CN104059336B - A kind of Basalt fiber composite rib and preparation method thereof - Google Patents
A kind of Basalt fiber composite rib and preparation method thereof Download PDFInfo
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- CN104059336B CN104059336B CN201410290224.0A CN201410290224A CN104059336B CN 104059336 B CN104059336 B CN 104059336B CN 201410290224 A CN201410290224 A CN 201410290224A CN 104059336 B CN104059336 B CN 104059336B
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Abstract
The invention discloses a kind of Basalt fiber composite rib and preparation method thereof, described Basalt fiber composite rib be by basalt fibre surface treated agent process after, the fiber bar material impregnated by matrix resin again and solidify, described basalt fibre is to be made by the composite twist rove of rove or textile process, its a diameter of 7～13 μm, its preparation method then includes that Fiber strength, infusing matrix resin and three steps of curing molding are made.Instant invention overcomes many defects present in existing fibreglass maker skill, use the operating procedures such as brushing, dipping, vacuum pressed, drying, not only making step is simple, quick, also can realize industrialized large-scale production, and cost of manufacture is cheap.
Description
Technical field
The present invention is a kind of Basalt fiber composite rib and preparation method thereof, particularly relates to composite reinforcing of basalt fibre reinforcing material making and preparation method thereof, belongs to the preparation field of composite.
Background technology
In existing field of compound material, fiber as composite reinforcing reinforcement mainly has glass fibre, carbon fiber, boron fibre, alumina fibre, silicon carbide fibre, polyethylene fibre etc., but the restriction due to price factor, major part fiber is all served only for military field, only glass fibre is also widely used for civil area, but in actual application, glass fibre there is also certain defect as composite reinforcing reinforcement, such as:
(1) the production process energy consumption of glass fibre is relatively big, is unfavorable for energy-conserving and environment-protective；
(2) preparation technology of glass fibre is to harmful, and especially glass fibre hair can produce stimulation to human body skin, can not be decomposed or absorb, it is likely that cause pulmonary disease even to produce canceration after sucking human body；
(3) environmental pollution is big, can not recycle or natural degradation, be unfavorable for the protection of environment after glass fibre composite reinforcing is discarded, etc..
Certainly, for overcoming the use defect of above-mentioned composite reinforcing reinforcement, there has been proposed the use using continuous basalt fiber as composite reinforcing reinforcement, for continuous basalt fiber it is understood that, it is with natural volcano effusive rock as raw material, after melting under the high temperature of 1450～1500 DEG C, the continuous fiber being fabricated by by platinum germanium alloy bushing wire drawing, there is high intensity, high-modulus, high temperature resistant, antioxidation, acid and alkali-resistance, radioprotective, electric insulation, adiabatic sound insulation, filterability is good, comprcssive strength is high, many premium properties such as damping and shear strength height, simultaneously, also it is a kind of novel environment-protection fiber.
nullExisting patent documentation CN101531806(polyphenyl dioctyl phthalate ethylene glycol fat/basalt fiber composite material and preparation method thereof 2009.9.16) and the CN103044877A(mono-kind composite containing treated basalt fiber and polymer and preparation method thereof 2013.04.17) all disclose and a kind of utilize basalt fibre as reinforcement for making the preparation method of composite，But we to above-mentioned preparation method obtain composite products and occur on the market carried out performance test by continuous basalt fiber composite，Test result shows，The mechanical property of composite is had a great impact by different technology conditions，It is mainly manifested in the composition of basalt fiber material system、The aspects such as the selection of Fiber strength and the structure of composite，And existing composite need to strengthen in mechanical property，For this，The present invention proposes a kind of Basalt fiber composite rib and preparation method thereof specially.
Summary of the invention
It is an object of the invention to provide a kind of Basalt fiber composite rib, after selecting basalt fibre surface treated successively and the infusing matrix resin of specific component content, the fiber bar material that mechanical property is more excellent compared with prior art can not only be obtained, the cost performance that fiber bar material makes can also be improved, simultaneously, more overcome the use defect of currently used relatively broad glass fibre, more use value.
Another object of the present invention is to provide the preparation method of a kind of Basalt fiber composite rib, overcome many defects present in existing fibreglass maker skill, there is the advantages such as making step is simple, quick, be suitably widely popularized use.
The present invention is achieved through the following technical solutions: a kind of Basalt fiber composite rib and preparation method thereof, described Basalt fiber composite rib be by basalt fibre surface treated agent process after, the fiber bar material impregnated by matrix resin again and solidify, counting by weight ratio, described basalt fibre includes following component:
SO2: 45～60%；
Al2O3: 12～19%；
CaO:6～12%；
Fe2O3FeO:9.1～15%, the Basalt fiber composite rib that the present invention relates to is to be made by the basalt fibre of specific component content, this basalt fibre is different from metal, glass and other carbide raw materials, it it is ore selected by volcanic rock, that heavily the component smelted of refining is stable, exploit the most very convenient, the performance of this basalt fibre is the most superior, wherein, and SO2It is the main component of basalt fibre, maintains chemical stability and the mechanical strength of fiber；And Al2O3Decapacitation improves outside the chemical stability of basalt fibre, same, moreover it is possible to improve its heat stability and mechanical strength.
In the present invention, described basalt fibre is to be made by the composite twist rove of rove or textile process, its a diameter of 7～13 μm.
In actual mechanical process, basalt fibre, after surface treated, can improve the composite performance of matrix resin and basalt fibre, here, described surface conditioning agent includes: by general formula RnSiX4-nThe organosilicon alkanes coupling agent represented, wherein, R includes methoxy or ethoxy, and n is 1,2 or 3.
For preferably realizing aforesaid operations, described surface conditioning agent is fertile blue inorganic agent or KH560 inorganic agent.
In the present invention, one or more in vinyl ester resins, epoxy resin and unsaturated polyester resin of described matrix resin.
Further, described matrix resin is vinyl ester resins, such as: urethane-modified vinyl ester resins, bisphenol A modified epoxy vinyl fat resin etc..
In the present invention, the preparation method of described Basalt fiber composite rib, comprise the steps:
(1) Fiber strength: surface conditioning agent is configured to the aqueous solution that concentration is 1～5%, and use painting tool that the painting of this aqueous solution is covered with the outer surface at basalt fibre, after brushing 1～11 time, basalt fibre is put into vacuum drying oven evacuation heating 20～40min removing moisture at 75～95 DEG C again, then, regulation vacuum drying oven temperature is 100～120 DEG C, and after reacting 80～100min, the surface completing basalt fibre processes；
(2) infusing matrix resin: be sequentially added into accelerator and firming agent in matrix resin, glue is prepared after stirring, matrix resin: accelerator: the weight proportion of firming agent is 400:(0.5～1.5): (0.5～1.5), using painting tool to be coated with by this glue to be covered with on the basalt fibre after surface treated, brushing number of times is 1～11 time；
(3) curing molding: basalt fibre step (2) prepared, according to 0 ° or 90 ° of direction orthogonal arrangement, is put into pressurization 0.5～1.5MPa in solidifying and molding device, is warming up to 110～130 DEG C, after curing reaction 0.5～1.5h, prepares Basalt fiber composite rib.
The present invention compared with prior art, has the following advantages and beneficial effect:
(1) Basalt fiber composite rib that the present invention relates to is to prepare after the surface treated successively of the basalt fibre by specific component content and infusing matrix resin, good chemical stability, heat stability and the mechanical strength having based on basalt fibre, the Basalt fiber composite rib being composited also has stronger mechanical property, can be widely applied to industry, building trade, petroleum industry and the aircraft industry etc. such as civilian.
(2) instant invention overcomes many defects present in existing fibreglass maker skill, use the operating procedures such as brushing, dipping, vacuum pressed, drying, not only making step is simple, quick, also can realize industrialized large-scale production, and cost of manufacture is cheap.
(3) present invention is reasonable in design, in actual mechanical process, fertile blue inorganic agent or KH560 inorganic agent can be used as surface conditioning agent, process for the surface of basalt fibre, thus reaching the purpose improving matrix resin with basalt fibre composite performance, using effect is good.
(4) matrix resin that the present invention relates to is selected from one or more in vinyl ester resins, epoxy resin and unsaturated polyester resin, especially vinyl ester resins, such as: urethane-modified vinyl ester resins, bisphenol A modified epoxy vinyl fat resin etc., tests prove that, when the basalt fibre muscle using vinyl ester resins dipping is tested, test result surface, its anti-flammability, degree of drawing and bending property test are better.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited to this.
Embodiment 1:
The present invention proposes a kind of Basalt fiber composite rib and preparation method thereof, this Basalt fiber composite rib be processed by basalt fibre surface treated agent after, then the fiber bar material being impregnated by matrix resin and solidifying.
The following is and technical solution of the present invention is further described:
In the present invention, basalt fibre is to be made by the composite twist rove of rove or textile process, and its diameter can be selected for 7 μm, counts by weight ratio, and basalt fibre includes following component:
SO2: 52.43%；
Al2O3: 18.33%；
CaO:7.68%；
Fe2O3FeO:10.53%；
Other are (such as: Na2O、K2O、MgO、TiO2Deng): 11.03%.
The Basalt fiber composite rib that the present invention relates to is to be made by the basalt fibre of specific component content, this basalt fibre is different from metal, glass and other carbide raw materials, it it is ore selected by volcanic rock, that heavily the component smelted of refining is stable, exploit the most very convenient, the performance of this basalt fibre is the most superior, wherein, SO2It is the main component of basalt fibre, maintains chemical stability and the mechanical strength of fiber；And Al2O3Decapacitation improves outside the chemical stability of basalt fibre, same, moreover it is possible to improve its heat stability and mechanical strength.
Surface conditioning agent includes: by general formula RnSiX4-nThe organosilicon alkanes coupling agent represented, wherein, R includes methoxy or ethoxy, n is 1,2 or 3, the surface being mainly used in basalt fibre processes, basalt fibre after surface treated agent process is during compound with matrix resin, it can be conducive to being formed between basalt fibre and matrix resin a good bonding interface, thus reach to improve the purpose of its composite performance, on this basis, the intensity of basalt fibre muscle, anti-wear performance etc. are all had good improvement result, and in the present embodiment, surface conditioning agent selects fertile blue inorganic agent.
Matrix resin is selected from one or more in vinyl ester resins, epoxy resin and unsaturated polyester resin, it is mainly used in the dipping of basalt fibre, on the basis of fully infiltration, matrix resin is i.e. filled in the surface of basalt fibre, after resin solidifies, can matrix resin with realize cast setting at basalt fibre depression in the surface and gap and couple, reach to improve the purpose of basalt fibre mechanical characteristic, in the present embodiment, matrix resin selects urethane-modified vinyl ester resins.
The preparation method of the Basalt fiber composite rib that the present embodiment relates to comprises the steps:
(1) Fiber strength: fertile blue inorganic agent is configured to the aqueous solution that concentration is 1%, and use painting tool that the painting of this aqueous solution is covered with the outer surface at basalt fibre, after brushing 11 times, basalt fibre is put into vacuum drying oven evacuation heating 20min at 75 DEG C again and removes moisture, then, regulation vacuum drying oven temperature is 100 DEG C, and after reacting 80min, the surface completing basalt fibre processes；
(2) infusing matrix resin: be sequentially added into accelerator and firming agent in urethane-modified vinyl ester resins, glue is prepared after stirring, matrix resin: accelerator: the weight proportion of firming agent is 400:0.5:0.5, using painting tool to be coated with by this glue to be covered with on the basalt fibre after surface treated, brushing number of times is 11 times；
(3) curing molding: basalt fibre step (2) prepared is according to 0 ° or 90 ° of direction orthogonal arrangement, put into pressurization 0.5MPa in solidifying and molding device, be warming up to 110 DEG C, after curing reaction 0.5h, preparing Basalt fiber composite rib, its fiber volume fraction is 37%.
Embodiment 2:
In the present embodiment, basalt fibre select diameter 9 μm, count by weight ratio, basalt fibre includes following component:
SO2: 52.43%；
Al2O3: 18.33%；
CaO:7.68%；
Fe2O3FeO:10.53%；
Other are (such as: Na2O、K2O、MgO、TiO2Deng): 11.03%.
Surface conditioning agent selects KH560 inorganic agent.
Matrix resin selects bisphenol A modified epoxy vinyl fat resin.
In the present invention, the preparation method of described Basalt fiber composite rib, comprise the steps:
(1) Fiber strength: KH560 inorganic agent is configured to the aqueous solution that concentration is 2%, and use painting tool that the painting of this aqueous solution is covered with the outer surface at basalt fibre, after brushing 11 times, basalt fibre is put into vacuum drying oven evacuation heating 30min at 80 DEG C again and removes moisture, then, regulation vacuum drying oven temperature is 110 DEG C, and after reacting 90min, the surface completing basalt fibre processes；
(2) infusing matrix resin: be sequentially added into accelerator and firming agent in bisphenol A modified epoxy vinyl fat resin, glue is prepared after stirring, matrix resin: accelerator: the weight proportion of firming agent is 400:1:1, using painting tool to be coated with by this glue to be covered with on the basalt fibre after surface treated, brushing number of times is 11 times；
(3) curing molding: basalt fibre step (2) prepared is according to 0 ° or 90 ° of direction orthogonal arrangement, put into pressurization 1.0MPa in solidifying and molding device, be warming up to 120 DEG C, after curing reaction 1h, preparing Basalt fiber composite rib, its fiber volume fraction is 37%.
Embodiment 3:
In the present embodiment, basalt fibre select diameter 13 μm, count by weight ratio, basalt fibre includes following component:
SO2: 52.43%；
Al2O3: 18.33%；
CaO:7.68%；
Fe2O3FeO:10.53%；
Other are (such as: Na2O、K2O、MgO、TiO2Deng): 11.03%.
Surface conditioning agent selects KH560 inorganic agent.
Matrix resin selects urethane-modified vinyl ester resins.
In the present invention, the preparation method of described Basalt fiber composite rib, comprise the steps:
(1) Fiber strength: KH560 inorganic agent is configured to the aqueous solution that concentration is 5%, and use painting tool that the painting of this aqueous solution is covered with the outer surface at basalt fibre, after brushing 11 times, basalt fibre is put into vacuum drying oven evacuation heating 40min at 95 DEG C again and removes moisture, then, regulation vacuum drying oven temperature is 120 DEG C, and after reacting 100min, the surface completing basalt fibre processes；
(2) infusing matrix resin: be sequentially added into accelerator and firming agent in urethane-modified vinyl ester resins, glue is prepared after stirring, matrix resin: accelerator: the weight proportion of firming agent is 400:1.5): 1.5), using painting tool to be coated with by this glue to be covered with on the basalt fibre after surface treated, brushing number of times is 11 times；
(3) curing molding: basalt fibre step (2) prepared is according to 0 ° or 90 ° of direction orthogonal arrangement, put into pressurization 1.5MPa in solidifying and molding device, be warming up to 130 DEG C, after curing reaction 1.5h, preparing Basalt fiber composite rib, its fiber volume fraction is 37%.
The Basalt fiber composite rib prepared in above-described embodiment 1～3 is carried out Mechanics Performance Testing, and test result is as shown in table 1:
Table 1
| Numbering | Fibre diameter | Fiber volume fraction | Hot strength | Elastic modelling quantity | Bending strength | Bending modulus |
| 1 | 7μm | 37% | 277.6 | 15.2 | 497.2 | 16.5 |
| 2 | 9μm | 37% | 261.9 | 14.8 | 495.3 | 15.8 |
| 3 | 13μm | 37% | 245.1 | 14.6 | 495.0 | 14.8 |
The above, be only presently preferred embodiments of the present invention, and the present invention not does any pro forma restriction, every above example is made according to the technical spirit of the present invention any simple modification, equivalent variations, within each falling within protection scope of the present invention.
Claims (1)
1. a Basalt fiber composite rib, it is characterized in that: described Basalt fiber composite rib be by basalt fibre surface treated agent process after, the fiber bar material impregnated by matrix resin again and solidify, counts by weight ratio, and described basalt fibre includes following component:
SiO2: 45～60%；
Al2O3:12～19%；
CaO:6～12%；
Fe2O3FeO:9.1～15%,
Described basalt fibre is to be made by the composite twist rove of rove or textile process, its a diameter of 7～13 μm,
Described surface conditioning agent includes: by general formula R nSiX4The organosilicon alkanes coupling agent that-n represents, wherein, R includes methoxy or ethoxy, and n is 1,2 or 3, and described surface conditioning agent is fertile blue inorganic agent or KH560 inorganic agent；One or more in vinyl ester resins, epoxy resin and unsaturated polyester resin of described matrix resin, described matrix resin is vinyl ester resins；
The preparation method of described Basalt fiber composite rib comprises the steps:
(1) Fiber strength: surface conditioning agent is configured to the aqueous solution that concentration is 1～5%, and use painting tool that the painting of this aqueous solution is covered with the outer surface at basalt fibre, after brushing 1～11 time, basalt fibre is put into vacuum drying oven evacuation heating 20～40min removing moisture at 75～95 DEG C again, then, regulation vacuum drying oven temperature is 100～120 DEG C, and after reacting 80～100min, the surface completing basalt fibre processes；
(2) infusing matrix resin: be sequentially added into accelerator and firming agent in matrix resin, glue is prepared after stirring, matrix resin: accelerator: the weight proportion of firming agent is 400:(0.5～1.5): (0.5～1.5), using painting tool to be coated with by this glue to be covered with on the basalt fibre after surface treated, brushing number of times is 1～11 time；
(3) curing molding: basalt fibre step (2) prepared, according to 0 ° or 90 ° of direction orthogonal arrangement, is put into pressurization 0.5～1.5MPa in solidifying and molding device, is warming up to 110～130 DEG C, after curing reaction 0.5～1.5h, prepares Basalt fiber composite rib.
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| CN107619212A (en) * | 2017-08-03 | 2018-01-23 | 江苏天龙玄武岩连续纤维股份有限公司 | Basalt scale composite reinforcing |
| CN109896748A (en) * | 2019-04-24 | 2019-06-18 | 衡水瑞纤新材料科技有限公司 | A kind of high-modulus basalt fibre composition |
| CN117487324A (en) * | 2023-11-27 | 2024-02-02 | 浙江鑫硕新材料有限公司 | Basalt fiber reinforced corrosion-resistant composite rib and preparation method thereof |
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