CN106589839B - A kind of high alkaline-resisting salt corrosion basalt fiber composite material - Google Patents
A kind of high alkaline-resisting salt corrosion basalt fiber composite material Download PDFInfo
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- CN106589839B CN106589839B CN201710091673.6A CN201710091673A CN106589839B CN 106589839 B CN106589839 B CN 106589839B CN 201710091673 A CN201710091673 A CN 201710091673A CN 106589839 B CN106589839 B CN 106589839B
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
- C08L63/10—Epoxy resins modified by unsaturated compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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Abstract
The invention discloses a kind of high alkaline-resisting salt corrosion basalt fiber composite materials, which includes following components：Basalt fibre, resin matrix, additive, curing agent and antifoaming agent, wherein the mass fraction that basalt fibre accounts for composite material is：60~88.4%；The mass fraction that resin matrix accounts for composite material is：10~35%；Additive accounts for resin matrix mass fraction：1~7%；Curing agent accounts for resin matrix mass fraction：1~40%；Antifoaming agent accounts for resin matrix mass fraction：0.1~3%.The composite material has high alkaline-resisting salt corrosion performance.
Description
Technical field
The present invention relates to a kind of basalt fiber composite materials, it particularly relates to a kind of high alkaline-resisting salt corrosion basalt
Fibrous composite.
Background technology
China's Mainland coastline is up to 18000 kilometers, and the city in 70% or more the whole nation is distributed in coastal area.At harbour and
Coastal region, reinforced concrete structures be chronically at seawater impregnate or the particular surroundings such as salt fog in, inevitably will be by
Physics to seawater and chemical attack, while there is also the corrosion of pore solution for inside concrete.This alkali and salt it is common
Effect causes concrete surface stripping or internal steel bar corrosion.The whole nation every year caused by seawater corrosion building loss and
Maintenance cost is up to billions of yuans.
Fibrous composite (FRP) because its high-strength light, insulation without magnetic, it is corrosion-resistant the advantages that, have been widely used for ocean
In engineering.In the fibrous composite for being applied and having studied at present, carbon fiber and aramid fiber have very high tension
Intensity and modulus, but material cost is very high, strongly limits their application.Simple glass fiber alkaline resistance properties is poor, special
Alkali-resistant glass fibre is of high cost, so it is of limited application.
Continuous basalt fiber (Continuous Basalt Fiber abbreviations basalt fibre) is with natural volcanic rock
(basalt or andesite) ore is as raw material, after melting at high temperature, the continuous fiber that is drawn by platinum rhodium bushing.Due to
There is the Fe of high level in basalt fibre ingredient2O3, FeO, make its not only and have that tensile strength is high, elasticity modulus is high, creep resistant
Deng mechanical property, but also have excellent alkaline-resisting salt chemistry erosion performance.Basalt fibre items mechanical index is above
Simple glass fiber；The long-term mechanical properties such as creep resistant, antifatigue are better than glass, aramid fiber, in civil engineering, traffic, ocean work
Journey etc. can replace common carbon fiber.Therefore it can be decided to be high performance structures material, be the strategic emerging industries in China,
With vast potential for future development.
When FRP material touches corrosive environment, as the first line of defence performance degradation occurs first for resin matrix, it
Deterioration velocity and degree of degeneration directly affect the corrosion resistance of FRP composite materials.Suitable pultrusion molding process and wide at present
In the general resin used, vinyl ester resin hot setting can occur volume contraction and generate contraction crack, be easy to corrosive medium
Into inside；Epoxy resin mechanical property and heat resistance are all preferable, but brittleness is big after solidification, easy to crack after being impacted, meeting
Substantially reduce its corrosion resistance.
Invention content
Technical problem：The technical problem to be solved by the present invention is to：It is multiple to provide a kind of high alkaline-resisting salt corrosion basalt fibre
Condensation material, the composite material have high alkaline-resisting salt corrosion performance.
Technical solution：In order to solve the above technical problems, the technical solution adopted by the present invention is：
A kind of high alkaline-resisting salt corrosion basalt fiber composite material, which includes following components：Basalt fibre,
Resin matrix, additive, curing agent and antifoaming agent, wherein
The mass fraction that basalt fibre accounts for composite material is：60~88.4%；
The mass fraction that resin matrix accounts for composite material is：10~35%；
Additive accounts for resin matrix mass fraction：1~7%；
Curing agent accounts for resin matrix mass fraction：1~40%；
Antifoaming agent accounts for resin matrix mass fraction：0.1~3%.
As preference, the resin matrix is vinylite, and the additive is that low volume shrinks modifying agent；
The curing agent is the mixed of benzoyl peroxide, the peroxidating 2 ethyl hexanoic acid tert-butyl ester and benzoyl peroxide tert-butyl ester composition
Close object；The antifoaming agent is BYK-A560.
As preference, the mass fraction that the curing agent accounts for resin matrix is 1~10%.
As preference, in the curing agent, benzoyl peroxide, the peroxidating 2 ethyl hexanoic acid tert-butyl ester and peroxidating
Mass ratio between the benzoyl tert-butyl ester is：2~3:3~4.5:1~1.5.
As preference, the additive is polyethylene.
As preference, the resin matrix is bisphenol A epoxide resin, and the additive is plasticized modifier, institute
The curing agent stated is acid anhydrides or polyamine, and the antifoaming agent is LX-205 organosilicons；Further include accelerating agent, the accelerating agent
For 2 methylimidazoles.
As preference, the mass fraction that the accelerating agent accounts for resin matrix is 0.1~5%.
As preference, the mass fraction that the curing agent accounts for resin matrix is 10~40%.
As preference, the additive is polypropylene glycol diglycidyl ether.
Advantageous effect：Compared with prior art, the embodiment of the present invention has the advantages that：The embodiment of the present invention it is profound
Military rock fibrous composite has good mechanical property and alkaline-resisting salt corrosion ability.It can be used as principal rod inside concrete structure
It uses, also can be used as supporting material outside concrete structure.In the embodiment of the present invention, vinylite is chosen, in vinyl tree
Low volume contracting agent polyethylene is added in fat, further decreases its cubical contraction, and it is micro- to reduce the contraction generated by cure shrinkage
Crackle, to greatly improve the alkaline-resisting salt corrosion performance of basalt fiber composite material.Toughening is added in bisphenol A epoxide resin
Agent polypropylene glycol diglycidyl ether (PPGDGE) reduces the brittleness of resin, reduces basalt fiber composite material because being rushed
The probability for hitting and cracking, to improve the alkaline-resisting salt corrosion performance of basalt fiber composite material.
Description of the drawings
Fig. 1 (a) is the basalt fiber composite material BFRP made of vinyl ester resin provided in present invention experiment
Muscle tensile strength retention rate is with corrosion age variation diagram；
Fig. 1 (b) is the basalt fiber composite material BFRP tendons made of E51 epoxy resin provided in present invention experiment
Tensile strength retention rate is with corrosion age variation diagram.
Specific implementation mode
With reference to embodiment, technical solution of the present invention is illustrated.
The embodiment of the present invention provides a kind of high alkaline-resisting salt corrosion basalt fiber composite material, including following components：The Black Warrior
Rock fiber, resin matrix, additive, curing agent and antifoaming agent, wherein
The mass fraction that basalt fibre accounts for composite material is：60~88.4%；
The mass fraction that resin matrix accounts for composite material is：10~35%；
Additive accounts for resin matrix mass fraction：1~7%；
Curing agent accounts for resin matrix mass fraction：1~40%；
Antifoaming agent accounts for resin matrix mass fraction：0.1~3%.
The preparation process of above-mentioned basalt fiber composite material is：
Resin matrix is prepared first, wherein when resin matrix selects vinyl ester resin, curing agent selects benzoyl peroxide
Formyl, the peroxidating 2 ethyl hexanoic acid tert-butyl ester and the benzoyl peroxide tert-butyl ester, antifoaming agent select BYKA560.Additive is selected
Low volume shrinks modifying agent, such as polyethylene.Additive ratio is the 1%-3% of vinyl ester matrix quality.
When resin matrix selects E51 epoxy resin, curing agent selects methyl tetrahydro phthalic anhydride, accelerating agent to select 2- methyl miaows
Azoles reduces solidification initiation temperature, and antifoaming agent selects LX-205 organosilicons.Additive selects toughener polypropylene glycol diglycidyl
Ether (PPGDGE).Additive quality is the 1~7% of epoxy resin-matrix weight.
Then basalt fiber composite material is prepared：By continuous basalt fiber precursor through above-mentioned resin infiltration, mould is utilized
Have molding machine and carry out just one-step forming, then carries out hot setting using the device that is heating and curing.Composite material is high using two benches
Temperature solidification：DSM430 vinyl ester resins are 80 DEG C of 2h initial solidifications, are cured after 120 DEG C of 2h.E51 epoxy resin uses 120 DEG C 4
Hour initial solidification cures after 160 DEG C of 2h.
Epoxy vingl ester resin DSM430 is chosen, low volume contracting agent polyethylene (PE) is added in resin, is further dropped
Its low cubical contraction reduces the contraction micro-crack generated by cure shrinkage, to greatly improve basalt fiber composite material
Alkaline-resisting salt corrosion performance.
Toughener polypropylene glycol diglycidyl ether (PPGDGE) is added in E51 epoxy resin, reduces the brittleness of resin,
Reduce the probability that basalt fiber composite material cracks because being impacted, to improve the alkaline-resisting of basalt fiber composite material
Salt corrosion performance.
As a preference, the resin matrix is vinylite.The additive is that low volume shrinks modification
Agent.Preferably, the additive is polyethylene (PE).The curing agent is benzoyl peroxide, peroxidating 2- ethyls
The mixture of hecanoic acid t-butyl ester and benzoyl peroxide tert-butyl ester composition.Preferably, in the curing agent, benzoyl peroxide first
Mass ratio between acyl, the peroxidating 2 ethyl hexanoic acid tert-butyl ester and the benzoyl peroxide tert-butyl ester is：2~3:3~4.5:1~
1.5.The mass fraction that the curing agent accounts for resin matrix is 1~10%.The antifoaming agent is BYK-A560.
As another preference, the basalt fiber composite material further includes accelerating agent.The accelerating agent is 2 first
Base imidazoles.The mass fraction that the accelerating agent accounts for resin matrix is 0.1~5%.The resin matrix is bisphenol-A epoxy tree
Fat.The additive is plasticized modifier, and the additive is polypropylene glycol diglycidyl ether (PPGDGE).Described
Curing agent is acid anhydrides or polyamine.The mass fraction that curing agent accounts for resin matrix is 10~40%.
The antifoaming agent is LX-205 organosilicons.
In order to confirm the validity of said program.The present invention verifies the present invention program to the Black Warrior by following tests method
The promotion of the alkaline-resisting salt corrosion performance of rock fibrous composite.
Test raw material
Using basalt fibre as reinforcing material.
When reisn base material uses DSM430 vinyl ester resins, the entitled D430, D430P1 of correspondence test specimen,
D430P2、D430P3.The additive is polyethylene (PE)；The curing agent is benzoyl peroxide, peroxidating 2- second
The mixture of base hecanoic acid t-butyl ester and benzoyl peroxide tert-butyl ester composition；The antifoaming agent is BYK-A560.Wherein, for
Test specimen D430, in curing agent between benzoyl peroxide, the peroxidating 2 ethyl hexanoic acid tert-butyl ester and the benzoyl peroxide tert-butyl ester
Mass ratio be：2:3:1.5, additive PE are 0.For test specimen D430P1, benzoyl peroxide, peroxidating 2- second in curing agent
Mass ratio between base hecanoic acid t-butyl ester and the benzoyl peroxide tert-butyl ester is：3:4:1, additive PE are the 1% of resin quality.
For test specimen D430P2, benzoyl peroxide, the peroxidating 2 ethyl hexanoic acid tert-butyl ester and the tertiary fourth of benzoyl peroxide in curing agent
Mass ratio between ester is：2.5:4.5:1.5, additive PE are the 2% of resin quality.For test specimen D430P3, in curing agent
Mass ratio between benzoyl peroxide, the peroxidating 2 ethyl hexanoic acid tert-butyl ester and the benzoyl peroxide tert-butyl ester is：3:3:
1.3, additive PE are the 3% of resin quality.
When reisn base material uses E51 epoxy resin, the entitled E51, E51PG4 of corresponding test specimen, E51PG5, E51PG7,
E51PG20.Additive selects polypropylene glycol diglycidyl ether (PPGDGE).Used in test specimen E51, E51PG4, test specimen E51PG5
Curing agent be acid anhydrides.Curing agent used in test specimen E51PG7 and test specimen E51PG20 is polyamine.Antifoaming agent is that LX-205 is organic
Silicon.Accelerating agent is 2 methylimidazoles.
The high alkaline-resisting salt corrosion basalt fiber composite material of table 1
Experiment process and result：
According to GB611-88 and GB1033-86, the modified solidification cubical contraction of vinyl ester resin is tested, as a result such as
Shown in table 2.The tensile property of vinylite and epoxy resin is tested according to GB/T-2567-2008, every group includes 5
A to repeat test specimen, the average value of acquired results is listed in table 3.According to the associated test standards of ACI (ACI)
ACI440.3R-04, to carrying out alkali salt by BFRP made of matrix (basalt fibre reinforcing composite material) muscle of modified resin
Solution corrosion is tested, and alkali salt solution component table is shown in Table 4, and experiment uses water bath with thermostatic control heating setting alkali salt solution temperature for 55 DEG C.
Corrosion spool is respectively 0,3,6,9 week.According to the tensile property of the front and back FRP tendons of GB/T-3354-1999 test corrosion, every group of packet
5 repetition test specimens are included, the average value of acquired results is listed in table 5.Wherein, B430 corresponds to BFRP tendons made of test specimen D430,
B430P1 corresponds to BFRP tendons made of test specimen D430P1, and B430P2 corresponds to BFRP tendons made of test specimen D430P2, and B430P3 is corresponded to
BFRP tendons made of test specimen D430P3, BE correspond to BFRP tendons made of test specimen E51, and BEPG4 is corresponded to made of test specimen E51PG4
BFRP tendons, BEPG5 correspond to BFRP tendons made of test specimen E51PG5, and BEPG7 corresponds to BFRP tendons made of test specimen E51PG7.
2 vinylite cubical contraction test result of table
3 resin mechanical property experimental results of table
4 manual simulation's alkali salt mixed chemical solution component proportion of table
5 BFRP tendons alkali salt solution of table impregnates tensile strength retention rate
As shown in Table 2, the cubical contraction of DSM430 resins is reduced to 3.98% by original 6.28%, illustrates polyethylene
Addition can effectively reduce the solidification cubical contraction of vinylite.As shown in Table 3, the addition of polyethylene is dropped to a certain extent
The low tensile strength and fracture elongation of vinylite, but do not significantly change the tensile property of vinylite；And gather
Although the addition of propylene glycol diglycidylether also reduces the tensile strength and elasticity modulus of epoxy resin to a certain extent,
But limitation is reduced, and resin fracture elongation percentage has been increased to 8.63% from 2.87%, toughening effect is notable.By number in table 5
It is grouped according to by different resins matrix, draws BFRP tendons tensile strength retention rate respectively with corrosion age variation diagram, such as Fig. 1.By Fig. 1
(a) it is found that low volume shrinks modified BFRP tendons after 55 DEG C of alkali salt solution effects, tensile strength retention rate is apparently higher than same item
Unmodified BFRP tendons under part.Low volume shrinks the BFRP tendons that modifying agent additive amount is 3% and shows relatively best resistance to alkali salt
Corrosive nature.After alkali salt solution corrosion 9 weeks, the tensile strength retention rate of D430P3 is unmodified under 76.39%, equal conditions
BFRP tendons are only 68.21%；By Fig. 1 (b) it is found that toughening modifying BFRP tendons are after 55 DEG C of alkali salt solution effects, plasticized modifier
The BFRP tendons that additive amount is 5% show relatively best alkaline-resisting salt corrosion performance.After alkali salt solution corrosion 9 weeks, the drawing of BEPG5
It is only 25.49% to stretch strength retention ratio unmodified BFRP tendons under 29.43%, equal conditions.
Claims (6)
1. a kind of high alkaline-resisting salt corrosion basalt fiber composite material, which is characterized in that the composite material includes following components：It is profound
Military rock fiber, resin matrix, additive, curing agent and antifoaming agent, wherein
The mass fraction that basalt fibre accounts for composite material is：60~88.4%；
The mass fraction that resin matrix accounts for composite material is：10~35%；
Additive accounts for resin matrix mass fraction：1~7%；
Curing agent accounts for resin matrix mass fraction：1~40%；
Antifoaming agent accounts for resin matrix mass fraction：0.1~3%；
The resin matrix is vinylite, and the additive is that low volume shrinks modifying agent；The curing agent is
The mixture of benzoyl peroxide, the peroxidating 2 ethyl hexanoic acid tert-butyl ester and peroxidized t-butyl perbenzoate composition；Described disappears
Infusion is BYK-A560；It is polyethylene that the low volume, which shrinks modifying agent,.
2. the alkaline-resisting salt corrosion basalt fiber composite material of height described in accordance with the claim 1, which is characterized in that the solidification
The mass fraction that agent accounts for resin matrix is 1~10%.
3. according to the alkaline-resisting salt corrosion basalt fiber composite material of height as claimed in claim 1 or 2, which is characterized in that described
In curing agent, the mass ratio between benzoyl peroxide, the peroxidating 2 ethyl hexanoic acid tert-butyl ester and peroxidized t-butyl perbenzoate
For：2~3:3~4.5:1~1.5.
4. a kind of high alkaline-resisting salt corrosion basalt fiber composite material, which is characterized in that the composite material includes following components：It is profound
Military rock fiber, resin matrix, additive, curing agent and antifoaming agent, wherein
The mass fraction that basalt fibre accounts for composite material is：60~88.4%；
The mass fraction that resin matrix accounts for composite material is：10~35%；
Additive accounts for resin matrix mass fraction：1~7%；
Curing agent accounts for resin matrix mass fraction：1~40%；
Antifoaming agent accounts for resin matrix mass fraction：0.1~3%；
The resin matrix is bisphenol A epoxide resin, and the additive is plasticized modifier, and the curing agent is acid anhydrides
Or polyamine, the antifoaming agent are LX-205 organosilicons；Further include accelerating agent, the accelerating agent is 2-methylimidazole；Institute
The plasticized modifier stated is polypropylene glycol diglycidyl ether.
5. high alkaline-resisting salt corrosion basalt fiber composite material according to claim 4, which is characterized in that the promotion
The mass fraction that agent accounts for resin matrix is 0.1~5%.
6. according to the alkaline-resisting salt corrosion basalt fiber composite material of height described in claim 4 or 5, which is characterized in that described solid
The mass fraction that agent accounts for resin matrix is 10~40%.
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| CN108929555A (en) * | 2017-05-24 | 2018-12-04 | 江苏创曦复合材料科技有限公司 | A kind of high-performance composite materials and preparation method thereof suitable for window frame |
| CN109879598A (en) * | 2019-04-24 | 2019-06-14 | 衡水瑞纤新材料科技有限公司 | A kind of high alkaline-resisting basalt fibre composition |
| CN114635291B (en) * | 2022-02-25 | 2023-10-13 | 哈尔滨工业大学 | Thermosetting resin coated inorganic nonmetallic fiber composite bundle and preparation method thereof |
| CN115418078A (en) * | 2022-09-20 | 2022-12-02 | 江苏绿材谷新材料科技发展有限公司 | Preparation method of high-durability carbon nanotube modified fiber reinforced composite material |
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| CN101235152A (en) * | 2007-06-13 | 2008-08-06 | 北京林业大学 | Basalt continuous fibre enhancement resin composite material and manufacturing method thereof |
| CN105504695B (en) * | 2016-02-01 | 2018-08-28 | 四川远鸣科技有限公司 | A kind of corrosion-resistant vinyl ester resin SMC sheet shape moulding compound of high-strength and high-modulus and preparation method thereof |
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Address after: 210093 Nanjing University Science Park, 22 Hankou Road, Gulou District, Nanjing City, Jiangsu Province Patentee after: Southeast University Address before: 211189 No. 2 Southeast University Road, Jiangning District, Nanjing, Jiangsu Patentee before: Southeast University |
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Application publication date: 20170426 Assignee: JIANGSU GREEN MATERIALS VALLY NEW MATERIAL T&D Co.,Ltd. Assignor: SOUTHEAST University Contract record no.: X2020980009971 Denomination of invention: A basalt fiber composite with high alkali salt resistance Granted publication date: 20180907 License type: Common License Record date: 20201225 |