CN102426884B - 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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- CN102426884B CN102426884B CN 201110266832 CN201110266832A CN102426884B CN 102426884 B CN102426884 B CN 102426884B CN 201110266832 CN201110266832 CN 201110266832 CN 201110266832 A CN201110266832 A CN 201110266832A CN 102426884 B CN102426884 B CN 102426884B
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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 onthe 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 adoptinga 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
The present invention relates to a kind of electric power transfer with the fiber composite plug of aerial condutor, 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.
Background technology
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 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 described two-layer structure, its internal layer are the carbon fiber composite portion, and skin is glass fibre compound inslation part.
The carbon fiber composite core rod of described three-decker, its internal layer are the glass fibre composite portion, and the intermediate layer is the carbon fiber composite portion, and skin is glass fibre compound inslation part.
No matter two-layer structure still is the carbon fiber composite core rod of three-decker, its outer field glass fibre 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 described three-decker is the glass fibre 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 is subjected to 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 ambiguity, direction is in a mess, and this is the problem of carbon fiber industry maximum.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 in deposit and the application power of this technology.Not only need the support of policy, the input of fund also needs the intervention of large-scale chemical fiber factory, the cost of Carbon Fiber Technology could 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 by 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 temperature and the mechanical performance of composite core rod.
Summary of the invention
The technical problem to be solved in the present invention 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 of the present invention is: a kind of aerial condutor that improves performance 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 by even dipping;
Described composite core rod is prepared from by 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, handles with ultrasonic unit in processing procedure;
Step 3: calcium carbonate crystal whisker and four jiaos of ZnOws are carried out surface treatment with coupling agent;
Step 4: prepare epoxy resin impregnated solution with calcium carbonate crystal whisker and four jiaos of ZnOws after step 3 processing, 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 described composite core rod at last; 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 phase;
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;
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 water-acetone soln in, 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 spends deionised water to there not being the chlorine particle, and activation 8h is stand-by down at 150 ℃ after super-dry;
The epoxy resin impregnated solution of preparation in the step 4, its preparation process is as follows: 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, first technical scheme of the present invention is: a kind of aerial condutor that improves performance preparation method of 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, handles with ultrasonic unit in processing procedure;
Step 3: calcium carbonate crystal whisker and four jiaos of ZnOws are carried out surface treatment with coupling agent;
Step 4: prepare epoxy resin impregnated solution with calcium carbonate crystal whisker and four jiaos of ZnOws after step 3 processing, 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 described composite core rod at last;
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 phase;
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;
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 water-acetone soln in, 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 spends deionised water to there not being the chlorine particle, activates 8h down at 150 ℃ after super-dry;
The epoxy resin impregnated solution of preparation in the step 4, its preparation process is as follows: 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 the electric power transfer 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 the cross-sectional view that the present invention improves the aerial condutor usefulness fiber composite plug of performance.
Fig. 2 is the detailed process flow figure of composite core rod of the present invention.
Fig. 3 is matrix reinforcing material surface-treated schematic diagram.
Fig. 4 is the preforming tool schematic diagram.
Fig. 5 is epoxy resin cure mould schematic diagram.
Embodiment
See also Fig. 1, the present invention proposes a kind of aerial condutor that improves performance 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 by 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 that continuous basalt fiber roving 1(is abbreviated as CBF) with the contrast of the physical property of various fiber materials:
Continuous basalt fiber roving 1(is abbreviated as CBF) be used for overhead wire lead aspect, have 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 0.031W/mK～0.038W/mK, is lower than carbon fiber.
3, high modulus of elasticity and tensile strength.The modulus of elasticity of CBF is: 9100kg/mm
2～11000kg/mm
2Though, being lower than carbon fiber and steel, its index is compared high by 30% with the soft aluminium that lead adopts, can satisfy the requirement of lead stretch-proof.The tensile strength of CBF is 3800～4800MPa, 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. 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 than carbon fiber height, 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 matrix reinforcing material surface-treated schematic diagram.
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, handles with ultrasonic unit in processing procedure, 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: prepare epoxy resin impregnated solution with calcium carbonate crystal whisker and four jiaos of ZnOws after step 4 processing, 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 the 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, i.e. temperature control is at 20 ℃ ± 2 ℃, and humidity is controlled 45% ~ 65%, and cleanliness factor is controlled thousand grades of purifications, to guarantee to obtain good product quality.
The detailed process of putting yarn, doubling, dehumidifying operation of step 1 is as follows: 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 decides on drawing tension.Thereafter enter 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 enter except wet zone, dry hot blast is removed the moisture of fiber surface, moisture thoroughly should 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 mechanical property and the interface performance of composite material.
Continuous basalt fiber roving 1 is being done before surface coarsening and lipophile transform, must be earlier as described in the step 2 with coupling agent to nanometer SiO
2Carry out surface treatment, brief description is as follows: 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 by 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 the high density polymer layer with the inorganic nano-particle strong bonded, improved the lipophile of nano particle, reduce hydrophily, eliminated the phenomenon of separating with organic phase.
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, make 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 will be chosen 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, enter the oven dry zone, in this zone, not only dry, also reach the effect of surface active, to be conducive to the epoxy resin impregnated of next step.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 enhancing effect, 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 for using at aerial condutor.
2, good combination property, coefficient of friction height, anti-wear performance and heat resistance height;
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:
| Project | Index |
| Composition | CaCO3 (purity 98%) |
| Outward appearance | White powder |
| Density (g/cm3) | 2.86 |
| Moisture | ＜1% |
| The pH value | 9-9.5 |
| Shape | Fiber |
| Length (um) | 20-30 |
| External diameter (um) | 0.5-1 |
Four jiaos of ZnOws were found 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 namely 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 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, solid four needle-like three-dimensional structures because of its uniqueness, 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 the incomparable premium properties of common zinc oxide.As 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 that material and goods are in the isotropism of aspects such as mechanical property, dimensional homogeneity, thermal contraction, thermal deformation and other serviceability;
3, You Yi thermal endurance: 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 may distil) may 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:
| Project | Index |
| Mass fraction % | ≥99.99 |
| Spicule length um | 10～150 |
| Spicule root diameter (RD) um | 0.7～5 |
| Specific heat J/gk | 5.52 |
| Shape | Four needle-likes |
| Sublimation point ℃ | 1720 |
| Intrinsic volume resistance Ω cm | 10 4～10 9 |
| Dielectric constant | 8.55 |
| Hot strength MPa | 1.2×10 4 |
| Modulus of elasticity MPa | 3.5×10 5 |
| Coefficient of thermal expansion %/℃ | 4×10 6 |
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 active force certain between whisker and matrix, need carry out surface modification with coupling agent to whisker.The surface treatment of whisker, and how to reduce the draw ratio that whisker damages to keep enough in surface treatment and processing and forming as far as possible be the key issue of performance whisker effect.
The surface of whisker and the surface of matrix form boundary layer oozing to sneak out in the journey, the feature 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 consumes, and impact strength and bending strength are improved.
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 form polymolecular layer (being the physical absorption layer) again outside the monolayer on whisker surface.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, use isopropyl three (isostearoyl base) titanate esters (KR-TTS) coupling agent to the calcium carbonate crystal whisker processing that organises in advance.Processing method is as follows: 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, stirs at 60 ℃ of following ultrasonic waves, filters then, is washed to neutrality, vacuumizes drying, airtight storing for future use under 120 ℃.
Introduce the surface preparation of four jiaos of ZnOws below: adopt wet treatment.A certain amount of silane coupler is added water-acetone soln in, regulate pH value to acid with hydrochloric acid, be hydrolyzed, then a certain amount of four jiaos of ZnOws are added wherein, stir 30 ~ 60min in water bath with thermostatic control, filtration under diminished pressure spends deionised water to there not being the chlorine particle.Activation 8h is stand-by down at 150 ℃ 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 as follows: 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 enters 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 with the length of 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 schematic diagram, 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 2 on every side enter and solidify the mould zone, in this zone it are carried out pultrusion.
See also Fig. 5, be epoxy resin cure mould schematic diagram, 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, to obtain best curing temperature and curing time, with internal strain control within the specific limits, guarantee not crack on the performance of material and microcosmic, the macroscopic view.
Preforming mould and curing mould are the structures of continuous one in length, to guarantee the good of product size and surface appearance.
Afterwards, the plug of curing enters cooled region again, traction zone and take-up axle, wherein tractive effort should be guaranteed its good stable, adopt the crawler type mode of traction, tractive effort is stabilized in ± 0.5% tractive effort scope in, can guarantee the good of the performance of goods and size outward appearance like this.
Following table is " an example plug of the invention process main performance index ", wherein " present case performance index " are the indexs that example of the invention process 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 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, illustrate 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, as toray, price about 290,000 yuan per ton, comprehensive product material cost reduces by 40%, have very high cost performance.
Claims (2)
1. aerial condutor fiber composite plug that improves performance is characterized in that: it comprises the continuous basalt fiber roving and is formed on epoxy resin part around this continuous basalt fiber roving by even dipping;
Described composite core rod is prepared from by 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, handles with ultrasonic unit in processing procedure;
Step 3: calcium carbonate crystal whisker and four jiaos of ZnOws are carried out surface treatment with coupling agent;
Step 4: prepare epoxy resin impregnated solution with calcium carbonate crystal whisker and four jiaos of ZnOws after step 3 processing, 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 described composite core rod at last; 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 phase;
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;
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 water-acetone soln in, 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 spends deionised water to there not being the chlorine particle, and activation 8h is stand-by down at 150 ℃ after super-dry;
The epoxy resin impregnated solution of preparation in the step 4, its preparation process is as follows: 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 ℃.
2. an aerial condutor that improves performance is with the preparation method of fiber composite plug, and 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, handles with ultrasonic unit in processing procedure;
Step 3: calcium carbonate crystal whisker and four jiaos of ZnOws are carried out surface treatment with coupling agent;
Step 4: prepare epoxy resin impregnated solution with calcium carbonate crystal whisker and four jiaos of ZnOws after step 3 processing, 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 described composite core rod at last;
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 phase;
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;
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 water-acetone soln in, 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 spends deionised water to there not being the chlorine particle, activates 8h down at 150 ℃ after super-dry;
The epoxy resin impregnated solution of preparation in the step 4, its preparation process is as follows: 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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| CN 201110266832 CN102426884B (en) | 2011-09-09 | 2011-09-09 | Fiber composite core rod with improved performances for overhead wire and preparation method thereof |
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| CN111081434B (en) * | 2019-12-31 | 2022-03-04 | 衡水瑞纤新材料科技有限公司 | Basalt fiber insulator core rod |
| CN113580709B (en) * | 2021-06-18 | 2023-05-12 | 四川佳宝科技有限公司 | Basalt fiber combined reinforced fabric |
| 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 |
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| CN101034601A (en) * | 2007-04-16 | 2007-09-12 | 中国人民解放军国防科学技术大学 | Heat-resisting and low expansion double capacity compound material core aluminum twisted wire and its making method |
| CN101246764A (en) * | 2007-02-12 | 2008-08-20 | Ls电线有限公司 | Composite for overhead transmission cable and method for preparing thereof |
| CN101325098A (en) * | 2007-06-12 | 2008-12-17 | 李玉国 | Carbon fiber composite reinforced-core cable |
| CN102024517A (en) * | 2009-09-15 | 2011-04-20 | 江苏嘉泰科技材料股份公司 | Composite material core used for enhanced cable, preparation process thereof and enhanced cable |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101246764A (en) * | 2007-02-12 | 2008-08-20 | Ls电线有限公司 | Composite for overhead transmission cable and method for preparing thereof |
| CN101034601A (en) * | 2007-04-16 | 2007-09-12 | 中国人民解放军国防科学技术大学 | Heat-resisting and low expansion double capacity compound material core aluminum twisted wire and its making method |
| CN101325098A (en) * | 2007-06-12 | 2008-12-17 | 李玉国 | Carbon fiber composite reinforced-core cable |
| CN102024517A (en) * | 2009-09-15 | 2011-04-20 | 江苏嘉泰科技材料股份公司 | Composite material core used for enhanced cable, preparation process thereof and enhanced cable |
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