CN102426884A - Fiber composite core rod with improved performances for overhead wire and preparation method thereof - Google Patents
Fiber composite core rod with improved performances for overhead wire and preparation method thereof Download PDFInfo
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- CN102426884A CN102426884A CN2011102668324A CN201110266832A CN102426884A CN 102426884 A CN102426884 A CN 102426884A CN 2011102668324 A CN2011102668324 A CN 2011102668324A CN 201110266832 A CN201110266832 A CN 201110266832A CN 102426884 A CN102426884 A CN 102426884A
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Abstract
The invention relates to a fiber composite core rod with improved performances for an overhead wire, comprising continuous basalt fiber twistless roving and an epoxy resin part, wherein the epoxy resin part is formed at the periphery of the continuous basalt fiber twistless roving by uniform dipping;The composite core rod is prepared by the following steps of: (1) using a coupling agent to carry out surface treatment on nano SiO2; (2) preparing infiltrate of the nano SiO2, and using the infiltrate of the nano SiO2 to carry out surface roughening and lipophilicity modification and treatment on the continuous basalt fiber twistless roving; (3) using the coupling agent to carry out surface treatment on calcium carbonate whiskers and square zinc oxide whiskers; (4) preparing epoxy resin dipping solution and conveying the continuous basalt fiber twistless roving into the epoxy resin dipping solution for full dipping; and (5) treating the continuous basalt fiber twistless roving by adopting a pulling-extruding process. The fiber composite core rod has the advantages of low manufacturing cost, higher cost performance, and excellent mechanization, heating and heat ageing resistance and creepage performances.
Description
Technical field
[0001] the present invention relates to the fiber composite plug of a kind of electric power transfer, relate in particular to a kind of low cost of manufacture, have high cost performance, have excellent machinery, heat and heat ageing, composite core rod of croop property and preparation method thereof with aerial condutor.
Background technology
[0002] aerial condutor is called capacity expansion conducting wire again.Existing aerial condutor is the carbon fiber complex core aerial condutor, and its structure is: the center is a carbon fiber composite core rod, and the periphery is the trapezoidal soft aluminium molded lines with the carbon fiber composite core rod concentric stranding.
The cross section of carbon fiber composite core rod is circular, vertically is uniform pole structure.Carbon fiber composite core rod is divided into the carbon fiber composite core rod of two-layer structure and the carbon fiber composite core rod of three-decker.
The carbon fiber composite core rod of said two-layer structure, its internal layer are the carbon fiber composite portion, and skin is a glass fiber compound inslation part.
The carbon fiber composite core rod of said three-decker, its internal layer are the glass fiber composite portion, and the intermediate layer is the carbon fiber composite portion, and skin is a glass fiber compound inslation part.
No matter two-layer structure still is the carbon fiber composite core rod of three-decker; Its outer field glass fiber compound inslation part is under certain mechanical performance situation; Can reduce the cost of product, can also play the effect of insulating barrier, in carbon fiber composite core rod, produce power consumption to avoid aerial condutor.
The internal layer of the carbon fiber composite core rod of said three-decker is the glass fiber composite portion, for the material cost that reduces product designs.
The carbon fiber complex core aerial condutor adopts the high-performance carbon fibre composite material as the lead plug, have the intensity height, in light weight, the coefficient of expansion is little, characteristics such as corrosion-resistant and high temperature resistant.This carbon fiber complex core aerial condutor, key technology is carbon fiber composite core rod, and existing product problem is that carbon fibre material is with high costs, and the raw material source receives restriction to a certain degree, has limited applying of aerial condutor.
Carbon fiber production major technology content is the precursor technology, though more domestic enterprises can produce the carbon fiber product of (or approaching) T300 level and T700 level, quality is also unstable, and this explanation precursor problem is not solved.Such as producing the fine base of polypropylene (PAN) the precursor manufacture grade carbon fiber that more generally uses now; Be not simply temperature to be burnt height; Just can make stay-in-grade carbon fiber; The acrylic fibers structure of making such as the fine base of polypropylene (PAN) is an ambiguity, and direction is in a mess, and this is the maximum problem of carbon fiber industry.Need give the appropriate mechanics of fiber and handle in suitable temperature in the manufacturing.The pith that carbon fiber is made is technical at precursor, but present domestic industry extremely is short of on the deposit of this technology and application power.Not only need the support of policy, the input of fund also needs the intervention of large-scale chemical fiber factory, could the cost of Carbon Fiber Technology be lowered.
Pultrusion is a kind of important method of making high-performance, low-cost continuous composite material; Pultrusion molding process requires matrix resin should have characteristics such as reaction speed is fast, viscosity is low, pot life is long, and fast pultrusion commonly used mainly is the unsaturated polyester resin of radical-curable with resin.The pultrude process function admirable of this resinoid, but have the lower shortcoming of heat resistance.Though the part resin has the better heat-resisting performance, the glass transition temperature Tg of solidfied material generally is not higher than 180 ℃, and often exists interface performance relatively poor for the high-performance carbon fibre composite material, brings the problem of hot strength and poor toughness.Though can obtain higher heat resistance through general purpose epoxy resin is carried out modification, be difficult to be applicable to large-scale production.
In sum, the problem that existing carbon fiber composite core rod exists is that carbon fiber is with high costs, and material source is not really extensive, and its heat resistance is low, and the interface performance of composite material is relatively poor, has influence on the temperature and the mechanical performance of composite core rod.
Summary of the invention
[0012] the present invention's technical problem that will solve is: overcome that existing carbon fiber composite core rod is with high costs, material source not extensively, the defective of low, the composite material interface difference of heat resistance, a kind of low cost of manufacture is provided, has high cost performance, has excellent machinery, heat and heat ageing, composite core rod of croop property and preparation method thereof.
In order to solve the problems of the technologies described above; First technical scheme that the present invention adopted is: a kind of aerial condutor that improves performance is used the fiber composite plug, and it comprises the continuous basalt fiber roving and is formed on this continuous basalt fiber roving epoxy resin part on every side through even dipping; Said composite core rod is prepared from following steps: step 1: with coupling agent with nanometer SiO
2Carry out surface treatment; Step 2: with the nanometer SiO after step 1 processing
2Preparation nanometer SiO
2Infiltrate, and use nanometer SiO
2Infiltrate carries out surface coarsening and lipophile transformation to the continuous basalt fiber roving, in processing procedure, handles with ultrasonic unit; Step 3: calcium carbonate crystal whisker and four jiaos of ZnOws are carried out surface treatment with coupling agent; Step 4: calcium carbonate crystal whisker and four jiaos of ZnOws with after step 3 processing prepare epoxy resin impregnated solution; Continuous basalt fiber roving after step 2 handled is sent in this epoxy resin impregnated solution fully dipping; Around this continuous basalt fiber roving, form epoxy resin structural, in processing procedure, handle with ultrasonic unit; Step 5: this continuous basalt fiber roving process pultrude process with step 4 obtains obtains said composite core rod at last.
Further qualification to above-mentioned first technical scheme is: in the step 1, choose the nanometer SiO of 70nm-120nm
2, adopt silane coupler and butyl methacrylate that nano particle is carried out surface treatment, improved the lipophile of nano particle, reduced hydrophily, eliminated the phenomenon of separating with organic facies.
Further qualification to above-mentioned first technical scheme is: the nanometer SiO described in the step 2
2The preparation process of infiltrate is: by mass concentration, and nanometer SiO
2Be 1%, film forming agent is 25%, and coupling agent is 5%, and lubricant is 35%, and antistatic agent is 34%, handles with ultrasonic unit.
Further qualification to above-mentioned first technical scheme is: in the step 3, use isopropyl three (isostearoyl base) titanate coupling agent that calcium carbonate crystal whisker is carried out surface preparation; The method that four jiaos of ZnOws are carried out surface preparation is: a certain amount of silane coupler is added in entry-acetone soln; Regulate pH value to acid with hydrochloric acid, be hydrolyzed, then a certain amount of four jiaos of ZnOws are added wherein; In water bath with thermostatic control, stir 30 ~ 60min; Filtration under diminished pressure,, for use at 150 ℃ of following activation 8h after super-dry with deionized water wash to there not being the chlorine particle.
Further qualification to above-mentioned first technical scheme is: the epoxy resin impregnated solution of preparation in the step 4; Its preparation process is following: add in the epoxy resin with the calcium carbonate crystal whisker of 5% ~ 6% mass ratio and 2% ~ 3% ZnOw in advance, stirred 30 minutes with electromagnetic stirrer at 20 ℃ ± 2 ℃.
In order to solve the problems of the technologies described above, second technical scheme that the present invention adopted is: a kind of preparation method who improves the aerial condutor of performance with the fiber composite plug, it comprises the steps:
Step 1: with coupling agent with nanometer SiO
2Carry out surface treatment;
Step 2: with the nanometer SiO after step 1 processing
2Preparation nanometer SiO
2Infiltrate, and use nanometer SiO
2Infiltrate carries out surface coarsening and lipophile transformation to the continuous basalt fiber roving, in processing procedure, handles with ultrasonic unit;
Step 3: calcium carbonate crystal whisker and four jiaos of ZnOws are carried out surface treatment with coupling agent;
Step 4: calcium carbonate crystal whisker and four jiaos of ZnOws with after step 3 processing prepare epoxy resin impregnated solution; Continuous basalt fiber roving after step 2 handled is sent in this epoxy resin impregnated solution fully dipping; Around this continuous basalt fiber roving, form epoxy resin structural, in processing procedure, handle with ultrasonic unit;
Step 5: this continuous basalt fiber roving process pultrude process with step 4 obtains obtains said composite core rod at last.
Further qualification to above-mentioned second technical scheme is: in the step 1, choose the nanometer SiO of 70nm-120nm
2, adopt silane coupler and butyl methacrylate that nano particle is carried out surface treatment, improved the lipophile of nano particle, reduced hydrophily, eliminated the phenomenon of separating with organic facies.
Further qualification to above-mentioned second technical scheme is: the nanometer SiO described in the step 2
2The preparation process of infiltrate is: by mass concentration, and nanometer SiO
2Be 1%, film forming agent is 25%, and coupling agent is 5%, and lubricant is 35%, and antistatic agent is 34% to mix.
Further qualification to above-mentioned second technical scheme is: in the step 3, use isopropyl three (isostearoyl base) titanate coupling agent that calcium carbonate crystal whisker is carried out surface preparation; The method that four jiaos of ZnOws are carried out surface preparation is: a certain amount of silane coupler is added in entry-acetone soln; Regulate pH value to acid with hydrochloric acid, be hydrolyzed, then a certain amount of four jiaos of ZnOws are added wherein; In water bath with thermostatic control, stir 30 ~ 60min; Filtration under diminished pressure, with deionized water wash to there not being the chlorine particle, after super-dry at 150 ℃ of following activation 8h.
Further qualification to above-mentioned second technical scheme is: the epoxy resin impregnated solution of preparation in the step 4; Its preparation process is following: add in the epoxy resin with the calcium carbonate crystal whisker of 5% ~ 6% mass ratio and the ZnOw of 2% ~ 3% mass ratio in advance, stirred 30 minutes with electromagnetic stirrer at 20 ℃ ± 2 ℃.
The beneficial effect that the present invention obtains is:
1, the composite material plug has high-temperature stability and excellent mechanical performance, and low cost of manufacture has high cost performance, can increase the lead transmission current effectively more than 2 times.
2, composite core rod of the present invention is compared with carbon fiber composite core rod, has high cost performance.
3, composite core rod of the present invention is used for electric power transfer and uses aerial condutor, compares with the carbon fiber complex core aerial condutor, has performances such as excellent heat and heat ageing, creep.
Description of drawings
Fig. 1 is that the present invention improves the cross-sectional view of the aerial condutor of performance with the fiber composite plug.
Fig. 2 is the detailed process flow figure of composite core rod of the present invention.
Fig. 3 is a matrix reinforcing material surface-treated sketch map.
Fig. 4 is the preforming tool sketch map.
Fig. 5 is an epoxy resin cure mould sketch map.
Embodiment
See also Fig. 1, the present invention proposes a kind of aerial condutor that improves performance and uses the fiber composite plug, and it comprises continuous basalt fiber roving 1 and is formed on this continuous basalt fiber roving 1 epoxy resin part 2 on every side through even dipping.
Aforesaid continuous basalt fiber roving 1, fibre diameter are 7um, and line density is 300-500tex, in order to temperature characterisitic, the mechanical performance of improving plug.
This continuous basalt fiber roving 1 is through nanometer SiO
2Carrying out surface coarsening handles.Above-mentioned nanometer SiO
2Be used for strengthening the interface performance of continuous basalt fiber roving 1.
The basalt fiber material wide material sources, material quality is good, as the wild phase of composite material, compares with carbon fiber, has tangible superiority of effectiveness.
Following table is the physical property contrast of continuous basalt fiber roving 1 (being abbreviated as CBF) and various fiber materials:
| Performance | CBF | The E glass | Carbon fiber | Aramid fiber | Rock wool |
| Density/(g/cm3) | 2.6～2.8 | 2.5～2.6 | 1.7～2.2 | 1.49 | 2.5 |
| Serviceability temperature (℃) | －260～880 | －60～350 | The highest by 2000 | The highest by 250 | The highest 600 ℃ |
| The coefficient of heat conduction (w/mk) | 0.031～0.038 | 0.034～0.040 | 5～185 | 0.04～0.13 | 0.034～0.048 |
| Specific volume resistance (Ω m) | 1×10 12 | 1×10 11 | 2×10 －5 | 3×10 13 | ? |
| Modulus of elasticity (Gpa) | 79.3～93.1 | 72.5～75.5 | 230～600 | 70～140 | ? |
| Tensile strength (Mpa) | 3000～4840 | 3100～3800 | 3500～6000 | 2900～3400 | ? |
Continuous basalt fiber roving 1 (being abbreviated as CBF) is used for overhead wire lead aspect, has following remarkable advantages:
1, significant resistance to elevated temperatures and thermal shock resistance.The serviceability temperature scope of CBF is-260 ℃～880 ℃.Good thermal shock stability remains unchanged under 500 ℃ of temperature, and original weight only loses 3% in the time of 900 ℃.This outstanding properties is suitable for producing under the electric current full load conditions aerial condutor use of resonance.Though maximum operation (service) temperature is lower than carbon fiber, in concrete aerial condutor application facet, its temperature applicable range can reach requirement fully.
2, the lower coefficient of heat conduction.The coefficient of heat conduction of CBF is 0.031 W/mK～0.038 W/mK, is lower than carbon fiber.
3, high modulus of elasticity and tensile strength.The modulus of elasticity of CBF is: 9100 kg/mm
2～11000 kg/mm
2Though, being lower than carbon fiber and steel, its index is compared high by 30% with the soft aluminium that lead is adopted, can satisfy the requirement of lead stretch-proof.The tensile strength of CBF is 3800～4800 MPa, and is all higher than large-tow carbon fiber.
4, chemical stability is good.Acid resistance and the alkali resistance of CBF are good.Performances such as its Xing of Nai Jiu ﹑ Xing of Nai Hou ﹑ UV resistant Zhao She ﹑ Xing of Nai Shui ﹑ is anti-oxidant all can be compared U.S.A with natural basalt stone.
5, excellent electric insulating and dielectric property.The specific volume resistance of CBF is higher to be 1 * 1012 Ω m.Be higher than carbon fiber far away.The plug that is used for aerial condutor can not produce eddy current loss and thermal losses and the power outages brought fully.
6, lower moisture absorption.The moisture absorption of CBF is lower than 0.1 %, is lower than carbon fiber.Can keep properties of product good for a long time.
7, coefficient of linear expansion is 6～8 * 10
-6/ ℃, though higher than carbon fiber, lower by 35% than the aluminum used coefficient of linear expansion of lead, can satisfy the application of aerial condutor.
8, has good creep resistance, the useful life of guaranteeing product.
9, have the excellent high-temperature pull-off force and keep, under 200 ℃, can keep 95% pull-off force.
Following table is the technical indicator of continuous basalt fiber roving 1:
Fig. 2 is the detailed process flow figure of composite core rod of the present invention, and Fig. 3 is a matrix reinforcing material surface-treated sketch map.
The aerial condutor that the present invention improves performance comprises the steps: with the preparation of fiber composite plug
Step 1: basalt fibre is at first through putting yarn, doubling, dehumidifying operation;
Step 2: with coupling agent with nanometer SiO
2Carry out surface treatment;
Step 3: with the nanometer SiO after step 2 processing
2Preparation nanometer SiO
2Infiltrate, and use nanometer SiO
2Infiltrate carries out surface coarsening and lipophile transformation to continuous basalt fiber roving 1, in processing procedure, handles with ultrasonic unit, guarantees to soak into evenly, disperses, and reaches the surface of good treatment effect;
Step 4: calcium carbonate crystal whisker and four jiaos of ZnOws are carried out surface treatment with coupling agent;
Step 5: calcium carbonate crystal whisker and four jiaos of ZnOws with after step 4 processing prepare epoxy resin impregnated solution; Continuous basalt fiber roving 1 after step 3 handled is sent in this epoxy resin impregnated solution fully dipping; Around this continuous basalt fiber roving 1, form epoxy tree part 2, in processing procedure, handle with ultrasonic unit;
Step 6: the traditional pultrude process of this continuous basalt fiber roving 1 process with step 5 obtains obtains composite core rod of the present invention at last.
In all processing procedures, to environmentally defined strict requirement.And in surface modification and dipping process, ultrasonic technology has been used in many places, to guarantee material mixing and to flood full and uniform, dispersion, substantial, guarantees that the fiber composite plug reaches requirement.The fiber composite plug that the present invention makes is compared with carbon fiber composite core rod, has high cost performance.
In all modification process operations, should guarantee environmental quality, promptly temperature is controlled at 20 ℃ ± 2 ℃, and humidity is controlled at 45% ~ 65%, and cleanliness factor is controlled at thousand grades of purifications, to guarantee to obtain good product quality.
The detailed process of putting yarn, doubling, dehumidifying operation of step 1 is following: the basalt fibre axle of requirement is installed on the pay off rack; The emitting tension force and must guarantee evenly of all yarn axis; Its tension force deviation is ± 15gf in; Nominal laying tension 0.8kgf～2kgf looks drawing tension and decides.Thereafter get into the doubling zone, the feed carrier in doubling zone should have higher hardness and fineness, and it is suitable to lead, and should not produce additional bad influence to yarn.Thereafter get into and remove wet zone, dry hot blast is removed the moisture of fiber surface, should moisture thoroughly be removed the yarn stabilized walking.
In each flow process, should keep yarn in each flow path device, the part that yarn is exposed is the least possible, to guarantee the surface state of yarn continous-stable.
Described continuous basalt fiber roving 1, be with the parallel precursor of multiply or the parallel precursor of sub-thread under the state of not twisting and close the basalt fibre goods that form, the surface is contained silane and is soaked into.But original silane soaks into and can not satisfy and the mechanics of epoxy resin part 2 bondings and the requirement of interface performance.At first should pass through nanometer SiO
2Surface coarsening and lipophile transformation to increase the compatibility between epoxy resin part 2 and the continuous basalt fiber roving 1, can improve the mechanical property and the interface performance of composite material.
Before continuous basalt fiber roving 1 is done surface coarsening and lipophile transformation, must be earlier as step 2 said with coupling agent to nanometer SiO
2Carry out surface treatment, brief description is following: because nano particle diameter is little, surperficial agglomeration is strong, and is lower with the organism adhesion, so, should improve the dispersion of nano-powder in different liquid phase mediums through surface treatment.Choose the nanometer SiO of 70nm-120nm
2, at first to nanometer SiO
2Carry out surface treatment.Adopt silane coupler and butyl methacrylate that nano particle is carried out surface treatment; Form the polymeric layer of chemical bonding like this in nanoparticle surface; Form high density polymer layer with the inorganic nano-particle strong bonded; Improved the lipophile of nano particle, reduced hydrophily, eliminated the phenomenon of separating with organic facies.
Continuous basalt fiber roving 1 is a kind of fragile fibre, must be through baster, with a kind of nanometer SiO in manufacture process
2Infiltrate evenly applies from the teeth outwards, forms layer protective layer.As the wild phase raw material, the roving basalt fibre is as the raw material of these goods, and it has passed through nanometer SiO
2Infiltrate is handled.
Introduce the described nanometer SiO of epimere below
2The preparation process of infiltrate: choose specific film forming agent, coupling agent, lubricant, antistatic agent, process the basalt fibre size according to specific program.Because itself has had coupling agent the raw material basalt fibre, so should choose a spot of coupling agent; Selected coupling agent should be identical with the coupling agent that basalt fibre has had.By mass concentration, nanometer SiO
2Be 1%, film forming agent is 25%, and coupling agent is 5%, and lubricant is 35%, and antistatic agent is 34%, in this ratio, for optimal proportion is selected; Its proportion uses in ± 20% scope; The collocation different with other technological parameter is with choosing different proportions.Handle with ultrasonic unit, to guarantee nanometer SiO
2The uniformity of infiltrate.
In the step 3, need in advance the nanometer SiO for preparing
2Infiltrate slowly imports in the nanometer infiltration apparatus, in this zone, handles with ultrasonic unit, guarantees to soak into evenly, disperses, and reaches the surface of good treatment effect.Afterwards, get into the oven dry zone,, not only dry, also reach the effect of surface active, to help the epoxy resin impregnated of next step in this zone.In this zone, temperature is controlled to be between 90 ℃-150 ℃.
In the step 4, above-mentioned calcium carbonate crystal whisker and four jiaos of ZnOws are as the modified matrix reinforcing material, are used for reinforced epoxy layer 2 basal body interface performance.Before the epoxy resin impregnated solution of preparation, need carry out surface preparation to calcium carbonate crystal whisker and four jiaos of ZnOws with coupling agent.
The size of calcium carbonate crystal whisker is minimum, is again high-purity material, does not have or internal structure defective seldom, and its intensity is far above the same material of stock size.In fact freshly prepd whisker, because do not have surperficial pit or crackle, therefore its intensity, mix it in the fiber near the theoretical strength of crystal, has good reinforced effects, size stability also improves greatly.
Calcium carbonate crystal whisker is that another novel inorganic after nano-calcium carbonate is filled, and is nontoxic, odorlessness, and the paulin pine shape solid (microscopically is the whiskers body) that is white in color has following performance and characteristics as a new generation's enhancing, this product of packing material:
1, the high mechanical strength of combination property, and in use can vibration damping, anti-skidding, noise reduction is inhaled ripple; This point is particularly suitable on aerial condutor, using.
2, good combination property, coefficient of friction is high, and anti-wear performance and heat resistance are high;
3, life of product can improve 30%;
4, can reduce the consumption of high value fiber material, product cost is reduced greatly;
5, raw material sources are abundant, and price is low, can not exert an influence to production because of the raw material problem.
Following table is the technical indicator of calcium carbonate crystal whisker:
Four jiaos of ZnOws came to light the forties in 20th century, were succeeded in developing in 1989 by the PANASONIC industry the earliest.The four acicular type zinc oxide crystal whisker outward appearance loose shape powder that is white in color; Microcosmic is three-dimensional four needle-like stereochemical structures, and promptly whisker has a core, stretches out four acicular crystals from the core radial direction; Every spicule is the monocrystal microfibre, and the angle of wantonly two spicules is 109 °.Centerbody diameter 0.7～1.4 μ m of whisker, spicule root diameter (RD) 0.5～14 μ m, spicule length is 3～200 μ m, image K-M shows that whisker has the monocrystalline property that dislocation is little, lattice defect is few; Atomic absorption spectrum shows that the whisker impurity content is few, and zinc oxide content is 99.95%, therefore is similar to monocrystalline.It is unique whisker with space multistory structure in all whiskers so far; Because of its unique solid four needle-like three-dimensional structures; Be readily embodied in the even distribution in the basis material, thereby isotropically improve the physical property of material, give the functional characteristic of the multiple uniqueness of material simultaneously.It has common zinc oxide incomparable premium properties.Like wear-resisting, enhancing, vibration damping, anti-skidding, noise reduction, suction ripple, performance such as anti-aging, antistatic, antibiotic.
Four jiaos of ZnOws are used for the main feature of aerial condutor aspect:
1, superhigh intensity: four acicular type zinc oxide crystal whisker is the plumbous zinc ore structure of monocrystal; Almost there is not fault of construction; Belong to desirable crystalline solid, have high mechanical strength and modulus of elasticity: hot strength and modulus of elasticity reach 1.0 * 104MPa and 3.5 * 105MPa respectively, near the theoretical strength value;
2, isotropism: special solid four acicular textures; Make it have the enhancing of completely isotropic, modifying function, guaranteed material and goods isotropism at aspects such as mechanical property, dimensional homogeneity, thermal contraction, thermal deformation and other serviceabilities;
3, the thermal endurance of excellence: the fusing point of zinc oxide is higher than 1800 ℃, and the high temperature that four acicular type zinc oxide crystal whisker can be anti-1720 ℃ (being higher than this temperature possibly distil) possibly cause the most advanced and sophisticated nanostructure of part impaired more than 1000 ℃ in the air under the normal pressure;
Following table is the technical indicator of four jiaos of ZnOws:
For the use of four jiaos of ZnOws and calcium carbonate crystal whisker, must consider and give full play to the effect that whisker strengthens that the reply whisker carries out surface modification.The perfect condition of Whisker reinforced resin is: whisker should evenly distribute in matrix, is spaced from each other between whisker, and is well soaked into by matrix resin.Be the dispersion of promotion inorganic crystal whisker in organic matrix, and give certain function power between whisker and matrix, need carry out surface modification to whisker with coupling agent.The surface treatment of whisker, and how in surface treatment and processing and forming, to reduce whisker damage as far as possible be the key issue of performance whisker effect to keep enough draw ratios.
The surface of whisker and the surface of matrix form boundary layer oozing to sneak out in the journey, the characteristic of boundary layer is directly connected to the overall performance of composite material, in order to obtain desirable boundary layer; Just must be according to matrix and reinforcing material surface characteristics different; Select suitable coupling agents, whisker improves the compatibility between itself and the matrix after coupling agent treatment; It is big that material when fracture whisker is extracted the energy that is consumed, and makes the raising of impact strength and bending strength.
The suction-operated of whisker and coupling agent.When the consumption of coupling agent was suitable, coupling agent formed monolayer (being chemisorbed layer) on the whisker surface, and this moment, the modified effect of whisker was best; When coupling agent consumption very little the time, coupling agent fails to coat fully whisker surface, poor-performing.And continue to increase to when excessive when the coupling agent consumption, because the intermolecular mutual association of long hydrocarbon chain makes modifier outside the surperficial monolayer of whisker, form polymolecular layer (being the physical absorption layer) again.Physical absorption force rate chemistry bonding force in these polymolecular layers is little, so the adhesive property that adds behind the epoxy resin is also relatively poor.
Introduce the surface preparation of calcium carbonate crystal whisker below: in order to improve the compatibility of calcium carbonate crystal whisker and epoxy resin layer 2, (coupling agent of KR-TTS) is to the calcium carbonate crystal whisker processing that organises to use isopropyl three (isostearoyl base) titanate esters in advance.Processing method is following: absolute ethyl alcohol and deionized water are made into ethanol water in the ratio of mass ratio 14:1, add the acetic acid of liquid quality fraction 43% and the coupling agent of mass fraction 21%, stir.The calcium carbonate crystal whisker that takes by weighing amount of calculation adds in the solvent, 60 ℃ of following ultrasonic stirring, filters then, and washing vacuumizes drying, airtight storing for future use to neutral under 120 ℃.
Introduce the surface preparation of four jiaos of ZnOws below: adopt wet treatment.A certain amount of silane coupler is added in entry-acetone soln, regulate pH value to acid, be hydrolyzed with hydrochloric acid; Then a certain amount of four jiaos of ZnOws are added wherein; In water bath with thermostatic control, stir 30 ~ 60min, filtration under diminished pressure, with deionized water wash to there not being the chlorine particle.For use at 150 ℃ of following activation 8h after super-dry.
In the step 5; After the surface preparation with calcium carbonate crystal whisker and four jiaos of ZnOws; Next prepare epoxy resin impregnated solution; Its preparation process is following: add in the epoxy resin with the calcium carbonate crystal whisker of 5% ~ 6% mass ratio and 2% ~ 3% ZnOw in advance, stirred 30 minutes with electromagnetic stirrer at 20 ℃ ± 2 ℃.
Above-mentioned epoxy resin impregnated solution is added in the epoxy resin infiltration apparatus.In this device, handle with ultrasonic wave, to guarantee the uniformity of dipping.
Be admitted to epoxy resin impregnated solution after continuous basalt fiber roving 1 oven dry that step 3 obtains and fully flood, form epoxy resin layer 2 in the outside of continuous basalt fiber roving 1.
Traditional pultrude process described in the step 6 mainly comprises operations such as preforming, curing, cooling, traction, take-up.
The continuous basalt fiber roving 1 that step 5 obtains gets into the preforming district.In this zone, adopt normal temperature control.Mould design should guarantee that the preforming diameter reduces gradually, and proportional control is between 800:1 ~ 1000:1 at the ratio of length radius; Can play the effect of dipping consolidation.Preforming tool typing length should have 15 times of length with top external diameter.It is big by 1% that the selection of diameter is made diameter than nominal.See also Fig. 4, be the preforming tool sketch map, resin and fiber label are 30, and the mould label is 40, and ultrasonic equipment is 50, and preforming district label is 60.
After the preforming, continuous basalt fiber roving 1 and epoxy resin layer on every side 2 get into and solidify the moulds zone, in this zone it are carried out pultrusion.
See also Fig. 5, be epoxy resin cure mould sketch map, the fibre bundle label is 100, and the composite core rod label is 200.Pultrusion die is divided into three zones: the first area is preheating zone 70, and temperature is more than 100 ℃, for the curing reaction of next stage is prepared.The raising of hydraulic pressure simultaneously is convenient to heat and is inwardly transmitted, and fibre bundle 100 is liquid in preheating zone 70; Second area is gel district 80, and the resin solidification reaction also produces phase transformation, is transformed into gel state from the thickness attitude, and fibre bundle 100 is gel states in gel district 80; The 3rd zone is flat-temperature zone 90, can prevent that jump in temperature from causing composite material to crack, and fibre bundle 100 is solid-state in flat-temperature zone 90.Near the mould outlet place, the goods that the surface speckles with film former can split away off from die surface.Choose adaptive mold temperature, ambient temperature, hauling speed,, with internal strain control within the specific limits, guarantee not crack on performance and microcosmic, the macroscopic view of material to obtain best curing temperature and curing time.
Preforming mould is the structure of continuous one on length with solidifying mould, to guarantee the good of product size and surface appearance.
Afterwards, the plug of curing gets into cooled region again, traction zone and take-up axle; Wherein tractive effort should be guaranteed its good stable property; Adopt the crawler type mode of traction, tractive effort is stabilized in ± 0.5% tractive effort scope in, can guarantee performance and size outward appearance good of goods like this.
Following table is " the present invention implements an example plug main performance index "; Wherein " present case performance index " are that the present invention implements the index that an example reaches; " present case explanation " is the index explanation of exemplifying embodiment, and " reporting original text B level index and explanation to a higher authorities for approval " is the standard-required of the GB " aerial condutor is used the fiber-reinforced resin matrix compound material plug " of contrast.Find out from the contrast index; In the precision of product size, dimensional stability, torsion test, flexing test, allow aspect maximum operating temperature, glass transition temperature, heat resistance, the high temperature tensile strength for a long time; All good than GB declaration original text index, explain that the present invention is a kind of very big improvement to original product.
Aspect cost, the about 3-4 of basalt fibre ten thousand is per ton, and mostly carbon fiber is import, like toray, price about 290,000 yuan per ton, comprehensive product material cost reduces by 40%, have very high cost performance.
Claims (10)
1. an aerial condutor that improves performance is used the fiber composite plug, it is characterized in that: it comprises the continuous basalt fiber roving and is formed on this continuous basalt fiber roving epoxy resin part on every side through even dipping;
Said composite core rod is prepared from following steps:
Step 1: with coupling agent with nanometer SiO
2Carry out surface treatment;
Step 2: with the nanometer SiO after step 1 processing
2Preparation nanometer SiO
2Infiltrate, and use nanometer SiO
2Infiltrate carries out surface coarsening and lipophile transformation to the continuous basalt fiber roving, in processing procedure, handles with ultrasonic unit;
Step 3: calcium carbonate crystal whisker and four jiaos of ZnOws are carried out surface treatment with coupling agent;
Step 4: calcium carbonate crystal whisker and four jiaos of ZnOws with after step 3 processing prepare epoxy resin impregnated solution; Continuous basalt fiber roving after step 2 handled is sent in this epoxy resin impregnated solution fully dipping; Around this continuous basalt fiber roving, form epoxy resin structural, in processing procedure, handle with ultrasonic unit;
Step 5: this continuous basalt fiber roving process pultrude process with step 4 obtains obtains said composite core rod at last.
2. the aerial condutor that improves performance as claimed in claim 1 is used the fiber composite plug, it is characterized in that: in the step 1, choose the nanometer SiO of 70nm-120nm
2, adopt silane coupler and butyl methacrylate that nano particle is carried out surface treatment, improved the lipophile of nano particle, reduced hydrophily, eliminated the phenomenon of separating with organic facies.
3. according to claim 1 or claim 2 the aerial condutor that improves performance is used the fiber composite plug, it is characterized in that: the nanometer SiO described in the step 2
2The preparation process of infiltrate is: by mass concentration, and nanometer SiO
2Be 1%, film forming agent is 25%, and coupling agent is 5%, and lubricant is 35%, and antistatic agent is 34%, handles with ultrasonic unit.
4. the aerial condutor that improves performance as claimed in claim 1 is used the fiber composite plug, it is characterized in that: in the step 3, use isopropyl three (isostearoyl base) titanate coupling agent that calcium carbonate crystal whisker is carried out surface preparation; The method that four jiaos of ZnOws are carried out surface preparation is: a certain amount of silane coupler is added in entry-acetone soln; Regulate pH value to acid with hydrochloric acid, be hydrolyzed, then a certain amount of four jiaos of ZnOws are added wherein; In water bath with thermostatic control, stir 30 ~ 60min; Filtration under diminished pressure,, for use at 150 ℃ of following activation 8h after super-dry with deionized water wash to there not being the chlorine particle.
5. use the fiber composite plug like claim 1 or the 4 described aerial condutors that improve performance; It is characterized in that: the epoxy resin impregnated solution of preparation in the step 4; Its preparation process is following: add in the epoxy resin with the calcium carbonate crystal whisker of 5% ~ 6% mass ratio and 2% ~ 3% ZnOw in advance, stirred 30 minutes with electromagnetic stirrer at 20 ℃ ± 2 ℃.
6. preparation method who improves the aerial condutor of performance with the fiber composite plug, it is characterized in that: it comprises the steps:
Step 1: with coupling agent with nanometer SiO
2Carry out surface treatment;
Step 2: with the nanometer SiO after step 1 processing
2Preparation nanometer SiO
2Infiltrate, and use nanometer SiO
2Infiltrate carries out surface coarsening and lipophile transformation to the continuous basalt fiber roving, in processing procedure, handles with ultrasonic unit;
Step 3: calcium carbonate crystal whisker and four jiaos of ZnOws are carried out surface treatment with coupling agent;
Step 4: calcium carbonate crystal whisker and four jiaos of ZnOws with after step 3 processing prepare epoxy resin impregnated solution; Continuous basalt fiber roving after step 2 handled is sent in this epoxy resin impregnated solution fully dipping; Around this continuous basalt fiber roving, form epoxy resin structural, in processing procedure, handle with ultrasonic unit;
Step 5: this continuous basalt fiber roving process pultrude process with step 4 obtains obtains said composite core rod at last.
7. the preparation method who improves the aerial condutor of performance with the fiber composite plug as claimed in claim 6 is characterized in that: in the step 1, choose the nanometer SiO of 70nm-120nm
2, adopt silane coupler and butyl methacrylate that nano particle is carried out surface treatment, improved the lipophile of nano particle, reduced hydrophily, eliminated the phenomenon of separating with organic facies.
8. like claim 6 or the 7 described preparation methods that improve the aerial condutor of performance with the fiber composite plug, it is characterized in that: the nanometer SiO described in the step 2
2The preparation process of infiltrate is: by mass concentration, and nanometer SiO
2Be 1%, film forming agent is 25%, and coupling agent is 5%, and lubricant is 35%, and antistatic agent is 34% to mix.
9. the preparation method who improves the aerial condutor of performance with the fiber composite plug as claimed in claim 6 is characterized in that: in the step 3, use isopropyl three (isostearoyl base) titanate coupling agent that calcium carbonate crystal whisker is carried out surface preparation; The method that four jiaos of ZnOws are carried out surface preparation is: a certain amount of silane coupler is added in entry-acetone soln; Regulate pH value to acid with hydrochloric acid, be hydrolyzed, then a certain amount of four jiaos of ZnOws are added wherein; In water bath with thermostatic control, stir 30 ~ 60min; Filtration under diminished pressure, with deionized water wash to there not being the chlorine particle, after super-dry at 150 ℃ of following activation 8h.
10. like claim 6 or the 9 described preparation methods that improve the aerial condutor of performance with the fiber composite plug; It is characterized in that: the epoxy resin impregnated solution of preparation in the step 4; Its preparation process is following: add in the epoxy resin with the calcium carbonate crystal whisker of 5% ~ 6% mass ratio and the ZnOw of 2% ~ 3% mass ratio in advance, stirred 30 minutes with electromagnetic stirrer at 20 ℃ ± 2 ℃.
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| CN111081434A (en) * | 2019-12-31 | 2020-04-28 | 衡水瑞纤新材料科技有限公司 | Basalt fiber insulator core rod |
| CN113580709A (en) * | 2021-06-18 | 2021-11-02 | 四川佳宝科技有限公司 | Basalt fiber combined reinforced fabric |
| CN113754383A (en) * | 2021-10-13 | 2021-12-07 | 昭通市宜昭高速公路投资开发有限公司 | Bendable concrete and preparation method thereof |
| CN118636505A (en) * | 2024-08-13 | 2024-09-13 | 四川省建筑设计研究院有限公司 | Process for manufacturing surface material of fiber composite pultrusion profile |
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| CN113754383A (en) * | 2021-10-13 | 2021-12-07 | 昭通市宜昭高速公路投资开发有限公司 | Bendable concrete and preparation method thereof |
| CN113754383B (en) * | 2021-10-13 | 2022-07-05 | 昭通市宜昭高速公路投资开发有限公司 | Bendable concrete and preparation method thereof |
| CN118636505A (en) * | 2024-08-13 | 2024-09-13 | 四川省建筑设计研究院有限公司 | Process for manufacturing surface material of fiber composite pultrusion profile |
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| CN102426884B (en) | 2013-09-04 |
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Effective date of registration: 20170103 Address after: 518000 Guangdong city of Shenzhen province Nanshan District Guangdong streets High-tech Park District Road No. 8 Keyuan Xunmei Technology Plaza 1 Building 9 layer 905 Patentee after: Shenzhen forever Technology Co., Ltd. Address before: 518000 Guangdong Province, Shenzhen Baoan District manhole Yabian Industrial Zone B, third students in District 5. Patentee before: Shenzhen Mengli Electronics Co., Ltd. |