent in second alcohol and water
Reacted in mixed solution, at 55~75 DEG C react 20~for 24 hours, reaction products therefrom successively use ethyl alcohol, water washing, finally exist
15 ~ 30min is centrifuged under the centrifugation rate of 8000~10000r/min obtains silane coupler modified glass fiber reinforcements；Institute
The silane coupling agent stated is one kind in vinyl type, epoxy base type, amine type or methacryloxy type；Institute
The mass ratio for stating load silver/titanium dioxide composite glass fiber and silane coupling agent is 1:12；The mixing of the second alcohol and water
In solvent, the volume ratio of second alcohol and water is 3:2；The volumetric usage of the ethyl alcohol and water mixed solvent is to load silver/titanium dioxide
The quality of titanium composite glass fiber is calculated as 400mL/g；
（8）By resin and step（7）Silane coupler modified glass fiber reinforcements obtained are added to twin-screw and squeeze
Go out melt blending in machine, squeeze out, is molded and composite glass fiber reinforced resin material is made.
The present invention has the advantages that：
Method through the 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 resin material mechanical property of glass fiber is more excellent, increases substantially the intensity and toughness of material, due to silver and titanium dioxide
Antibacterial characteristics make composite material possess excellent anti-microbial property.In addition, the method and process of the present invention is simple, it is of low cost,
Practicability is good.Composite glass fiber can be as the filler of injected plastics material, to increase the mechanical performance of plank, bulk and resist
Bacterium characteristic.
Specific implementation mode
With reference to embodiment, the present invention will be described in detail, and embodiment is only the preferred embodiment of the present invention,
It is not limitation of the invention.For convenience of description, resin-based materials are by taking nylon resin as an example, but those skilled in the art are easy
Know and is not limited thereto.
Embodiment 1
A kind of preparation method of high-performance composite glass fiber reinforced resin material, includes the following steps：
（1）Prepare 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, and in 500 DEG C of annealing, glass is made；By glass obtained
Glass is heated to 1050 DEG C of the temperature of wire drawing viscosity, is drawn into the glass fibre of about 10 μm or so of diameter；
（2）Glass fibre pre-processes：After taking 45 parts of glass fibre split-phases, in the HCl solution of a concentration of 1mol/L of 100ml
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 solns separated in glass fibre are made
The NH4Cl solution of 5ml a concentration of 40% is added in acid, acid as buffer, sour processing time is 30min；Through rinse dehydration,
Drying, obtains pretreated glass fiber；
（3）Weigh graphene quantum dot（Grain size about 2 ~ 5nm）It is configured to the dispersion solution of a concentration of 0.1mg/ml, solvent is
Water, acetone or dimethyl sulfoxide (DMSO)；Ultrasonic agitation（500W ultrasonic powers, 200rpm mixing speeds）60ml graphene quantum dots disperse
Solution is added to a concentration of 0.01mol/L silver nitrate solutions, and controlling reaction temperature is 45 DEG C, and a concentration of 0.1mol/L bis- is added dropwise
Citric acid monohydrate trisodium continues that 90min is stirred by ultrasonic；20ml graphene quantum dots are added dropwise and disperse 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）Weigh porous graphene（2 ~ 5 layers, hole size about 3 ~ 6nm）It is configured to the graphene point of a concentration of 0.8mg/ml
Solution is dissipated, solvent is water, acetone or dimethyl sulfoxide (DMSO)；Ultrasonic agitation（500W ultrasonic powers, 200rpm mixing speeds）100ml stones
Black alkene disperses solution, and step is added（3）Glass fibre obtained is stirred by ultrasonic 10min, 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）By 0. 1M titanium sources（Titanium source is potassium fluotitanate）It is added in 1 M sulfuric acid solutions, is uniformly mixed；Step is added
（4）Glass fibre obtained, 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；
（6）By step（5）Load silver/titanium dioxide composite glass fiber obtained is with silane coupling agent in second alcohol and water
It reacts, is reacted at 60 DEG C for 24 hours in mixed solution, reaction products therefrom uses ethyl alcohol, water washing successively, finally in 8000r/min
Centrifugation rate under centrifugation 30min obtain silane coupler modified glass fiber reinforcements, the silane coupling agent is second
Alkenyl type；The mass ratio of the load silver/titanium dioxide composite glass fiber and silane coupling agent is 1:12；The ethyl alcohol
Volume ratio with the in the mixed solvent of water, second alcohol and water is 3:2；The volumetric usage of the ethyl alcohol and water mixed solvent is to load
The quality of silver/titanium dioxide composite glass fiber is calculated as 400mL/g；
（7）By nylon resin and step（6）The silane coupler modified glass fiber reinforcements of middle gained are by being extruded into
Type technique carries out compound.Material is weighed by following weight parts：66 parts of nylon resin；Silane coupler modified glass fiber reinforcement
30 parts of body；4 parts of other auxiliary agents（Other auxiliary agents include that antioxidant, plasticizer, ultraviolet-resistant absorbent, lubricant, impact change
One or more in property agent, heat stabilizer, toughener）；Above-mentioned material is squeezed out and is granulated through double screw extruder,
Middle glass fiber reinforcements are added by side feeding, and extruder screw rotating speed is 125 revs/min, and temperature is 265 DEG C, you can obtains height
Performance composite glass fiber reinforced polyamide material.
Embodiment 2
A kind of preparation method of high-performance composite glass fiber reinforced resin material, includes the following steps：
（1）Prepare 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, and in 500 DEG C of annealing, glass is made；By glass obtained
Glass is heated to 1050 DEG C of the temperature of wire drawing viscosity, is drawn into the glass fibre of about 10 μm or so of diameter；
（2）Glass fibre pre-processes：After taking 45 parts of glass fibre split-phases, in the HCl solution of a concentration of 1mol/L of 100ml
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 solns separated in glass fibre are made
The NH4Cl solution of 5ml a concentration of 40% is added in acid, acid as buffer, sour processing time is 30min；Through rinse dehydration,
Drying, obtains pretreated glass fiber；
（3）Weigh graphene quantum dot（Grain size about 2 ~ 5nm）It is configured to the dispersion solution of a concentration of 0.3mg/ml, solvent is
Water, acetone or dimethyl sulfoxide (DMSO)；Ultrasonic agitation（500W ultrasonic powers, 200rpm mixing speeds）50ml graphene quantum dots disperse
Solution is added to a concentration of 0.03mol/L silver nitrate solutions, and controlling reaction temperature is 45 DEG C, and a concentration of 0.8mol/L bis- is added dropwise
Citric acid monohydrate trisodium continues that 90min is stirred by ultrasonic；10ml graphene quantum dots are added dropwise and disperse 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 cleans, drying, for use；The volume of graphene quantum dot dispersion, silver nitrate solution and two citric acid monohydrate trisodiums
Than being 4:3:2；
（4）Weigh porous graphene（2 ~ 5 layers, hole size about 3 ~ 6nm）It is configured to the graphene point of a concentration of 0.2mg/ml
Solution is dissipated, solvent is water, acetone or dimethyl sulfoxide (DMSO)；Ultrasonic agitation（500W ultrasonic powers, 200rpm mixing speeds）100ml stones
Black alkene disperses solution, and step is added（3）Glass fibre obtained is stirred by ultrasonic 10min, 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）By 0. 3M titanium sources（Titanium source is isopropyl titanate）It is added in 1 M sulfuric acid solutions, is uniformly mixed；Step is added
（4）Glass fibre obtained, 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；
（6）By step（5）Load silver/titanium dioxide composite glass fiber obtained is with silane coupling agent in second alcohol and water
It reacts, is reacted at 60 DEG C for 24 hours in mixed solution, reaction products therefrom uses ethyl alcohol, water washing successively, finally in 8000r/min
Centrifugation rate under centrifugation 30min obtain silane coupler modified glass fiber reinforcements, the silane coupling agent is ring
Oxygroup type；The mass ratio of the load silver/titanium dioxide composite glass fiber and silane coupling agent is 1:12；The ethyl alcohol
Volume ratio with the in the mixed solvent of water, second alcohol and water is 3:2；The volumetric usage of the ethyl alcohol and water mixed solvent is to load
The quality of silver/titanium dioxide composite glass fiber is calculated as 400mL/g；
（7）By nylon resin and step（6）The silane coupler modified glass fiber reinforcements of middle gained are by being extruded into
Type technique carries out compound.Material is weighed by following weight parts：66 parts of nylon resin；Silane coupler modified glass fiber reinforcement
30 parts of body；4 parts of other auxiliary agents（Other auxiliary agents include that antioxidant, plasticizer, ultraviolet-resistant absorbent, lubricant, impact change
One or more in property agent, heat stabilizer, toughener）；Above-mentioned material is squeezed out and is granulated through double screw extruder,
Middle glass fiber reinforcements are added by side feeding, and extruder screw rotating speed is 125 revs/min, and temperature is 265 DEG C, you can obtains height
Performance composite glass fiber reinforced polyamide material.
Embodiment 3
A kind of preparation method of high-performance composite glass fiber reinforced resin material, includes the following steps：
（1）Prepare 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, and in 500 DEG C of annealing, glass is made；By glass obtained
Glass is heated to 1050 DEG C of the temperature of wire drawing viscosity, is drawn into the glass fibre of about 10 μm or so of diameter；
（2）Glass fibre pre-processes：After taking 45 parts of glass fibre split-phases, in the HCl solution of a concentration of 1mol/L of 100ml
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 solns separated in glass fibre are made
The NH4Cl solution of 5ml a concentration of 40% is added in acid, acid as buffer, sour processing time is 30min；Through rinse dehydration,
Drying, obtains pretreated glass fiber；
（3）Weigh graphene quantum dot（Grain size about 2 ~ 5nm）It is configured to the dispersion solution of a concentration of 0.8mg/ml, solvent is
Water, acetone or dimethyl sulfoxide (DMSO)；Ultrasonic agitation（500W ultrasonic powers, 200rpm mixing speeds）50ml graphene quantum dots disperse
Solution is added to a concentration of 0.03mol/L silver nitrate solutions, and controlling reaction temperature is 45 DEG C, and a concentration of 0.5mol/L bis- is added dropwise
Citric acid monohydrate trisodium continues that 90min is stirred by ultrasonic；20ml graphene quantum dots are added dropwise and disperse 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 cleans, drying, for use；The volume of graphene quantum dot dispersion, silver nitrate solution and two citric acid monohydrate trisodiums
Than being 3:2:1；
（4）Weigh porous graphene（2 ~ 5 layers, hole size about 3 ~ 6nm）It is configured to the graphene point of a concentration of 0.5mg/ml
Solution is dissipated, solvent is water, acetone or dimethyl sulfoxide (DMSO)；Ultrasonic agitation（500W ultrasonic powers, 200rpm mixing speeds）80ml stones
Black alkene disperses solution, and step is added（3）Glass fibre obtained is stirred by ultrasonic 10min, 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）By 0.2M titanium sources（Titanium source is ammonium titanium fluoride）It is added in 1 M sulfuric acid solutions, is uniformly mixed；Step is added（4）
Glass fibre obtained is warming up to 110 DEG C, after reacting 3h, with concentrated ammonia solution tune pH value to 7, after being aged 12 hours, cleans,
It is dry, obtain load silver/titanium dioxide composite glass fiber；
（6）By step（5）Load silver/titanium dioxide composite glass fiber obtained is with silane coupling agent in second alcohol and water
It reacts, is reacted at 60 DEG C for 24 hours in mixed solution, reaction products therefrom uses ethyl alcohol, water washing successively, finally in 8000r/min
Centrifugation rate under centrifugation 30min obtain silane coupler modified glass fiber reinforcements, the silane coupling agent is ammonia
Base type；The mass ratio of the load silver/titanium dioxide composite glass fiber and silane coupling agent is 1:12；The ethyl alcohol and
The volume ratio of the in the mixed solvent of water, second alcohol and water is 3:2；The volumetric usage of the ethyl alcohol and water mixed solvent with load silver/
The quality of titanium dioxide composite glass fiber is calculated as 400mL/g；
（7）By nylon resin and step（6）The silane coupler modified glass fiber reinforcements of middle gained are by being extruded into
Type technique carries out compound.Material is weighed by following weight parts：66 parts of nylon resin；Silane coupler modified glass fiber reinforcement
30 parts of body；4 parts of other auxiliary agents（Other auxiliary agents include that antioxidant, plasticizer, ultraviolet-resistant absorbent, lubricant, impact change
One or more in property agent, heat stabilizer, toughener）；Above-mentioned material is squeezed out and is granulated through double screw extruder,
Middle glass fiber reinforcements are added by side feeding, and extruder screw rotating speed is 125 revs/min, and temperature is 265 DEG C, you can obtains height
Performance composite glass fiber reinforced polyamide material.
Embodiment 4
A kind of preparation method of high-performance composite glass fiber reinforced resin material, includes the following steps：
（1）Prepare glass fibre：By 51% SiO2,15%B2O3,6%Na2O, 9.8%Al2O3,18%CaO and 0.2% multi wall
Carbon nanotube（OD about 8nm）It after crushing, stirring mixing, 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 the 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 of a concentration of 1mol/L of 100ml
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 solns separated in glass fibre are made
The NH4Cl solution of 5ml a concentration of 40% is added in acid, acid as buffer, sour processing time is 30min；Through rinse dehydration,
Drying, obtains pretreated glass fiber；
（3）Weigh graphene quantum dot（Grain size about 2 ~ 5nm）It is configured to the dispersion solution of a concentration of 0.3mg/ml, solvent is
Water, acetone or dimethyl sulfoxide (DMSO)；Ultrasonic agitation（500W ultrasonic powers, 200rpm mixing speeds）50ml graphene quantum dots disperse
Solution is added to a concentration of 0.03mol/L silver nitrate solutions, and controlling reaction temperature is 45 DEG C, and a concentration of 0.8mol/L bis- is added dropwise
Citric acid monohydrate trisodium continues that 90min is stirred by ultrasonic；10ml graphene quantum dots are added dropwise and disperse 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 cleans, drying, for use；The volume of graphene quantum dot dispersion, silver nitrate solution and two citric acid monohydrate trisodiums
Than being 4:3:2；
（4）Weigh porous graphene（2 ~ 5 layers, hole size about 3 ~ 6nm）It is configured to the graphene point of a concentration of 0.2mg/ml
Solution is dissipated, solvent is water, acetone or dimethyl sulfoxide (DMSO)；Ultrasonic agitation（500W ultrasonic powers, 200rpm mixing speeds）100ml stones
Black alkene disperses solution, and step is added（3）Glass fibre obtained is stirred by ultrasonic 10min, 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）Weigh Zinc oxide quantum dot（Grain size about 5 ~ 10nm）It is configured to the dispersion liquid of a concentration of 0.5mg/ml, solvent is
Water；Ultrasonic agitation（500W ultrasonic powers, 200rpm mixing speeds）80ml zinc oxide fluid dispersions, by step（4）Glass obtained
Fiber is added thereto, and ultrasonic agitation speed halves, and impregnates 60min, during which avoids fibre matting, influences to coat effect；Take out glass
Glass fiber cleans, drying, for use；
（6）By 0. 3M titanium sources（Titanium source is potassium fluotitanate）It is added in 1 M sulfuric acid solutions, is uniformly mixed；Step is added
（5）Glass fibre obtained, 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；
（7）By step（6）Load silver/titanium dioxide composite glass fiber obtained is with silane coupling agent in second alcohol and water
It reacts, is reacted at 60 DEG C for 24 hours in mixed solution, reaction products therefrom uses ethyl alcohol, water washing successively, finally in 8000r/min
Centrifugation rate under centrifugation 30min obtain silane coupler modified glass fiber reinforcements, the silane coupling agent is first
Base acryloyl-oxy base type；The mass ratio of the load silver/titanium dioxide composite glass fiber and silane coupling agent is 1:12；
The volume ratio of the in the mixed solvent of the second alcohol and water, second alcohol and water is 3:2；The volume of the ethyl alcohol and water mixed solvent is used
Amount is calculated as 400mL/g with the quality for loading silver/titanium dioxide composite glass fiber；
（8）By nylon resin and step（7）The silane coupler modified glass fiber reinforcements of middle gained are by being extruded into
Type technique carries out compound.Material is weighed by following weight parts：66 parts of nylon resin；Silane coupler modified glass fiber reinforcement
30 parts of body；4 parts of other auxiliary agents（Other auxiliary agents include that antioxidant, plasticizer, ultraviolet-resistant absorbent, lubricant, impact change
One or more in property agent, heat stabilizer, toughener）；Above-mentioned material is squeezed out and is granulated through double screw extruder,
Middle glass fiber reinforcements are added by side feeding, and extruder screw rotating speed is 125 revs/min, and temperature is 265 DEG C, you can obtains height
Performance composite glass fiber reinforced polyamide material.
Embodiment 5
A kind of preparation method of high-performance composite glass fiber reinforced resin material, includes the following steps：
（1）Prepare glass fibre：By 51% SiO2,15%B2O3,6%Na2O, 10%Al2O3,17.5%CaO and 0.5% multi wall
Carbon nanotube（OD about 8nm）It after crushing, stirring mixing, 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 the 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 of a concentration of 1mol/L of 100ml
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 solns separated in glass fibre are made
The NH4Cl solution of 5ml a concentration of 40% is added in acid, acid as buffer, sour processing time is 30min；Through rinse dehydration,
Drying, obtains pretreated glass fiber；
（3）Weigh graphene quantum dot（Grain size about 2 ~ 5nm）It is configured to the dispersion solution of a concentration of 0.3mg/ml, solvent is
Water, acetone or dimethyl sulfoxide (DMSO)；Ultrasonic agitation（500W ultrasonic powers, 200rpm mixing speeds）50ml graphene quantum dots disperse
Solution is added to a concentration of 0.03mol/L silver nitrate solutions, and controlling reaction temperature is 45 DEG C, and a concentration of 0.8mol/L bis- is added dropwise
Citric acid monohydrate trisodium continues that 90min is stirred by ultrasonic；10ml graphene quantum dots are added dropwise and disperse 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 cleans, drying, for use；The volume of graphene quantum dot dispersion, silver nitrate solution and two citric acid monohydrate trisodiums
Than being 4:3:2；
（4）Weigh porous graphene（2 ~ 5 layers, hole size about 3 ~ 6nm）It is configured to the graphene point of a concentration of 0.2mg/ml
Solution is dissipated, solvent is water, acetone or dimethyl sulfoxide (DMSO)；Ultrasonic agitation（500W ultrasonic powers, 200rpm mixing speeds）100ml stones
Black alkene disperses solution, and step is added（3）Glass fibre obtained is stirred by ultrasonic 10min, 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）Weigh Zinc oxide quantum dot（Grain size about 5 ~ 10nm）It is configured to the dispersion liquid of a concentration of 1mg/ml of 100ml, solvent
For water；Ultrasonic agitation（500W ultrasonic powers, 200rpm mixing speeds）100ml zinc oxide fluid dispersions, by step（4）Glass obtained
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 cleans, drying, for use；
（6）By 0. 3M titanium sources（Titanium source is titanium tetrachloride）It is added in 1 M sulfuric acid solutions, is uniformly mixed；Step is added
（5）Glass fibre obtained, 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；
（7）By step（6）Load silver/titanium dioxide composite glass fiber obtained is with silane coupling agent in second alcohol and water
It reacts, is reacted at 60 DEG C for 24 hours in mixed solution, reaction products therefrom uses ethyl alcohol, water washing successively, finally in 8000r/min
Centrifugation rate under centrifugation 30min obtain silane coupler modified glass fiber reinforcements, the silane coupling agent is first
Base acryloyl-oxy base type；The mass ratio of the load silver/titanium dioxide composite glass fiber and silane coupling agent is 1:12；
The volume ratio of the in the mixed solvent of the second alcohol and water, second alcohol and water is 3:2；The volume of the ethyl alcohol and water mixed solvent is used
Amount is calculated as 400mL/g with the quality for loading silver/titanium dioxide composite glass fiber；
（8）By nylon resin and step（7）The silane coupler modified glass fiber reinforcements of middle gained are by being extruded into
Type technique carries out compound.Material is weighed by following weight parts：66 parts of nylon resin；Silane coupler modified glass fiber reinforcement
30 parts of body；4 parts of other auxiliary agents（Other auxiliary agents include that antioxidant, plasticizer, ultraviolet-resistant absorbent, lubricant, impact change
One or more in property agent, heat stabilizer, toughener）；Above-mentioned material is squeezed out and is granulated through double screw extruder,
Middle glass fiber reinforcements are added by side feeding, and extruder screw rotating speed is 125 revs/min, and temperature is 265 DEG C, you can obtains height
Performance composite glass fiber reinforced polyamide material.
Comparative example 1
A kind of preparation method of high-performance composite glass fiber reinforced resin material, includes the following steps：
（1）Prepare 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, and in 500 DEG C of annealing, glass is made；By glass obtained
Glass is heated to 1050 DEG C of the temperature of wire drawing viscosity, is drawn into the glass fibre of about 10 μm or so of diameter；
（2）Glass fibre pre-processes：After taking 45 parts of glass fibre split-phases, in the HCl solution of a concentration of 1mol/L of 100ml
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 solns separated in glass fibre are made
The NH4Cl solution of 5ml a concentration of 40% is added in acid, acid as buffer, sour processing time is 30min；Through rinse dehydration,
Drying, obtains pretreated glass fiber；
（3）By 0. 3M titanium sources（Titanium source is isopropyl titanate）It is added in 1 M sulfuric acid solutions, is uniformly mixed；Step is added
（3）Glass fibre obtained, 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；
（4）By step（3）Carried titanium dioxide composite glass fiber obtained is with silane coupling agent in the mixed of second alcohol and water
It closes and is reacted in solution, reacted at 60 DEG C for 24 hours, reaction products therefrom uses ethyl alcohol, water washing successively, finally 8000r/min's
30min is centrifuged under centrifugation rate and obtains silane coupler modified glass fiber reinforcements, and the silane coupling agent is ethylene
Base type；The mass ratio of the load silver/titanium dioxide composite glass fiber and silane coupling agent is 1:12；The ethyl alcohol and
The volume ratio of the in the mixed solvent of water, second alcohol and water is 3:2；The volumetric usage of the ethyl alcohol and water mixed solvent with load silver/
The quality of titanium dioxide composite glass fiber is calculated as 400mL/g；
（5）By nylon resin and step（4）The silane coupler modified glass fiber reinforcements of middle gained are by being extruded into
Type technique carries out compound.Material is weighed by following weight parts：66 parts of nylon resin；Silane coupler modified glass fiber reinforcement
30 parts of body；4 parts of other auxiliary agents（Other auxiliary agents include that antioxidant, plasticizer, ultraviolet-resistant absorbent, lubricant, impact change
One or more in property agent, heat stabilizer, toughener）；Above-mentioned material is squeezed out and is granulated through double screw extruder,
Middle glass fiber reinforcements are added by side feeding, and extruder screw rotating speed is 125 revs/min, and temperature is 265 DEG C, you can obtains height
Performance composite glass fiber reinforced polyamide material.
Comparative example 2
A kind of preparation method of high-performance composite glass fiber reinforced resin material, includes the following steps：
（1）Prepare 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, and in 500 DEG C of annealing, glass is made；By glass obtained
Glass is heated to 1050 DEG C of the temperature of wire drawing viscosity, is drawn into the glass fibre of about 10 μm or so of diameter；
（2）Glass fibre pre-processes：After taking 45 parts of glass fibre split-phases, in the HCl solution of a concentration of 1mol/L of 100ml
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 solns separated in glass fibre are made
The NH4Cl solution of 5ml a concentration of 40% is added in acid, acid as buffer, sour processing time is 30min；Through rinse dehydration,
Drying, obtains pretreated glass fiber；
（3）Compound concentration is 0.03mol/L silver nitrate solutions, ultrasonic agitation（500W ultrasonic powers, 200rpm stirring speed
Degree）, pretreated glass fibre is added thereto, controlling reaction temperature is 45 DEG C, and the hydrations of a concentration of 0.8mol/L bis- are added dropwise
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）By 0. 3M titanium sources（Titanium source is isopropyl titanate）It is added in 1 M sulfuric acid solutions, is uniformly mixed；Step is added
（3）Glass fibre obtained, 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；
（5）By step（4）Load silver/titanium dioxide composite glass fiber obtained is with silane coupling agent in second alcohol and water
It reacts, is reacted at 60 DEG C for 24 hours in mixed solution, reaction products therefrom uses ethyl alcohol, water washing successively, finally in 8000r/min
Centrifugation rate under centrifugation 30min obtain silane coupler modified glass fiber reinforcements, the silane coupling agent is second
Alkenyl type epoxy base type, amine type or methacryloxy type；The load silver/titanium dioxide compound glass is fine
The mass ratio of dimension and silane coupling agent is 1:12；The volume ratio of the in the mixed solvent of the second alcohol and water, second alcohol and water is 3:
2；The volumetric usage of the ethyl alcohol and water mixed solvent is calculated as with the quality for loading silver/titanium dioxide composite glass fiber
400mL/g；
（6）By nylon resin and step（5）The silane coupler modified glass fiber reinforcements of middle gained are by being extruded into
Type technique carries out compound.Material is weighed by following weight parts：66 parts of nylon resin；Silane coupler modified glass fiber reinforcement
30 parts of body；4 parts of other auxiliary agents（Other auxiliary agents include that antioxidant, plasticizer, ultraviolet-resistant absorbent, lubricant, impact change
One or more in property agent, heat stabilizer, toughener）；Above-mentioned material is squeezed out and is granulated through double screw extruder,
Middle glass fiber reinforcements are added by side feeding, and extruder screw rotating speed is 125 revs/min, and temperature is 265 DEG C, you can obtains height
Performance composite glass fiber reinforced polyamide material.
The above composite glass fiber reinforced resin material is subjected to Mechanics Performance Testing and anti-microbial property test.
Mechanics Performance Testing：
Antibiotic property is tested：
Anti-microbial property detection is with reference to People's Republic of China (PRC) state light industry standard QB/T2591-2003, using film applicator coating,
The antibiotic rate of 6 ~ 48h of sample is investigated, total plate count is measured to be counted with reference to GB/T4789.2-2003；Naval stores is hot-forming
The antibacterial model 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/ pieces, C is that antibacterial model is averaged bacterial count recovered, cfu/ pieces.Sterilization rate test knot
Fruit such as following table：
In addition, the wearability to test the above resin material and the antibacterial effect after long-term practical abrasion, by antibacterial model
It carries out simulation and uses wear testing, it is 3~4 abrasive material that wear testing, which selects Mohs' hardness, and friction is imitated using 2 years for 1000 times
Effect afterwards.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 model 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 it is interpreted as the limitation to the scope of the claims of the present invention, 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-performance composite glass fiber reinforced resin material, includes the following steps：
（1）Prepare glass fibre：By 50 ~ 55% SiO2、10~15%B2O3、5~10%Na2O、10~15%Al2O3, 15 ~ 20%CaO and
It after the mixing of 0.1 ~ 0.5% multi-walled carbon nanotube crushing, stirring, 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 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, glass is made；Glass obtained is heated to 1050 DEG C of the temperature of wire drawing viscosity, is drawn into glass fibre；
（2）Glass fibre pre-processes：After taking 5 ~ 50 parts of glass fibre split-phases, carried out in the HCl solution of a concentration of 1 ~ 2mol/L
Acidleach is handled, and acidleach processing is carried out under the conditions of 90 ~ 95 DEG C of constant temperature, and the Na separated in glass fibre is made2O-B2O3Phased soln in
A concentration of 40% NH is added in acid in sour4For Cl solution as buffer, sour processing time is 30 ~ 60min；Through rinse dehydration, dry
It is dry, obtain pretreated glass fiber；
（3）The dispersion solution that the graphene quantum dot that grain size is 2 ~ 10nm is configured to a concentration of 0.1 ~ 1mg/ml is weighed, solvent is
Water, acetone or dimethyl sulfoxide (DMSO)；50 ~ 60ml graphene quantum dots are stirred by ultrasonic and disperse solution, it is added to a concentration of 0.01 ~
0.03mol/L silver nitrate solutions, controlling reaction temperature are 45 ~ 60 DEG C, and a concentration of 0.1~0.8mol/L, bis- citric acid monohydrates are added dropwise
Trisodium continues 60 ~ 120min of ultrasonic agitation；10 ~ 20ml graphene quantum dots are added dropwise and disperse 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 the graphene dispersion solution that porous graphene is configured to a concentration of 0.2 ~ 0.8mg/ml, solvent be water, acetone or
Dimethyl sulfoxide (DMSO)；80 ~ 100ml graphene dispersion solution is stirred by ultrasonic, step is added（3）Glass fibre obtained, ultrasonic agitation
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）The dispersion liquid that Zinc oxide quantum dot is configured to a concentration of 0.5 ~ 1mg/ml is weighed, solvent is water；Ultrasonic agitation 80 ~
100ml zinc oxide fluid dispersions, by step（4）Glass fibre obtained is added thereto, 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 sources are added in 1 M sulfuric acid solutions, are uniformly mixed；Step is added（5）Glass fibre obtained,
110 DEG C are warming up to, after reacting 3 ~ 5h, with concentrated ammonia solution tune pH value to 7, after being aged 12 hours, is cleaned, it is dry, it is loaded
Silver/titanium dioxide composite glass fiber；
（7）By step（6）The mixing of load silver/titanium dioxide composite glass fiber and silane coupling agent obtained in second alcohol and water
Reacted in solution, react 20 at 55~75 DEG C~for 24 hours, reaction products therefrom uses ethyl alcohol, water washing successively, finally 8000~
15 ~ 30min is centrifuged under the centrifugation rate of 10000r/min obtains silane coupler modified glass fiber reinforcements；
（8）By resin and step（7）Silane coupler modified glass fiber reinforcements obtained are added to double screw extruder
Middle melt blending squeezes out, and is molded and composite glass fiber reinforced resin material is made.
2. the preparation method of high-performance composite glass fiber reinforced resin material according to claim 1, which is characterized in that
The porous graphene is 2 ~ 5 layers, and hole size is the porous graphene of 3 ~ 6nm.
3. the preparation method of high-performance composite glass fiber reinforced resin material according to claim 1, which is characterized in that
The titanium source is potassium fluotitanate, ammonium titanium fluoride, isopropyl titanate or titanium tetrachloride.
4. the preparation method of high-performance composite glass fiber reinforced resin material according to claim 1, which is characterized in that
The Zinc oxide quantum dot grain size is 5 ~ 10nm.
5. high-performance composite glass fiber reinforced resin material obtained method according to claim 1 to 4.
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| CN109458498B (en) * | 2018-12-25 | 2024-02-27 | 浙江鸿盛新材料科技集团股份有限公司 | High-strength PTFE composite pipe and preparation method thereof |
| CN112457659B (en) * | 2020-11-10 | 2023-04-21 | 惠州市中诚复合材料科技有限公司 | Glass fiber reinforced high-strength engineering plastic and preparation method thereof |
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| 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 |
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