CN100482608C - Preparation method of hybrid size for improving basalt fiber performance and modification method - Google Patents
Preparation method of hybrid size for improving basalt fiber performance and modification method Download PDFInfo
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- CN100482608C CN100482608C CNB2006100344688A CN200610034468A CN100482608C CN 100482608 C CN100482608 C CN 100482608C CN B2006100344688 A CNB2006100344688 A CN B2006100344688A CN 200610034468 A CN200610034468 A CN 200610034468A CN 100482608 C CN100482608 C CN 100482608C
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- organic compound
- basalt fibre
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Abstract
A process for improving the performance of basalt fibers features that an ultrasonic forced continuous coating technique is used for coating hybridized slurry on the surface of each basalt fiber to improve its tension strength and the resistance to high temp. A process for preparing said hybridized slurry is also disclosed.
Description
[technical field]
The invention belongs to fiber and field of compound material thereof, relate in particular to the method for a kind of basalt fibre surface modification slurry, basalt fibre modification.
[background technology]
Basalt fibre is a kind of novel inorganic reinforcement, is raw material by single basalt ore, and its cost of material is cheap, and reserves are abundant, have outstanding price advantage.Basalt fibre is mainly by SiO
2, Al
2O
3, Fe
2O
3, CaO, MgO, K
2O, TiO
2Constitute, have good mechanics, chemistry, thermomechanical property, especially high temperature resistant, the performance of aspects such as resistant to chemical media and thermal insulation, insulation, sound-proofing properties is more excellent, compares with the obvious advantage with traditional glass fibre.In addition, the basalt fibre goods can not discharge toxic substance in air and water medium, promptly become the matrix of soil after the degraded, and are environmentally friendly, belong to the ecological sanitation material.Therefore, can be in building, metallurgy, oil, chemical industry, automobile, shipbuilding, electronics, medical science, papermaking, agricultural, aerospace are that other all many-sides are used widely.
The performance of basalt fiber composite material depends on the bulk properties of fiber and body material, and the interface of fiber and matrix coheres the transfer mode with interfacial stress, then 2 closely related with the fiber surface performance.The basalt fibre smooth surface, surface energy is low, and a little less than itself and the resin matrix cohesive strength, the interface performance of matrix material is poor, thereby influences the performance fully of the whole excellent properties of matrix material.Therefore need effectively handle the basalt fibre surface, in the hope of passing through design to the basalt fibre surface tissue, improve the surface property of fiber, optimize basalt fibre and resin matrix interfacial phase performance purpose thereby reach, basalt fiber composite material is more widely used in each field.
In the prior art, less about the research of basalt fibre surface modifying method, mainly continue to use the used silane coupling agent method of traditional glass fiber surface modification at present.Though this method can increase the interfacial adhesion strength of fiber and resin, reduced the impelling strength of material simultaneously.
[summary of the invention]
The objective of the invention is to: a kind of hybrid size preparation method, basalt fibre surface modifying method that is used to improve basalt fiber performance is provided, can effectively improve the performance of fiber, the moulding process of its matrix material and whole synthesis performance are improved.
For achieving the above object, the present invention proposes a kind of organic-inorganic nano hybrid size that is used for the basalt fibre surface modification, described organic-inorganic nano hybrid size is reacted through hydridization by organic constituent and inorganic component and obtains, described organic constituent is low-molecular-weight organic compound or the macromolecular organic compound that contains reactive group, described inorganic component is metal oxide or nonmetal oxide, in the described organic-inorganic nano hybrid size, the mass ratio of inorganic component and organic constituent is 1-10: 100.
Above-mentioned organic-inorganic nano hybrid size, described metal oxide comprises one or more in titanium, aluminium, zirconium, iron, tin, zinc, barium, the nickel oxide, nonmetal oxide comprises one or more of silicon, phosphorous oxides.Described reactive group comprises two keys, hydroxyl, carboxyl, amido, isocyanate group, epoxide group or acetylene group.
For achieving the above object, the present invention proposes the preparation method of the organic-inorganic nano hybrid size that is used for the basalt fibre surface modification, comprise the steps:
At first the presoma with metal or nonmetal oxide joins the alcoholic acid aqueous solution of pH value for 3-12, wherein said oxide precursor, water, alcoholic acid mole proportioning are 1: 1-7: 8-20, under 20-70 ℃, in whipped state, reacted 2-10 hour, make inorganic nano-particle pioneer liquid; Wherein said metal oxide comprises one or more in titanium, aluminium, zirconium, iron, tin, zinc, barium, the nickel oxide, and nonmetal oxide comprises one or more of silicon, phosphorous oxides;
Adopt γ-An Jibingjisanyiyangjiguiwan, (γ-phenylacetylene imino-) propyl-triethoxysilicane or 3-aminopropyl three ethoxy silane and organic compound reactions, with the mole proportioning of organic compound be 1-5: 1, reaction conditions is: 20-80 ℃, stirred 2-10 hour, and made the modification organic compound; Or adopt γ-An Jibingjisanyiyangjiguiwan, (γ-phenylacetylene imino-) propyl-triethoxysilicane or 3-aminopropyl three ethoxy silane and the inorganic nano-particle pioneer liquid that makes to react, with the mole proportioning of inorganic nano-particle pioneer liquid be 1: 20-30, reaction conditions is: 20-80 ℃, stirred 2-10 hour, and made modified inorganic nano-particle pioneer liquid;
Synthetic inorganic nano-particle pioneer's liquid and modification organic compound are carried out the hydridization reaction, or modified inorganic nano-particle pioneer liquid and organic compound are carried out the hydridization reaction, the hydridization reaction conditions is: temperature 20-80 ℃, stirred 2-15 hour;
Described organic compound is the organic compound that contains two keys, hydroxyl, carboxyl, amino, epoxy group(ing), isocyanate group or acetylene group.
Described organic compound is bisphenol A type epoxy resin or polyimide or phenylethylene-maleic anhydride oligopolymer.
The present invention proposes a kind of basalt fibre surface modifying method simultaneously, its step comprises: 1) hybrid size with above-mentioned preparation method's preparation is dissolved in the organic solvent, be mixed with the coating solution that the basalt fibre modification is used, 2) described coating solution is coated in basalt fibre surface, 3) dry processing.
Above-mentioned method of modifying, described step 2) comprise, adopt ultrasonic mode of forcing coating continuously, fiber is forced dipping.The described ultrasonic condition of coating of forcing continuously is: ultrasonic power is 10-1000W, and temperature is under the 20-50 ℃ of condition, speed 0.1-10m/min.
Above-mentioned method of modifying, the temperature that oven dry is handled in described step 3) is 50-150 ℃, drying time is 3-60 minute.
Above-mentioned basalt fibre surface modifying method, described organic solvent comprise ketone, alcohol or the mixture of the two.In the described coating solution, the organic compound amount in the hybrid size and the mass ratio of organic solvent are 1-15: 100.Described ketone is acetone, and alcohol is ethanol, ethylene glycol, propyl alcohol.
Since adopted above scheme, mating surface coating technology of the present invention and ultrasonic immersing modification technology, and the hybrid size that modification provided by the invention is used, method of modifying have following advantage:
One, the hybrid size that adopts modification of the present invention to use carries out the coating processing to the basalt fibre surface, its surface property is improved, and with the infiltration speed raising of matrix resin, the infiltration amount increases, effect of impregnation may is improved, and this provides sound assurance to forming high-quality interface structure.
Two, the ultrasonic coated technique that forces continuously that is adopted can make coated substance be coated in every fiber surface equably, eliminates the coating difference between fibrous bundle, simultaneously under action of ultrasonic waves as much as possible reinforcing fiber be coated with combining of interlayer.
Three, the basalt fibre surface is carried out coating and is handled and can make the fiber bodies performance obtain to a certain degree optimization, and the fiber bodies tensile strength improves, and resistance to elevated temperatures is improved.
Four, the basalt fibre surface is carried out coating and is handled the interfacial adhesion strength of basalt fiber composite material is improved, and impelling strength also has improvement to a certain degree simultaneously.
[embodiment]
Embodiment one
Adopt mole to consist of tetraethoxy 1 ± 0.1, deionized water 4 ± 0.2, the mixing solutions of dehydrated alcohol 15 ± 0.5 prepare nano silicon pioneer liquid, its reaction conditions is 9.0 ± 0.2 for the pH value of solution value, 50 ± 5 ℃ of temperature of reaction in 6 hours reaction times, at the uniform velocity stir.Adopt γ-An Jibingjisanyiyangjiguiwan and bisphenol type epoxy E-51 reaction simultaneously, its mole proportioning is 1.2: 1, and 45 ± 5 ℃ of temperature of reaction in 7 hours reaction times, at the uniform velocity stir.Then inorganic nano-particle pioneer liquid is mixed with modified epoxy and carry out the hydridization reaction, its quality proportioning is the inorganic nano-particle protonatomic mass: epoxy E-51 quality=4.5: 100,47 ± 5 ℃ of temperature of reaction, 5 hours reaction times.With the anhydrous propanone is solvent, is 2: 100 preparation fibre modification coating solutions by epoxy quality in the hybrid size and acetone mass ratio.Adopt ultrasonic wave to force dipping technique that the 1K basalt fibre is applied, ultrasonic power is 200W, and impregnating speed is 2m/min, dries 40 minutes under 70 ± 2 ℃ of temperature then.The wetting property of basalt fibre before and after the contrast coating is handled finds that the infiltration speed of coating processing back fiber improves 40%, and the infiltration amount is brought up to 150mg by 100mg, has improved 50%.Adopt mould pressing process to prepare basalt fibre/epoxy composite material, composite material interface performance before and after the contrast coating is handled found that the interlaminar shear strength of coating processing back matrix material reaches 100MPa, has improved 20% than untreated.
Embodiment two
Adopt mole to consist of tetraethoxy 1 ± 0.1, deionized water 4 ± 0.2, the mixing solutions of dehydrated alcohol 18 ± 0.5 prepares nano silicon pioneer liquid, its reaction conditions is 4 ± 0.2 for the pH value of solution value, 45 ± 2 ℃ of temperature of reaction, in 6 hours reaction times, at the uniform velocity stir preparation inorganic nano-particle pioneer liquid.Then (γ-phenylacetylene imino-) propyl-triethoxysilicane progressively is added drop-wise in the inorganic particulate pioneer liquid,, makes modified inorganic nano-particle pioneer liquid in 50 ℃ of reactions 6 hours.The inorganic nano-particle pioneer liquid of modification and phenylacetylene-capped isomery polyimide solution are carried out the hydridization reaction, and its quality is than inorganic nano-particle protonatomic mass: isomery polyimide=6: 100,60 ± 1 ℃ of temperature of reaction, 8 hours reaction times.With the dehydrated alcohol is solvent, is 4: 100 preparation fibre modification coating solutions by polyimide quality in the hybrid size and ethanol mass ratio.Adopt ultrasonic wave to force dipping technique that basalt fibre is applied, ultrasonic power is 400W, and impregnating speed is 5m/min, dries 60 minutes under 80 ± 2 ℃ of temperature then.Analyze coating and handle the variation of front and back basalt fibre bulk properties, found that, coating is handled back fiber bodies synnema tensile strength by untreated 2.5GPa, brings up to 3.0GPa, has improved 20%.After 600 ℃ of hot environments, the basalt fibre strength retention of handling through coating is 85%, and its strength retention of untreated fibers only is 40%.In addition, basalt fibre/composite polyimide material interface shear strength improves 30%, and the matrix material shock resistance improves 10%.
Embodiment three
Adopting the mole ratio of components is tetrabutyl titanate 1 ± 0.1, deionized water 3 ± 0.5, and the mixing solutions of dehydrated alcohol 18 ± 0.5 prepares the nano titanium oxide precursor, its reaction conditions is 2.5 ± 0.1 for the pH value of solution value, 30 ± 2 ℃ of temperature of reaction in 10 hours reaction times, at the uniform velocity stir.Adopt the reaction of 3-aminopropyl three ethoxy silane and phenylethylene-maleic anhydride oligopolymer, both mole proportionings are 1.1: 1, and 50 ℃ of temperature of reaction in 7 hours reaction times, at the uniform velocity stir.Then inorganic nano-particle pioneer liquid is mixed with modified phenylethylene-MALEIC ANHYDRIDE oligopolymer and carry out the hydridization reaction, its quality proportioning is the inorganic nano-particle protonatomic mass: modification oligopolymer quality=10: 100,50 ± 5 ℃ of temperature of reaction, 5 hours reaction times.With the mol ratio is anhydrous propanone: dehydrated alcohol=1: 1 mixing solutions is a solvent, is 6: 100 preparation fibre modification coating solutions by organic phase quality in the hybrid size and solvent quality ratio.Adopt ultrasonic wave to force dipping technique that basalt fibre is applied, ultrasonic power is 600W, and impregnating speed is 1m/min, dries 30 minutes under 60 ± 2 ℃ of temperature then.Analyze coating and handle the variation of front and back basalt fibre bulk properties, found that, coating is handled back fiber bodies synnema tensile strength by untreated 2.5GPa, brings up to 3.2GPa, has improved 28%.Preparation basalt fibre/unsaturated polyester composite, the infiltration speed of fiber and unsaturated polyester improves 50%, the infiltration amount increases to 160mg, improved 60%, adopt coating modified circle, interface that handles the back matrix material and intensity by 60MPa, bring up to 92MPa, improved more than 50%, the shock resistance of material monolithic improves 20%.
The present invention is applicable to basalt fibre and two dimension or three-dimensional woven, knitting, establishment or the loop bonding structural upright fabric of 1K, 3K, 6K, 9K and 12K, is applicable to preparation epoxy matrix composite, phenolic aldehyde based composites, polyimide-based composite material, unsaturated polyester based composites and thermoplastic matrix resin's matrix material.
Claims (8)
1, a kind of preparation method who is used for the organic-inorganic nano hybrid size of basalt fibre surface modification comprises the steps:
At first the presoma with metal or nonmetal oxide joins the alcoholic acid aqueous solution of pH value for 3-12, wherein said oxide precursor, water, alcoholic acid mole proportioning are 1: 1-7: 8-20, under 20-70 ℃, in whipped state, reacted 2-10 hour, make inorganic nano-particle pioneer liquid; Wherein said metal oxide comprises one or more in titanium, aluminium, zirconium, iron, tin, zinc, barium, the nickel oxide, and nonmetal oxide comprises one or more of silicon, phosphorous oxides;
Adopt γ-An Jibingjisanyiyangjiguiwan, (γ-phenylacetylene imino-) propyl-triethoxysilicane or 3-aminopropyl three ethoxy silane and organic compound reactions, the mole proportioning of γ-An Jibingjisanyiyangjiguiwan, (γ-phenylacetylene imino-) propyl-triethoxysilicane or 3-aminopropyl three ethoxy silane and organic compound is 1-5: 1, reaction conditions is: 20-80 ℃, stirred 2-10 hour, and made the modification organic compound; Or adopt γ-An Jibingjisanyiyangjiguiwan, (γ-phenylacetylene imino-) propyl-triethoxysilicane or 3-aminopropyl three ethoxy silane and the inorganic nano-particle pioneer liquid that makes to react, the mole proportioning of γ-An Jibingjisanyiyangjiguiwan, (γ-phenylacetylene imino-) propyl-triethoxysilicane or 3-aminopropyl three ethoxy silane and inorganic nano-particle pioneer liquid is 1: 20-30, reaction conditions is: 20-80 ℃, stirred 2-10 hour, and made modified inorganic nano-particle pioneer liquid;
Synthetic inorganic nano-particle pioneer's liquid and modification organic compound are carried out the hydridization reaction, or modified inorganic nano-particle pioneer liquid and organic compound are carried out the hydridization reaction, the hydridization reaction conditions is: temperature 20-80 ℃, stirred 2-15 hour;
Described organic compound is the organic compound that contains two keys, hydroxyl, carboxyl, amino, epoxy group(ing), isocyanate group or acetylene group.
2, preparation method according to claim 1 is characterized in that: described organic compound is bisphenol A type epoxy resin or polyimide or phenylethylene-maleic anhydride oligopolymer.
3, a kind of basalt fibre surface modifying method, its step comprises: 1) will be dissolved in the organic solvent by the hybrid size of claim 1 or 2 described preparation method's preparations, be mixed with the coating solution that the basalt fibre modification is used, 2) described coating solution is coated in basalt fibre surface, 3) the oven dry processing.
4, method of modifying as claimed in claim 3, it is characterized in that: described step 2) comprising: adopt the ultrasonic mode of coating of forcing continuously that fiber is forced dipping, immersion condition is: ultrasonic power is 10-1000W, and temperature is under the 20-50 ℃ of condition, speed 0.1-10m/min.
5, method of modifying as claimed in claim 3 is characterized in that: the temperature that oven dry is handled in the described step 3) is 50-150 ℃, and drying time is 3-60 minute.
6, as each described basalt fibre surface modifying method among the claim 3-5, it is characterized in that: in the described coating solution, the organic compound amount in the hybrid size and the mass ratio of organic solvent are 1-15: 100.
7, as each described basalt fibre surface modifying method among the claim 3-5, it is characterized in that: described organic solvent comprises ketone, alcohol or the mixture of the two.
8, basalt fibre surface modifying method as claimed in claim 7 is characterized in that: described ketone is acetone, and described alcohol is ethanol, ethylene glycol, propyl alcohol.
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| CN106237380A (en) * | 2016-08-30 | 2016-12-21 | 覃华贤 | A kind of medical nano composite and preparation method thereof |
| CN106673474B (en) * | 2017-01-13 | 2019-02-05 | 昆明理工大学 | A kind of dispersing method of foamed concrete basalt chopped fiber |
| CN107118580B (en) * | 2017-05-09 | 2020-11-24 | 安徽梦谷纤维材料科技有限公司 | Preparation method of basalt fiber reinforced wood-plastic composite material |
| CN108059364A (en) * | 2017-12-28 | 2018-05-22 | 安徽宏实光机电高科有限公司 | A kind of preparation method of basalt fibre response type size |
| CN111499209A (en) * | 2019-01-31 | 2020-08-07 | 四川思络普防护网工程有限公司 | Preparation process of basalt fiber for side slope protective net |
| CN110256107B (en) * | 2019-07-18 | 2022-01-18 | 西华大学 | Polyurethane foam heat-insulation and decoration integrated plate and preparation method thereof |
| CN115321842B (en) * | 2022-09-16 | 2023-05-05 | 四川轻化工大学 | Corrosion-resistant basalt fiber and preparation method thereof |
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