CN109153051A - The method of high-performance carbon fibre is recycled from inorganic coagulation material - Google Patents

The method of high-performance carbon fibre is recycled from inorganic coagulation material Download PDF

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CN109153051A
CN109153051A CN201880000082.6A CN201880000082A CN109153051A CN 109153051 A CN109153051 A CN 109153051A CN 201880000082 A CN201880000082 A CN 201880000082A CN 109153051 A CN109153051 A CN 109153051A
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carbon fiber
acid
recycling
sample
carbon
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朱继华
苏玫妮
陈丕钰
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Shenzhen University
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Shenzhen University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09B—DISPOSAL OF SOLID WASTE
    • B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09B—DISPOSAL OF SOLID WASTE
    • B09B5/00—Operations not covered by a single other subclass or by a single other group in this subclass

Abstract

A method of recycling high-performance carbon fibre from inorganic coagulation material, it includes the following steps: that carbon fiber reinforced inorganic (cement base) composite material is placed in electrolyte by (A) in 25 DEG C~75 DEG C of reaction temperature, and wherein the electrolyte contains the catalyst of NaCl and 1.0g/L~5g/L that weight ratio is 0.5%~3%；(B) it is powered to the Carbon Fiber Reinforced Cement Composites placed in the electrolytic solution, wherein the Carbon Fiber Reinforced Cement Composites are connected with the anode of power supply, and control current density is 3333.3~6666.7mA/m2；(C) is powered after reaction 0.5-200 hours, and the carbon fiber regenerant of generation is taken out from the electrolyte.

Description

The method of high-performance carbon fibre is recycled from inorganic coagulation material
Technical field
The present invention relates to the recycling and reuse of carbon fiber, more particularly to one kind, and high-performance is recycled from inorganic coagulation material The method of carbon fiber.
Background technique
Carbon fiber is with tensile strength is big, Young's modulus is high, corrosion resistance is strong, inert atmosphere superhigh temperature resistant, electromagnetic wave The advantages that shielding is excellent, good biocompatibility and soft plasticity are strong.Carbon fiber technology of preparing passes through the hair of over half a century Exhibition, has developed miscellaneous carbon fiber material, such as viscose carbon fiber, polyacrylonitrile fibre (PAN), pitch fibers, polyphenyl And imidazoles fiber and polyester fiber etc..
Carbon fiber enhancement resin base composite material (Carbon Fiber Reinforced Plastic, CFRP) is with carbon For fiber as reinforcement, organic resin epoxy is the composite material that matrix is made.CFRP has from heavy and light, corrosion-resistant, anti- The advantages that tensile strength is high, it is more and more wider in fields applications such as aerospace, industry manufacture and sports goods.2012, world's model Carbon fiber demand in enclosing is 4.35 ten thousand tons, and prediction the year two thousand twenty is up to 130,000 tons.
In field of civil engineering, after the solidification of organic resin epoxy cementitious material can be used in CFRP, structure is pasted or is arranged in Structural bearing capacity is improved in surface or inside.Epoxide-resin glue contains various polarity group and active very big epoxy group, while ring The cohesive strength of oxygen solidfied material is also very big, so its glue-joint strength is very high.But since epoxide-resin glue is ageing-resistant, corrosion-resistant, resistance to Hygrothermal Properties are poor, and antistripping, cracking resistance, shock resistance be not also high, since the nineties in last century, also adopt in civil engineering Material is sent out with the cement-based materials such as inorganic coagulation material, such as various modified cement pastes, mortar and/or concrete or base Deng, bonding CFRP, formation carbon fiber reinforced inorganic (cement base) composite material, and then reinforcing construction structure.Inorganic coagulation material The high excellent mechanicals performance such as strong with toughness of, intensity excellent with corrosion resistance performance, with traditional building work such as cement or concrete Journey structural material bonding is preferable, therefore reinforcement material (CFRP) can work together with original structure, and reinforcement performance is more preferable.
However, extensive use of the high performance fibrous composite such as CFRP in field of civil engineering, also brings extremely tight The building castoff of weight handles problem.Meanwhile high-performance fiber enhancing composite material still maintains good after the life termination phase Performance, economic value is higher, realize high-performance fiber enhancing composite material recycle and reuse have Important Economic value and Social effect.But using the CFRP of cement-based gelling material structural strengthening after dismounting, the building waste of carbon fibre material On can be attached be difficult removing inorganic material, the processing difficulty such as cement it is bigger.
About the recycling and application study of fibre reinforced composites waste, there are a large amount of scholars and mechanism to participate in, The developed countries such as external especially American-European and Japan rely on the leading advantage of its industry and technology, begin to carry out fiber increasing very early The recycle and reuse research of strong composite scrap object.However, existing various carbon fiber recovery methods, both for ring Oxygen resin glue is basis material and cementitious material, and for the carbon fiber of carbon fiber reinforced inorganic composite material recycling research mesh It is preceding to be not yet publicly reported.
In consideration of it, the present invention provides a kind of technical feasibility, easy to operate and high financial profit, environmental protection is combined The method that high-performance carbon fibre is recycled from inorganic coagulation material, not only contributes to the recycling and reusing of carbon fibre material, may be used also To solve the problems, such as the processing of building waste, have important economic value and social effect.
Summary of the invention
It is a primary object of the present invention to it to provide a kind of method that high-performance carbon fibre is recycled from inorganic coagulation material, Wherein the carbon fiber recovery method provided by the invention is with processing step is simple, difficulty is low, the rate of recovery is high, at low cost and fiber Damage the advantages that small.
Another object of the present invention is to it to provide a kind of method that high-performance carbon fibre is recycled from inorganic coagulation material, Wherein the carbon fiber recovery method provided by the invention can not only recycle carbon fiber, additionally it is possible to while resin material is recycled, and Inorganic coagulation material is decomposed, to reduce the building waste processing difficulty containing CFRP, and makes fibre reinforced water to a greater extent Cement-based composite material waste is recycled, and has the great value of environmental protection and important social effect.
Another object of the present invention is to it to provide a kind of method that high-performance carbon fibre is recycled from inorganic coagulation material, Wherein the required chemical reagent small toxicity of the carbon fiber recovery method provided by the invention, the requirement to production equipment be low, reaction Mild condition.The carbon fiber recovery method provided by the invention is without being sheared and/or being broken to carbon fibre reinforced composite Therefore broken processing can recycle the material of arbitrary dimension.Meanwhile without being cut to carbon fibre reinforced composite It cuts and/or break process recycles but also the mechanical property for the carbon fibre material that recycling obtains almost does not receive any damage The economic value of the carbon fibre material arrived is higher.
Another object of the present invention is to its provide it is a kind of for recycling high-performance carbon fibre from inorganic coagulation material Composition.
Other advantage and characteristics of the invention are able to fully demonstrate and can be by appended rights by following detailed descriptions The combination of the means and device specially pointed out in it is required that is achieved.
According to the present invention, the present invention that can be realized foregoing purpose and other purposes and advantage is recycled from inorganic coagulation material The method of high-performance carbon fibre includes the following steps:
(A) carbon fiber reinforced inorganic (cement base) composite material is placed in electrolyte by the reaction temperature in 25 DEG C~75 DEG C In, wherein the electrolyte contains the catalyst of NaCl and 1.0g/L~5g/L that weight ratio is 0.5%~3%；
(B) it is powered to the Carbon Fiber Reinforced Cement Composites placed in the electrolytic solution, wherein the fibre reinforced water Cement-based composite material is connected with the anode of power supply, and control current density is 3333.3~6666.7mA/m2, wherein the electric current is close The size of degree is soaked in the electrolyte according to carbon fibre material in the carbon fiber reinforced inorganic (cement base) composite material Surface area size calculated；With
(C) it is powered after reaction 0.5-200 hours, the carbon fiber regenerant of generation is taken out from the electrolyte.
In one embodiment, wherein further comprising step after step (C):
(D) the carbon fiber regenerant taken out from the electrolyte is rinsed, to remove inorganic (cement base) gel rubber material.
In one embodiment, wherein according to step (D), carbon fiber regenerant surface is equipped with the hole being spaced apart Hole.
In one embodiment, wherein according to step (D), the interval between each described hole is greater than 0.1mm, and washing pressure is high In 0.1MPa, washing time is no less than 3 seconds.
According to present pre-ferred embodiments, the present invention further provides one kind for recycling high-performance from inorganic coagulation material The electrolyte of carbon fiber, contains:
0.5%~3% NaCl；
The HNO of 1.0g/L~5g/L3；With
80%~98% water.
By the understanding to subsequent description and attached drawing, further aim of the present invention and advantage will be fully demonstrated.
These and other objects of the invention, feature and advantage, by following detailed descriptions, drawings and claims are obtained To fully demonstrate.
Detailed description of the invention
The structural schematic diagram of carbon fiber electrically chemical recovery system is shown in Figure 1A.
The structural schematic diagram of Carbon Fiber Reinforced Cement Composites test specimen is shown in Figure 1B and Fig. 1 C.
The carbon fiber regenerant recycled from Carbon Fiber Reinforced Cement Composites is shown in Fig. 2.
The cement base and carbon fiber of the Carbon Fiber Reinforced Cement-based Composites without electrochemistry recovery processing is shown in Fig. 3 A The interface to connect.
The details amplification at position at box in Fig. 3 A is shown in Fig. 3 B.
The interface that the cement-based material of carbon fiber regenerant is shown in Fig. 3 C and carbon fiber connects.
The details amplification at position at box in Fig. 3 C is shown in Fig. 3 D.
The amount for the carbon fiber that different grouping Carbon Fiber Reinforced Cement Composites sample recycles is shown in Fig. 4.
Fig. 5 is shown in reaction process, the voltage of different grouping Carbon Fiber Reinforced Cement Composites sample.
The carbon mono-filaments that the recycling of different grouping Carbon Fiber Reinforced Cement Composites sample obtains are shown in Fig. 6 Tensile strength.
The boundary for the carbon fiber that the recycling that different grouping Carbon Fiber Reinforced Cement Composites sample is shown in Fig. 7 obtains Face shear strength.
The surface breakdown mode of carbon fibre precursor is shown in Fig. 8 A.
I20S is shown in Fig. 8 B2.0H1The carbon fiber that the recycling of group Carbon Fiber Reinforced Cement Composites sample obtains Surface breakdown mode.
I40S is shown in Fig. 8 C2.0H1The carbon fiber that the recycling of group Carbon Fiber Reinforced Cement Composites sample obtains Surface breakdown mode.
I20S is shown in Fig. 8 D2.0H3The carbon fiber that the recycling of group Carbon Fiber Reinforced Cement Composites sample obtains Surface breakdown mode.
I40S is shown in Fig. 8 E2.0H3The carbon fiber that the recycling of group Carbon Fiber Reinforced Cement Composites sample obtains Surface breakdown mode.
I20S is shown in Fig. 8 F2.0H5The carbon fiber that the recycling of group Carbon Fiber Reinforced Cement Composites sample obtains Surface breakdown mode.
I40S is shown in Fig. 8 G2.0H5The carbon fiber that the recycling of group Carbon Fiber Reinforced Cement Composites sample obtains Surface breakdown mode.
The SEM scan image on carbon fibre precursor surface is shown in Fig. 9 A.
I20S is shown in Fig. 9 B2.0H1The carbon fiber that the recycling of group Carbon Fiber Reinforced Cement Composites sample obtains SEM scan image.
I40S is shown in Fig. 9 C2.0H1The carbon fiber that the recycling of group Carbon Fiber Reinforced Cement Composites sample obtains SEM scan image.
I20S is shown in Fig. 9 D2.0H3The carbon fiber that the recycling of group Carbon Fiber Reinforced Cement Composites sample obtains SEM scan image.
I40S is shown in Fig. 9 E2.0H3The carbon fiber that the recycling of group Carbon Fiber Reinforced Cement Composites sample obtains Table SEM scan image.
I20S is shown in Fig. 9 F2.0H5The carbon fiber that the recycling of group Carbon Fiber Reinforced Cement Composites sample obtains SEM scan image.
I40S is shown in Fig. 9 G2.0H5The carbon fiber that the recycling of group Carbon Fiber Reinforced Cement Composites sample obtains SEM scan image.
The AFM scan image on carbon fibre precursor surface is shown in Figure 10 A and Figure 10 B.
I20S is shown in Figure 10 C and Figure 10 D2.0H1The recycling of group Carbon Fiber Reinforced Cement Composites sample obtains Carbon fiber AFM scan image.
I40S is shown in Figure 10 E and Figure 10 F2.0H1The recycling of group Carbon Fiber Reinforced Cement Composites sample obtains Carbon fiber AFM scan image.
I20S is shown in Figure 10 G and Figure 10 H2.0H3The recycling of group Carbon Fiber Reinforced Cement Composites sample obtains Carbon fiber AFM scan image.
I40S is shown in Figure 10 I and Figure 10 J2.0H3The recycling of group Carbon Fiber Reinforced Cement Composites sample obtains Carbon fiber Table A FM scan image.
I20S is shown in Figure 10 K and Figure 10 L2.0H5The recycling of group Carbon Fiber Reinforced Cement Composites sample obtains Carbon fiber AFM scan image.
I40S is shown in Figure 10 M and Figure 10 N2.0H5The recycling of group Carbon Fiber Reinforced Cement Composites sample obtains Carbon fiber AFM scan image.
The XPS (x-ray photoelectron spectroscopy scanning) that carbon fibre precursor surface is shown in Figure 11 A scans full spectrogram picture.
The XPS scanning C1s high-resolution narrow spectrogram picture on carbon fibre precursor surface is shown in Figure 11 B.
I20S is shown in Figure 11 C2.0H1The carbon fiber that the recycling of group Carbon Fiber Reinforced Cement Composites sample obtains XPS scan full spectrogram picture.
I20S is shown in Figure 11 D2.0H1The carbon fiber that the recycling of group Carbon Fiber Reinforced Cement Composites sample obtains XPS scan C1s high-resolution narrow spectrogram picture.
I20S is shown in Figure 11 E2.0H3The carbon fiber that the recycling of group Carbon Fiber Reinforced Cement Composites sample obtains XPS scan full spectrogram picture.
I20S is shown in Figure 11 F2.0H3The carbon fiber that the recycling of group Carbon Fiber Reinforced Cement Composites sample obtains XPS scan C1s high-resolution narrow spectrogram picture.
I20S is shown in Figure 11 G2.0H5The carbon fiber that the recycling of group Carbon Fiber Reinforced Cement Composites sample obtains XPS scan full spectrogram picture.
I20S is shown in Figure 11 H2.0H5The carbon fiber that the recycling of group Carbon Fiber Reinforced Cement Composites sample obtains XPS scan C1s high-resolution narrow spectrogram picture.
Figure 12 is shown under condition of different temperatures, the carbon that the recycling of Carbon Fiber Reinforced Cement Composites sample obtains The amount of fiber.
Figure 13 is shown under condition of different temperatures, in reaction process, Carbon Fiber Reinforced Cement Composites sample Voltage.
Figure 14 is shown under condition of different temperatures, obtains from the recycling of Carbon Fiber Reinforced Cement Composites sample The monofilament tensile strength of carbon fiber.
Figure 15 is shown under condition of different temperatures, obtains from the recycling of Carbon Fiber Reinforced Cement Composites sample The interface shear strength of carbon fiber.
I20S is shown in Figure 16 A2.0H3T1The carbon fiber that the recycling of group Carbon Fiber Reinforced Cement Composites sample obtains The surface breakdown mode of dimension.
I40S is shown in Figure 16 B2.0H1The carbon fiber that the recycling of group Carbon Fiber Reinforced Cement Composites sample obtains Surface breakdown mode.
I20S is shown in Figure 16 C2.0H3T2The carbon fiber that the recycling of group Carbon Fiber Reinforced Cement Composites sample obtains The surface breakdown mode of dimension.
I40S is shown in Figure 16 D2.0H3T2The carbon fiber that the recycling of group Carbon Fiber Reinforced Cement Composites sample obtains The surface breakdown mode of dimension.
I20S is shown in Figure 16 E2.0H3T3The carbon fiber that the recycling of group Carbon Fiber Reinforced Cement Composites sample obtains The surface breakdown mode of dimension.
I40S is shown in Figure 16 F2.0H3T3The carbon fiber that the recycling of group Carbon Fiber Reinforced Cement Composites sample obtains The surface breakdown mode of dimension.
I20S is shown in Figure 17 A2.0H3T1The carbon fiber that the recycling of group Carbon Fiber Reinforced Cement Composites sample obtains The SEM scan image of dimension.
I40S is shown in Figure 17 B2.0H3T1The carbon fiber that the recycling of group Carbon Fiber Reinforced Cement Composites sample obtains The SEM scan image of dimension.
I20S is shown in Figure 17 C2.0H3T2The carbon fiber that the recycling of group Carbon Fiber Reinforced Cement Composites sample obtains The SEM scan image of dimension.
I40S is shown in Figure 17 D2.0H3T2The carbon fiber that the recycling of group Carbon Fiber Reinforced Cement Composites sample obtains The SEM scan image of dimension.
I20S is shown in Figure 17 E2.0H3T3The carbon fiber that the recycling of group Carbon Fiber Reinforced Cement Composites sample obtains The table SEM scan image of dimension.
I40S is shown in Figure 17 F2.0H3T3The carbon fiber that the recycling of group Carbon Fiber Reinforced Cement Composites sample obtains The SEM scan image of dimension.
I20S is shown in Figure 18 A2.0Group Carbon Fiber Reinforced Cement Composites sample recycles under different temperatures gradient The XRD scanning spectra of obtained carbon fiber.
I40S is shown in Figure 18 B2.0Group Carbon Fiber Reinforced Cement Composites sample recycles under different temperatures gradient The XRD scanning spectra of obtained carbon fiber.
I20S is shown in Figure 19 A2.0H3T1The carbon fiber that the recycling of group Carbon Fiber Reinforced Cement Composites sample obtains The XPS of dimension scans full spectrogram picture.
I20S is shown in Figure 19 B2.0H3T1The carbon fiber that the recycling of group Carbon Fiber Reinforced Cement Composites sample obtains The XPS of dimension scans C1s high-resolution narrow spectrogram picture.
I20S is shown in Figure 19 C2.0H3T2The carbon fiber that the recycling of group Carbon Fiber Reinforced Cement Composites sample obtains The XPS of dimension scans full spectrogram picture.
I20S is shown in Figure 19 D2.0H3T2The carbon fiber that the recycling of group Carbon Fiber Reinforced Cement Composites sample obtains The XPS of dimension scans C1s high-resolution narrow spectrogram picture.
I20S is shown in Figure 19 E2.0H3T3The carbon fiber that the recycling of group Carbon Fiber Reinforced Cement Composites sample obtains The XPS of dimension scans full spectrogram picture.
I20S is shown in Figure 19 F2.0H3T3The carbon fiber that the recycling of group Carbon Fiber Reinforced Cement Composites sample obtains The XPS of dimension scans C1s high-resolution narrow spectrogram picture.
I20S is shown in Figure 20 A2.0Group Carbon Fiber Reinforced Cement Composites sample in different catalysts concentration next time Receive the XRD scanning spectra of obtained carbon fiber.
I40S is shown in Figure 20 B2.0Group Carbon Fiber Reinforced Cement Composites sample in different catalysts concentration next time Receive the XRD scanning spectra of obtained carbon fiber.
Specific embodiment
It is described below to be disclosed for so that those skilled in the art manufacture and use the present invention.Middle offer described below compared with Good embodiment only as the example and modification that will be apparent to those skilled in the art, does not constitute the limit to the scope of the invention System.General Principle defined in described below can be applied to without departing substantially from spirit of that invention and invention scope other embodiments, Optional substitution, modification, equivalent implementation and application.
Figure 1A to Figure 20 B of reference book attached drawing, according to present pre-ferred embodiments for from inorganic coagulation material The method of recycling high-performance carbon fibre is described in detail, and illustratively, is explained using Carbon Fiber Reinforced Cement-based Composites specific real Mode is applied, wherein the method for the recycling carbon fiber from Carbon Fiber Reinforced Cement Composites (waste) includes following steps It is rapid:
(A) reaction temperature in 25 DEG C~75 DEG C places Carbon Fiber Reinforced Cement Composites in the electrolytic solution, In the electrolyte contain weight ratio be 0.5%~3% NaCl and 1.0g/L~5g/L catalyst；
(B) it is powered to the Carbon Fiber Reinforced Cement Composites placed in the electrolytic solution, wherein the fibre reinforced water Cement-based composite material is connected with the anode of power supply, and control current density is 3333.3~6666.7mA/m2, wherein the electric current is close The size of degree is soaked in the electrolyte according to carbon fibre material in the carbon fiber reinforced inorganic (cement base) composite material Surface area size calculated；With
(C) it is powered after reaction 0.5-200 hours, the carbon fiber regenerant of generation is taken out from the electrolyte.
It is noted that the one of the method for high-performance carbon fibre is recycled described in of the invention from inorganic coagulation material In a little embodiments, the method that high-performance carbon fibre is recycled from inorganic coagulation material is further wrapped after the step (C) Include step:
(D) the carbon fiber regenerant taken out from the electrolyte is rinsed, to remove cement base gel.
Further, in the step (D), wherein carbon fiber regenerant surface is equipped with the hole being spaced apart Hole, particularly, the interval between each described hole are greater than 0.1mm, and washing pressure is higher than 0.1MPa, and washing time is no less than 3 seconds. Herein, electrolyte refers to being used to return from Carbon Fiber Reinforced Cement Composites containing NaCl, water and catalyst Receive carbon fiber.Illustratively, NaCl concentration is measured by weight percentage respectively, such as NaCl concentration can be x1 (0.5%), x2 (1%), x3 (2%) and x4 (3%).The yardstick of electric current (I) size is mA, such as 20mA, 40mA.In this example, when ignoring When the thickness of CFRP, it is 2 × 100mm × 30mm=6000mm that CFRP test specimen, which is exposed to the experiment surface area (A) in electrolyte,2, Therefore corresponding current density (i=I/A) is respectively 3333.3,6666.7mA/m2.Specific carbon fiber reinforced cement base is compound The grouping of material and experiment parameter are shown in Table 5.1, and wherein the number of Carbon Fiber Reinforced Cement Composites test specimen is by action current Intensity, NaCl concentration, HNO3Concentration and temperature determine jointly, for example test specimen numbers " I20S2.0H3T40", first part " I20 " is The constant current strength for referring to that test specimen applies is 20mA, second part " S2.0" refer to that concentration NaCl is deionized water in electrolyte The 2% of amount, Part III " H3" refer to the HNO added in every liter of electrolyte3Concentration is 3g/L.Part IV " T40" refer to experiment The temperature of electrolyte is maintained at 40 DEG C in the process.Show that test carries out (temperature is 25 degree) at room temperature when no Part IV
As shown in Figure 1A of Figure of description, returned from (electrochemistry) of CFRP enhancing cement-base composite material recycling carbon fiber Receipts system includes DC power supply, provides one-way only operation electric current for system；Anode and cathode material, wherein fibre reinforced water to be recycled Cement-based composite material plate (recycling sample) is connected as anode with positive pole, and stainless steel substrates are as cathode and power cathode phase Even；Electrolyte contains NaCl, water (solvent) and catalyst；Data logger (Datalog), with recycling sample and stainless steel substrates Parallel connection, monitor sample voltage change.Illustratively, Carbon Fiber Reinforced Cement Composites plate is placed in parallel with stainless steel substrates, And the two distance is fixed as 50mm.
As shown in Fig. 2 of Figure of description, through a chemical treatment, recycle to obtain from Carbon Fiber Reinforced Cement Composites Carbon fiber regenerant, quality is softer.
As shown in Fig. 3 A and Fig. 3 B of Figure of description, the Carbon Fiber Reinforced Cement-based Composites without electrochemistry recovery processing The interface that connects with carbon fiber of cement base, prismatic groove structure is complete and rule, and powerful machine can be formed with carbon fiber The defects of tool interlocking, interface only has minimum hole, can't see crack crackle.
As shown in Fig. 3 C and Fig. 3 D of Figure of description, boundary that the cement-based material and carbon fiber of carbon fiber regenerant connect The regular diamond shape groove structure in face, which is chopped off by vertical and horizontal large fracture, is divided into broken junior unit, is in puffy, together When there are also many biggish crackle holes distributions wherein, porosity acutely increases, and interface has completely lost and carbon fiber Mechanical snap effect, cohesive force sharp fall.
As shown in Fig. 4 of Figure of description, different grouping Carbon Fiber Reinforced Cement Composites sample is recycled The amount of carbon fiber is different, and carbon fiber yield is with HNO3Concentration increase, which is presented, first increases the trend that drops afterwards, HNO3Concentration is 3g/L When, carbon fiber yield is maximum.In HNO3Concentration is in 1g/L grouping, and carbon fiber yield is substantially reduced.
As shown in Fig. 5 of Figure of description, in reaction process, different grouping Carbon Fiber Reinforced Cement Composites sample Voltage change.Wherein H0The voltage highest of group sample, relative fluctuation are maximum；H5The voltage of group sample is lower than H0Group, but still compare It is higher；H3With H1Group sample voltage is lower.On the whole, I40 serial sample voltage ratio I20 series is big, S3.0Serial sample voltage Compare S2.0It is serial big.
As shown in Fig. 6 of Figure of description, the recycling of different grouping Carbon Fiber Reinforced Cement Composites sample is obtained Carbon mono-filaments tensile strength, wherein the monofilament tensile strength of the carbon fiber recycled is with HNO3Concentration increases and is in decline Trend, in the HNO of 0~3 (g/L)3The tensile strength fall of concentration ranges, carbon fiber is smaller, the HNO of 3~5 (g/L)3It is dense Section is spent, the carbon fiber tensile strength recycled sharply declines.
As shown in Fig. 7 of Figure of description, the recycling of different grouping Carbon Fiber Reinforced Cement Composites sample is obtained Carbon fiber interface shear strength, wherein the interface shear strength of the carbon fiber recycled is with HNO3Concentration increase and under Drop, but H1And H3The carbon fiber that group recycling obtains is bigger than precursor shear strength.
As shown in Fig. 8 A of Figure of description, the surface breakdown mode of carbon fibre precursor is DB.
As shown in Fig. 8 B of Figure of description, I20S2.0H1Group Carbon Fiber Reinforced Cement Composites sample recycles The surface breakdown mode of the carbon fiber arrived is DB.
As shown in Fig. 8 C of Figure of description, I40S2.0H1Group Carbon Fiber Reinforced Cement Composites sample recycles The surface breakdown mode of the carbon fiber arrived is DB.
As shown in Fig. 8 D of Figure of description, I20S2.0H3Group Carbon Fiber Reinforced Cement Composites sample recycles The surface breakdown mode of the carbon fiber arrived is CB.
As shown in Fig. 8 E of Figure of description, I40S2.0H3Group Carbon Fiber Reinforced Cement Composites sample recycles The surface breakdown mode of the carbon fiber arrived is CB.
As shown in Fig. 8 F of Figure of description, I20S2.0H5Group Carbon Fiber Reinforced Cement Composites sample recycles The surface breakdown mode of the carbon fiber arrived is CB.
As shown in Fig. 8 G of Figure of description, I40S2.0H5Group Carbon Fiber Reinforced Cement Composites sample recycles The surface breakdown mode of the carbon fiber arrived is EB.
As shown in Fig. 9 A of Figure of description, the SEM scan image on carbon fibre precursor surface shows that its surface is smooth.
As shown in Fig. 9 B and Fig. 9 C of Figure of description, I20S2.0H1Group and I40S2.0H1Group carbon fiber reinforced cement base is multiple The carbon fiber surface that the recycling of condensation material sample obtains does not see crackle crack other than being attached with minimal amount of cement gel The defects of pit, very completely.
As shown in Fig. 9 D and Fig. 9 E of Figure of description, I20S2.0H3Group and I40S2.0H3Group carbon fiber reinforced cement base is multiple The carbon fiber surface that the recycling of condensation material sample obtains is very clean, few cement gel particle residual, but in individual radicals Carbon fiber surface discovery has transversal crack, forms weak floor in cracks, carbon fiber tensile strength is caused to decline.
As shown in Fig. 9 F and Fig. 9 G of Figure of description, I20S2.0H5Group and I40S2.0H5Group carbon fiber reinforced cement base is multiple The cement gel particle for the carbon fiber surface that the recycling of condensation material sample obtains is more, has longitudinal crack in carbon fiber surface discovery And transversal crack, and depth is not shallow, reduces the stress section of carbon fiber, therefore H5The stretching for the carbon fiber that series recycling obtains Intensity degradation.
As shown in Figure 10 A to Figure 10 N of Figure of description, each grouping Carbon Fiber Reinforced Cement Composites sample The AFM scan image for recycling obtained carbon fiber shows to work as HNO3When concentration is lower, a small amount of oxidations of electrochemistry removal process are carved Erosion will increase the interface shear strength of carbon fiber, and HNO3When concentration is increased to a certain extent, excessive oxide etch makes instead The interface shear strength of carbon fiber reduces.
As shown in Figure 11 A to Figure 11 H of Figure of description, each grouping Carbon Fiber Reinforced Cement Composites sample is returned The XPS for receiving obtained carbon fiber scans full spectrogram picture and C1s high-resolution narrow spectrogram picture shows that carbon fiber is undergone in removal process A degree of oxidation, content of surface oxygen increase, and improve surface-active, and O~C=O key occurs, and greatly improves carbon The chemical bonds ability of fiber and epoxy resin；From the point of view of the carbon ratio and functional group content for the carbon fiber that recycling obtains, HNO3When concentration is 1 (g/L), carbon fiber degree of oxidation is too low, works as HNO3When concentration is 3 (g/L), carbon fiber degree of oxidation is best, Increase HNO3Concentration only increases carbon fiber surface C=O key.
As shown in Figure 12 of Figure of description, under condition of different temperatures, Carbon Fiber Reinforced Cement Composites sample From low to high trend is presented with the raising of temperature in the amount for recycling obtained carbon fiber, when temperature is 40 DEG C, carbon fiber yield It is maximum.
As shown in Figure 13 of Figure of description, under condition of different temperatures, in reaction process, carbon fiber reinforced cement base is compound The voltage of sample of material shows that the voltage of Carbon Fiber Reinforced Cement Composites sample is lower, the voltage of different grouping sample Difference value very little shows that under the high temperature conditions the system resistance value of sample is very small, and the voltage of all samples is recycled in electrochemistry Period kept stable.
As shown in Figure 14 of Figure of description, under condition of different temperatures, from Carbon Fiber Reinforced Cement Composites sample The obtained monofilament tensile strength of carbon fiber of recycling the trend for falling before and then slowly rising always is presented as the temperature increases.
As shown in Figure 15 of Figure of description, under condition of different temperatures, from Carbon Fiber Reinforced Cement Composites sample The recycling obtained interface shear strength of carbon fiber increased with temperature, occur falling before and then increasing downward trend again.
As shown in Figure 16 A to Figure 16 F of Figure of description, each grouping Carbon Fiber Reinforced Cement Composites sample The surface breakdown mode for recycling obtained carbon fiber, in addition to I40S2.0H3T2Failure mode be CB, the failure mode of other samples It is DB.
As shown in Figure 17 A to Figure 17 F of Figure of description, each grouping Carbon Fiber Reinforced Cement Composites sample The defects of recycling obtained carbon fiber surface crackle crack is less, illustrates the oxidation and corruption of shortening reduction return period removal process Lose equivalent damage.
As shown in Figure 19 A to Figure 19 F of Figure of description, each grouping Carbon Fiber Reinforced Cement Composites sample The XPS for recycling obtained carbon fiber scans full spectrogram picture and XPS scanning C1s high-resolution narrow spectrogram picture shows compared to room temperature shape State T0(25 DEG C), the oxygen that carbon fiber surface introduces under the condition of high temperature are more；It is T in temperature1When (40 DEG C), the carbon fiber that recycles The oxygen content and strongly hydrophilic functional group O~C=O content in dimension table face are most, with temperature continue rise both and under Drop；However carbon fiber surface C~Cl linkage content is up to 8.2%, by more serious chlorination, cause carbon fiber tensile strength and Shear strength declines to a certain degree.
Further, herein will be in conjunction with following specific examples, the present invention will be described in detail.
Example 1: the preparation of raw material (Carbon Fiber Reinforced Cement Composites)
The Carbon Fiber Reinforced Cement Composites of this experiment are made of CFRP and cement-based gelling material two large divisions.
CFRP material selection Nan Jinghai opens up the HITEX-C300 model carbon cloth of composite material company production, is that 12K is mono- To woven cloth, density 300g/m2.The extremely common composite Portland cement of China Resources board PO42.5R in the cement selection Dongguan place of production.Silicon Powder is the willing silicon powder in west for originating from Shanghai, and high molecular polymer is the redispersible powder of DY-5025 (Germany) model.Select Hong Kong card The short silk of carbon fiber of this Co., Ltd production, length is about 3mm.Select the sodium chloride (analysis of Xi Long Chemical Co., Ltd. production It is pure) and HNO3(analysis is pure), the mass fraction that the mass fraction of sodium chloride is 99.5%, B is 65% -68%.Increase in carbon fiber In strong cement-base composite material, carbon cloth occupy intermediate, and the specific ingredient and content of cement-based material are shown in Table 1.1.
Carbon Fiber Reinforced Cement Composites sample dimensions are 30mm × 245mm × 4mm.Along carbon fiber reinforced cement base Thickness of composite material direction is respectively the cement-based material of about 2 millimeters thicks up and down, and centre is carbon cloth, such as Figure 1B and Fig. 1 C institute Show.It is divided into three regions along its length, being respectively as follows: an area is trial zone (Test region), is used to recycling carbon The region of fiber, length 100mm；Two areas, that is, protection zone (Protected region), the region insulation waterproof, to ensure to try It is in the same size to test the holding of area's area during the experiment, length 80mm；Three area Ji Jie electricity of area (Electrical Connection region), it is used to connection line stainless steel substrates connector, guarantees Circuit Connectivity, length 65mm, in order to take Better electric conductivity is obtained, wherein back 20mm is carbon cloth, is connect with stainless steel substrates.Therefore, above-mentioned carbon fiber reinforced cement In based composites carbon fibre material be soaked in the surface area size in above-mentioned recyclable device in electrolyte be 100mm × 30mm × 2=6000mm2。
The manufacturing process of composite material close to field of civil engineering construction method, pours demoulding after 1 day, then puts into as far as possible Standard curing room conserves 28 days.Composite material after maintenance is placed 7 days in laboratory conditions, is spontaneously dried, then into The encapsulation of row protection zone.Protection zone is formed by five layers, from inside and outside respectively Kraft spy silicon rubber-insulating tape-epoxy sealing Glue-insulating tape-epoxy sealing glue.It is uniform in clean and dry one layer of composite panel test specimen protection zone external coating first Kraft spy's silicon rubber, be placed in the lower 24 hours naturally dries of laboratory condition；Then it is wrapped up in silicone rubber using insulating tape； Then sealing is carried out using epoxy sealing glue, is placed in the lower spontaneous curing in 48 hours of laboratory condition；Then insulating tape is reused Package；It finally reuses epoxy sealing glue and carries out sealing, be placed in the lower spontaneous curing in 48 hours of laboratory condition.
The specific component content of 1.1 carbon fiber reinforced cement based cementitious material of table
Example 2: recovery experiment system and experiment parameter design
As shown in Figure 1A of attached drawing, carbon fiber (experiment) recovering system mainly includes four parts composition: DC power supply, One-way only operation electric current is provided for system；Anode and cathode, recycling sample are connected as anode with positive pole, consumption degradation cement base rubber Body, stainless steel substrates are connected as cathode with power cathode；Electrolyte, NaCl base soln and catalyst including various concentration HNO3；Data logger (Datalog), monitor sample voltage change in parallel with recycling sample and stainless steel substrates.Recycle sample with Stainless steel substrates are placed in parallel and distance is fixed as 50m.
Experimental design mainly considers that parameter includes current density, the NaCl concentration in solution, catalyst HNO3Concentration and Temperature influence etc..In order to more effectively study influence of each parameter to carbon fiber recovering effect and efficiency, this researching and designing two A campaign.
In First Series experimental design, it is contemplated that: (1) two current strength (20mA, 40mA), based on institute in example 1 It is big to state the surface area that carbon fibre material in Carbon Fiber Reinforced Cement Composites is soaked in above-mentioned recyclable device in electrolyte Small is 100mm × 30mm × 2=6000mm2, it is known that corresponding two current density (3333.3mA/m2、6666.7mA/m2)；(2) The sodium chloride concentration (2%, 3%) of two electrolyte；(3) four catalyst concentration of nitric acid (0g/L, 1g/L, 3g/L and 5g/L). It can thus be concluded that 16 kinds of Parameter Conditions, every kind of experimental condition includes 3 parallel test specimens, and detailed test specimen grouping and experiment parameter are shown in Table 1.
In second series experimental design, the resulting more excellent scheme of First Series is chosen first, considers temperature on this basis Spend the influence to carbon fiber performance and recovery efficiency.Therefore, second series test parameters include: (1) two current value (20mA, 40mA), corresponding two current densities (3333.3mA/m2,6666.7mA/m2)；The sodium chloride concentration of (2) electrolyte (2%)；(3) catalyst concentration of nitric acid (3g/L) and (4) three temperature gradients (40 DEG C, 60 DEG C and 75 DEG C).Thus may be used 6 kinds of Parameter Conditions are obtained, every kind of experimental condition includes 3 parallel test specimens, and detailed test specimen grouping and experiment parameter are shown in Table 2.Value It is noted that the maximum temperature of experimental setup is only 75 DEG C in order to realize recycling at normal temperatures and pressures, do not consider excessively high Temperature condition.
Test specimen is numbered by action current intensity, NaCl concentration, HNO3Concentration and temperature determine jointly, such as test specimen number “I20S2.0H3T40", the constant current strength that first part " I20 " refers to that test specimen applies is 20mA, and second part " S2 " refers to electricity Solving concentration NaCl in liquid is the 2% of deionized water quality, Part III " H3" refer to the HNO added in every liter of electrolyte3Concentration is 3g/L.Part IV " T40 " refers to that the temperature of electrolyte in experimentation is maintained at 40 DEG C.Show that test exists when no Part IV (temperature is 25 degree) is carried out in room temperature
Example 3: experimental test procedures
The monitoring of 3.1 sample voltages
The HIOKI-LR8400 model data recorder (Datalog) of Zhi Electric Co., Ltd of Japan production is selected, often 1 data of hour acquisition.Adopting frequent rate is 1h/ times, supply frequency 50HZ.
The test of 3.2 carbon mono-filaments tensile properties
According to carbon mono-filaments tensile strength test specification ISO 11566 [54], Agilent company of the U.S. production is selected 150 model nanometer stretching instrument of nano UTM carries out carbon mono-filaments stretching experiment；Test macro is UTM-Bionix Standard Toecomp Quasistatic.Test parameter setting it is as follows: 750 μ N of imposed load, rate of extension for 0.2 μm/ S, load resolution ratio are 50nN, and displacement resolution < 0.1nm, stretching resolution ratio is 35nm, actuator maximum displacement 1mm.Test temperature Degree is 20 DEG C -30 DEG C, air humidity 40%.
Before carrying out carbon mono-filaments extension test, carbon mono-filaments need to be fixed on to the photo paper having a size of 15mm 20mm On, it is the circular hole of diameter 6mm among photo paper, carbon mono-filaments is sticked to circular hole horizontal direction diametrically using paste glue, Fiber is unable to tension or excessively relaxes.
After sample completes, it is placed in laboratory condition one day, to glue naturally dry.Sample nanometer can be put into draw Instrument fixture is stretched, then finally starts to be tested along cutting by photo paper two sides.Carbon mono-filaments testing length is 61mm, The sample that each sample need to be tested is 20, and carbon mono-filaments intensity results are 20 sample strength average values.Filament stretch is strong It is as follows to spend formula:
σ in formulaf- monofilament tensile strength (MPa)
Ff- single wire fracture peak load (N)
D-filament diameter (mm)
The laser diameter measuring instrument of Changchun industry photoelectricity technology corporation, Ltd. production is selected to measure carbon mono-filaments diameter.By sample It is placed on specimen holder, using diffraction principle, measures the Dark stripe of diffraction spacing of monofilament, list can be calculated by formula scales The accurate diameter of silk, formula are as follows:
D=kL λ/xk=L λ/S (2-2)
D-filament diameter (nm) in formula
S-dark line diameter (cm)
Distance of the L-sample to diffraction screen
xkDistance of the very dark line of-kth to optical axis
Parameter setting: L=60cm, λ=532nm
The test of 3.3 carbon mono-filaments interface shear strengths
It selects the HM410 composite material interface characteristic evaluating device of Dong Rong Co., Ltd. of Japan production to carry out droplet embedding to survey Examination.Test parameter sets as follows: test speed 0.12mm/min, and microscope multiplying power is 2 times.
According to literature research[55], the diameter range for testing resin balls is preferably chosen to be 40 μm~80 μm.Each test sample Resin balls are 5, and interface shear strength result takes its average value.Interface shear strength formula is as follows:
F-payload values (μ N) in formula
D-filament diameter (μm)
L-resin bulb diameter (μm)
3.4 environmental scanning electron microscopes (ESEM) test
The Quanta TM 250FEG model environmental scanning electron microscope for selecting FEI Co. of the U.S. obtains recycling Carbon fiber surface pattern situation carries out observation analysis.High vacuum mode is selected, operating distance is about 10mm, and test acceleration voltage is 20KV.It is more clear accurate surface topography in order to obtain, needs to increase the electric conductivity of carbon fiber, therefore sample is being tested Before, metal spraying processing is first carried out in ion sputtering instrument.
3.5 atomic force microscope (AFM) test
The ICON-PT-PKG model scanning probe microscopy for selecting the production of U.S.'s Brooker company, the carbon that recycling is obtained Fiber is tested, and the two and three dimensions figure of its surface microscopic topographic and fluctuating situation can be obtained.
Therefore the Sample Scan range of this experiment selects 4 μm, using tapping-mode, sweep speed 1.0Hz.In order to guarantee The length of successfully tested rate, carbon mono-filaments is not lower than 20mm.
Analytical calculation is carried out to image using 1.8 software of NanoScope Analysis, in four kinds of roughness meters of software Up in formula, Ra is selected to characterize roughness, calculation formula is as follows:
N in formulaxThe step number of-X-axis
NyThe step number of-Y-axis
3.6X ray analysis instrument (XRD)
The D8Advance model high-resolution X-ray analyzer for selecting the production of Bruker company of Germany, to recycling carbon fiber It is scanned detection, qualitative can obtain the crystal structure information of surface composition.Using Continuous PSD fast mode, Operating voltage is 40KV, and operating current 200mA, copper test target emanation wavelength is 154mm, and scanning angle is 10 °~80 °, step A length of 0.02 °, every step sweep time is 0.2S.Material phase analysis is carried out to map using Jade5.0 software.
3.7X- X-ray photoelectron spectroscopy X (XPS)
Select ULVAC-PHI VPII model photoelectron spectrograph, to the obtained carbon fiber of recycling first carry out 0eV~ The full spectrum of 800eV range scans, and obtains its surface-element information, then carry out high resolution scanning to C1s, soft using XPSPeak4.1 Part carries out Gaussian function to result and Lorentzian is fitted, the type and content situation information of functional-analytical group.When test, need Guarantee that carbon fiber is smooth to be placed on testboard.The x-ray source of monochromator be Al target, test elements include: C, O, Cl, N, Si, Ca, select 90 ° as incidence angle.
Example 4: electrochemistry recovery process design
Recovery process step relates generally to three parts: (A) is by ready Carbon Fiber Reinforced Cement Composites (plate) It is placed on electrolyte；(B) it is powered to the Carbon Fiber Reinforced Cement Composites placed in the electrolytic solution, wherein the carbon fiber increases Strong cement-base composite material is connected with the anode of power supply, and controls electric current in suitable magnitude range；(C) is powered reaction suitably Time (generally 8-240), after hour, the carbon fiber regenerant of generation was taken out from the electrolyte.In recycling provided by the invention In technique, according to different grouping, size of current is controlled in 20mA and 40mA；Sodium chloride concentration (weight percent) is controlled in 2.0% and 3.0%；Catalyst HNO3Concentration is controlled in 0%, 1%, 3% and 5%), totally 16 kinds of group test samples.It is detailed Sample packet and experiment parameter are shown in Table 4.1.Sample number is by size of current, NaCl concentration and catalyst HNO3Concentration is jointly true It is fixed, such as sample number " I20S2.0H1", the electric current that first part " I20 " refers to that sample applies is 20mA, second part " S2.0” Refer to that NaCl concentration is 2.0% in electrolyte, Part III " H1" refer to the HNO added in every liter of electrolyte3Concentration is 1g.Tool The experiment parameter and grouping situation of body are as shown in table 5.1.Electrochemistry return period is 8 days, and after recycling, sample is taken out, The cement base colloid on surface is removed, then the carbon fiber cleaning, drying that will be obtained carries out various tests.
The grouping of 4.1 experiment sample of table and parameter
Example 5: the cleaning of the carbon fiber recycled removes glue
First Series Experimentation An electrochemical return period is 8 days, and second series Experimentation An electrochemical return period is 4 days.It is returning Receipts process, cement base gel have a small amount of dissolution, have subtle gelling material particles in solution and on stainless steel substrates cathode.Recycling knot Shu Hou takes out test specimen in calm liquid, it can be found that inorganic glue still links together with carbon fiber, as shown in Figure 2.Therefore, it obtains The carbon fiber regenerant arrived is the mixture of carbon fiber and cement base inorganic glue.In other words, the carbon fiber recycled still with Cement base inorganic glue connection is connected together.However, electrochemistry recycling is after reaction, cement base gel rubber material can become very soft, It can be removed easily with hard broad wool brush or rigid plate.However, similar strength rejecting may be such that carbon fiber surface remains There is one layer of colloid, it is difficult to remove.In order to preferably remove cement base gel method, can carbon fiber regenerant surface every 0.1mm or more inserts a hole, and then the water flow with hydraulic pressure in 0.1MPa or more is rinsed, and flushing time is 3 seconds or more, to remove water Mud base inorganic glue.
Example 6: the performance test of the carbon fiber recycled
The hardness determination of 6.1 carbon fiber regenerants
After electrochemical reaction, obtained carbon fiber regenerant includes carbon fiber and inorganic glue, generally plate or Strip.Coating pencil hardness test method tests its hardness.
The QHQ-A type pencil hardometer for selecting the production of AIPLI Instrument Ltd., according to specification GB/T6739-2006/ It is consistent flat to be placed in surface texture under the conditions of temperature (23 ± 2) DEG C and relative humidity (50 ± 5) % by ISO15184:1998 Plate, pencil are downwardly against on composite material surface under the load of 750g with 45° angle, with the speed of 0.5mm/s~1mm/s towards remote Direction from operator pushes 10mm, since the most soft rank 9B of pencil, until composite material generates the visible cohesion in surface and breaks It is bad, and service precision is the vernier caliper measurement collapse dept of 0.02mm.The obtained detailed hardness level of composite material is tested to see Table 6.1.
6.1 composite material sample hardness of table and cohesional failure depth
Note: huttriall refers to that the part hardness >=9H in sample, soft portion refer to the part of hardness < 9H.Pencil hardometer it is soft Hardness is from low to high successively are as follows: 9B-8B-7B-6B-5B-4B-3B-2B-1B-HB-F-H-2H-3H-4H-5H-6H-7H-8H-9 H
From table it can be seen that, Carbon Fiber Reinforced Cement Composites sample is respectively grouped after electrochemistry removal process, There is a degree of softening, influencing the most significant factor of its softening degree is catalyst HNO3, HNO3Concentration is bigger, composite wood Expect that the degradation being subject to is more serious, hardness is lower.H0The sample hardness of series is divided into two parts, and huttriall hardness is far longer than 9H, the minimum hardness in soft portion is also 2B, and soft portion's area very little, illustrates the electrochemical action for only leaning on sodium chloride solution, carbon fiber Dimension enhancing cement-base composite material sample is far from reaching the degree for destroying softening, and softens uneven.H1In series, I20S2.0H1And I40S2.0H1Sample be still divided into huttriall and soft portion's two parts, the hardness of huttriall is respectively to be greater than 9H and 9H, soft The hardness in portion is respectively 5B and 9B, I20S3.0H1And I40S3.0H1Sample hardness be respectively 7B and 9B.The above result shows that NaCl Concentration is bigger, and Carbon Fiber Reinforced Cement Composites sample softening degree is bigger, and being embodied in hardness is exactly to become softer；Together Sample, the Carbon Fiber Reinforced Cement Composites sample that electric current increase will cause is softer.H3And H5The hardness of serial sample is small In 9B, the cohesional failure depth caused by test relatively from the point of view of, can equally obtain above-mentioned conclusion.
Fig. 3 A to Fig. 3 D of attached drawing show the SEM scanning result to carbon fiber regenerant, and wherein Fig. 3 A is without electrification The interface that the cement base of the Carbon Fiber Reinforced Cement-based Composites of recovery processing connects with carbon fiber is learned, prismatic groove structure is suitable Complete and rule can form powerful mechanical snap effect with carbon fiber, and interface only has minimum hole, can't see crack and split The defects of line.Fig. 3 B is the partial enlargement (10000 times of amplification) in Fig. 3 A at box, therefrom it can be found that some by cement slurry With the network structure of the interlaced insertion of high molecular polymer, these structures increase the intensity and adhesive property of material itself. Fig. 3 C is I40S3.0H1The interface that the cement-based material and carbon fiber of middle carbon fiber regenerant connect, it can be seen that diamond shape groove Structure is chopped off by vertical and horizontal large fracture and is divided into broken junior unit, is in puffy, while there are also many biggish Crackle hole is distributed wherein, and porosity acutely increases, and interface has completely lost to be acted on the mechanical snap of carbon fiber, bonding Power sharp fall.Figure D is the partial enlargement (10000 times of amplification) in figure C at box, it can be seen that is white inside crack The mutual embedded network structure of loose shape structure, cement slurry and polymer has been destroyed, and cement-based material is in Voiding, carbon The cohesive force of fiber and cement-based interface has been lost.
The yield of 6.2 carbon fibers
It can be seen that, the quality of carbon fibre precursor is 841mg from the following table 6 .2, this quality is the carbon fiber of 30mm × 100mm It ties up cloth and weighs gained, it should be pointed out that H0Series is recycled due to this group of Carbon Fiber Reinforced Cement Composites sample The carbon fiber regenerant hardness arrived is larger, cannot effortless removal cement-based material easily, returned so being defined as carbon fiber Receipts amount is 0g/L, is not listed in this table.The amount of carbon fiber that different grouping sample recycles has different, intuitively not With carbon fiber yield between grouping, as shown in Figure 4.It can be found that carbon fiber yield is with HNO3After first increasing is presented in concentration increase Drop trend, HNO3When concentration is 3g/L, carbon fiber yield is maximum.In H1In group (1g/L), I20S2.0And I40S2.0Yield Obvious much lower, only 233mg and 286mg, the reason is that it is only recovered to the carbon fiber in soft portion, and the area in soft portion is accounted in recovery area It is smaller.H5The carbon fiber recycling of serial sample is less, and it is bigger to be primarily due to deterioration suffered by carbon fiber, surface layer peeling, becomes At very thin very undercoat silk, it is attached on cement-based material, also has loss in wash phase.I40 series carbon fiber yield is overall On, S lower than I20 series3.0Series carbon fiber yield ratio S2.0Low when 1g/L (B be except) shows larger current and larger Sodium chloride concentration causes the deterioration of carbon fiber bigger.It is unfavorable for carbon fiber recycling.
Carbon fiber yield under the conditions of 6.2 different parameters of table
Note: 1) DB: expression failure mode is inorganic rouge layer stripping damage
2) CB: indicate that failure mode is carbon fiber and inorganic rouge interface delaminating damage
3) EB: expression failure mode is carbon fiber surface layer stripping damage
In order to determine whether electric current plays a role in the softening of Carbon Fiber Reinforced Cement Composites sample, setting pair Than experiment, by Carbon Fiber Reinforced Cement Composites sample difference soaking in catalyst B (HNO3) dosage be respectively 1g/L, In the 2.0%NaCl solution of 3g/L, 5g/L, 8g/L and 10g/L dosage, it is respectively designated as S2.0H1、S2.0H3、S2.0H5、S2.0H8With S2.0H10, the time is 8 days.
Carbon Fiber Reinforced Cement Composites have different, lighter before and after soaking, and surface occurs some small Hole, in order to more precisely judge catalyst B (HNO3) treatment effect, carry out hardness test, the results are shown in Table 6.3.From table It arrives, treated, and composite hardness is still very high, works as HNO3When concentration reaches 10g/L, composite hardness 3B, not by Machine tool cannot complete cement colloid to dispose, and for a long time in high concentration catalyst B (HNO3) under solution soaking, carbon Fibre property has very big deterioration.Show that electric current plays an important role in Carbon Fiber Reinforced Cement Composites softening, electricity It is more efficient that chemical method processing meets material.
Composite hardness after the processing of table 6.3B electrolyte
The detection of 6.3 sample voltages
It is seen from fig 5 that the voltage of all samples is in electrochemistry kept stable return period, without very big wave It is dynamic.Different grouping sample voltage has different, H0(0g/L) organizes the voltage highest of sample, and relative fluctuation is maximum, and reason may It is there is no catalyst HNO3It is slow to the emollescence of Carbon Fiber Reinforced Cement Composites sample, porosity very little, sample This electric conductivity is bad, therefore voltage is higher, fluctuates larger.H5The voltage of serial sample is lower than H0Series, but still it is relatively high, In H5In series, the destruction of sample cement-based material is very serious, has been applied to carbon fiber, and voltage is higher to may be and carbon It is related that the deterioration of fiber causes resistance to increase.H3(3g/L) and H1(1g/L) group sample voltage is lower, this is because electrochemical action Mitigation is compared to Carbon Fiber Reinforced Cement Composites effect, the deterioration of carbon fiber is very slight, and electric conductivity is preferable.In totality On, I40 serial sample voltage ratio I20 series is big, S3.0Serial sample voltage ratio S2.0It is serial big, show that voltage and NaCl concentration are got over Greatly, resistance value is bigger, thus voltage is bigger.
From table 5.5, it can be seen that, the carbon fiber diameter recycled does not change, and illustrates in electrochemistry removal process carbon fiber Although the effects of tieing up the corrosion by electrochemical oxidation and acid, carbon fiber surface is peeled off without lamella substantially.Through detecting, carbon The monofilament tensile strength of fiber precursor is 3588MPa, I20S in the carbon fiber recycled2.0H1Tensile strength be up to 3072MPa reaches the 85.62% of carbon fibre precursor；I40S3.0H5The minimum 2162MPa of tensile strength, only carbon fiber is former The 60.26% of silk.The monofilament tensile strength for the carbon fiber that other recycling obtain occurs in various degree compared to carbon fibre precursor Decline, is detailed in Fig. 6.
As shown in Fig. 6 of attached drawing, the monofilament tensile strength of the carbon fiber recycled is with HNO3Concentration increases and is in decline Trend, in the HNO of 0~3 (g/L)3The tensile strength fall of concentration ranges, carbon fiber is smaller, the HNO of 3~5 (g/L)3It is dense Degree section carbon fiber tensile strength sharply declines, and illustrates HNO3Concentration is higher, deteriorated caused by carbon fiber it is more serious, especially Work as HNO3After concentration is more than 3 (g/L).Work as HNO3When concentration is 1 (g/L) and 3 (g/L), between the carbon fiber under different parameters effect Tensile strength difference is little, H1Series carbon fiber tensile strength is between 2987MPa~3072MPa, H3Series carbon fiber stretches strong Degree is in 2898MPa~2974MPa range intervals, and I20 series carbon fiber tensile strength ratio I40 series is high, S2.0Series carbon fiber Tensile strength ratio S3.0Intensity wants high；Work as HNO3When concentration is 5 (g/L), the strength difference of carbon fiber is smaller between different parameters, But be still that low current serial sample is higher than high current serial sample, low sodium chloride concentration serial sample is than high concentration series sample This height.
The interface shearing performance for the carbon fiber that 6.4 recycling obtain
From table 6.4, it can be seen that, the interface shear strength of carbon fibre precursor and inorganic rouge is 27.09MPa, and failure mode is The interface shear strength of DB, the carbon fiber recycled are larger, in addition to H5The sample shear strength of series, other series is both greater than Equal to carbon fibre precursor, failure mode and HNO3Concentration is related, H1The failure mode of serial sample is DB, H3Serial sample is destroyed Mode is CB, H5The failure mode of serial sample is EB, with HNO3The increase of concentration destroys position and is transferred to from inorganic rouge layer Boundary layer arrives carbon fiber surface layer again.
The interface shear strength of the recycling carbon fiber of table 6.4
Note: 1) DB: expression failure mode is epoxy resin layer stripping damage
2) CB: indicate that failure mode is carbon fiber and epoxy resin interface stripping damage
3) EB: expression failure mode is carbon fiber surface layer stripping damage
It will be seen in fig. 7 that the interface shear strength for the carbon fiber that recycling obtains is with HNO3Concentration increases and declines, still H1And H3The carbon fiber that series recycling obtains is bigger than precursor shear strength, illustrates the electrochemical oxidation under the conditions of B of low concentration It can be improved shear strength.It can see from Fig. 8 A, the failure mode of carbon fibre precursor is DB, and inorganic rouge layer is stripped, carbon fiber Dimension table face is bonding with one layer of smooth resin；Fig. 8 B and Fig. 8 C are I20S respectively2.0H1And I40S2.0H1Destruction image, although broken Bad mode is still DB, but the coarse concave-convex surface of resin layer of carbon fiber surface bonding, especially I20S2.0H1Sample, explanation H1The cohesive force of the carbon fiber and inorganic rouge of series is stronger, it may be possible to due under the B of low concentration, the microstructure of carbon fiber surface It is oxidized and etches more preferably, mechanical snap effect is stronger；In Fig. 8 D and Fig. 8 E, I20S2.0H3And I40S2.0H3Failure mode Although CB, after stripping damage, carbon fiber surface is bonded with acicular elongated inorganic rouge, and needle-shaped resin not only increases destruction Surface area, and play the role of similar reinforcing bar Rib Reinforced, mechanical snap power is greatly improved, increases the caking property with inorganic rouge Can, thus S2.0The shear strength of serial sample is still higher than carbon fibre precursor.In HNO3When concentration is 1 (g/L) and 3 (g/L), I20 serial sample shear strength ratio I40 series is high, I20S3.0H1；S2.0Serial sample shear strength ratio S3.0It is serial high；In H5System Column, low current and the sample shear strength that B low concentration acts on are bigger, but due to excessive oxide etch, electric current and B parameter pair The influence of shear strength is very small, sees from Fig. 8 F and Fig. 8 G, I20S2.0H5Separation mode be CB, carbon fiber surface do not set Rouge residual, it is seen that the longitudinal groove structure on surface shows that the adhesive property of carbon fiber and inorganic rouge declines；I40S2.0H5Destruction Mode is EB, it can be seen that carbon fiber surface has been stripped fraction epidermis, it may be possible to which epidermis has been oxidized to fragile piece at this Layer, is no longer firm entirety with carbon fiber ontology；Show HNO3When concentration is 5%, the carbon fiber recycled is by relatively tight The oxidation and corrosiveness of weight, reduce carbon fiber surface adhesive property.
Example 7: the detection of the carbon fiber recycled
7.1SEM scanning
It is found through detection, S2.0Series and S3.0The microscopic appearance difference for the carbon fiber that series recycling obtains is very small, so S is listed at this2.0The SEM image for the carbon fiber that series recycling obtains.It can see from Fig. 9 A, carbon fibre precursor surface is very It is smooth, the defects of not seeing crackle crack pit.Recovered obtained carbon fiber surface is attached with a small amount of gel Grain, this be clean not enough thoroughly caused by residual.See from Fig. 9 B and Fig. 9 C, I20S2.0H1And I40S2.0H1What recycling obtained Carbon fiber surface is other than being attached with minimal amount of cement gel, the defects of not seeing crackle crack pit, very completely, table It is bright under the conditions of the B of 1 (g/L) concentration, electrochemistry removal process does not cause serious oxidation bad on the obtained carbon fiber of recycling Change, so the tensile strength fall for the carbon fiber that series recycling obtains is little.It is found from Fig. 9 D and Fig. 9 E, I20S2.0H3 And I40S2.0H3It is very clean to recycle obtained carbon fiber surface, few cement gel particle residual, but in the carbon of individual radicals Fiber surface discovery has transversal crack, forms weak floor in cracks, causes carbon fiber tensile strength to decline, therefore H3Series is returned Receive obtained carbon fiber tensile strength ratio H1Series is low.Show that carbon fiber was recycling under the conditions of the catalyst B of 3g/L concentration The oxidative degradation degree that journey is subject to increases.See from Fig. 9 F and Fig. 9 G, I20S2.0H5And I40S2.0H5Recycle obtained carbon fiber surface The cement gel particle in face is more, has longitudinal crack and transversal crack in carbon fiber surface discovery, and depth is not shallow, reduces carbon The stress section of fiber, therefore H5The tensile strength degradation for the carbon fiber that series recycling obtains, only reaches carbon fibre precursor The 60.26%~66.64% of intensity.Illustrate that carbon fiber receives sternly in removal process under the conditions of the catalyst B of 5g/L concentration The oxidative degradation of weight.The carbon fiber image that I20 series and I40 series recycle in comparison diagram 10, discovery I40 series recycle The surface defect of the carbon fiber arrived is more, and the damage for illustrating that the carbon fiber that high current effect obtains recycling is subject to is more serious.
7.2AFM scanning
The surface microscopic topographic of carbon fiber plays very important influence to its interfacial bond property, by roughness and pattern Structure is characterized, and carbon fibre precursor and the AFM scan test result for recycling obtained carbon fiber are shown in Table 7.1 and Figure 10 respectively, It is pointed out that S2.0Series and S3.0The carbon fiber that the recycling of series obtains difference in roughness and appearance structure is little, So listing S at this2.0The carbon fiber afm image that series recycling obtains.
Table 7.1 recycles the roughness of obtained carbon fiber
It can see from Figure 10 A and Figure 10 B, carbon fibre precursor surface is very smooth, there is no longitudinal groove structure, almost without Epidermis bulge-structure, the roughness being calculated are 144nm.From Figure 10 C to Figure 10 F it can be found that in H1Carbon fiber series, by It being acted in the oxide etch of removal process, there is apparent longitudinal groove structure and epidermis bulge-structure in carbon fiber surface, these Fine structure plays the role of similar reinforcing bar Rib Reinforced, greatly improves the mechanical snap of carbon fiber and inorganic rouge, increases Carbon fiber surface surface roughness, I20S2.0H1And I40S2.0H1Roughness be respectively 180nm and 178nm, increase specific surface area, change Kind wellability, improves interfacial bond property, therefore, H1The carbon fiber shear strength that series recycling obtains is former much higher than carbon fiber Silk.See from Figure 10 G to Figure 10 J, works as HNO3When concentration increases to 3, carbon fiber surface still has longitudinal groove structure, but compares H1Weak, the I20S of series2.0H3The bulge-structure of carbon fiber surface increases, and I40S2.0H3Only different apparent longitudinal groove knots Structure, the roughness being calculated are respectively 208nm and 162nm, and longitudinal groove structure dies down, and the machinery of carbon fiber surface is caused to be stung Cooperation decline, thus H3The carbon fiber interface shear strength ratio H that series recycling obtains1Series is low, but still it is former to be higher than carbon fiber Silk, shows HNO3Concentration increases, and the deteriorations such as oxide etch for causing carbon fiber to be subject to enhancing causes interface shear strength to weaken. See from Figure 10 K to Figure 10 N, HNO3When concentration continues to increase to 5, I20S2.0H5And I40S2.0H5Carbon fiber surface is almost seen not To longitudinal groove structure, only mixed bulge-structure, the roughness being calculated is respectively 104nm and 121nm, it should be pointed out that , I40S2.0H5Longitudinal groove be production when cause, not caused by oxide etch.Excessive oxide etch makes active carbon granule It falls off, longitudinal groove structure can not be formed, the mechanical snap power of carbon fiber sharply declines, and leads to H5The carbon fiber that series recycling obtains Shear strength decline, slightly below carbon fibre precursor are tieed up, and the bonding between the protrusion means of severe oxidation and carbon fiber ontology becomes It is weak, when carrying out the dial-out of resin droplet, it is easy to happen removing, causes EB failure mode.It is above-mentioned to show to work as HNO3Concentration is lower When, a small amount of oxide etch of electrochemistry removal process will increase the interface shear strength of carbon fiber, and HNO3Concentration increases to one When determining degree, excessive oxide etch instead reduces the interface shear strength of carbon fiber.
7.3XPS scanning
It is detected, the full spectrum of XPS scanning and the narrow spectrum of C1s high-resolution of the carbon fiber recycled are shown in Figure 11 A to Figure 11 H, left Column are that the scanning of sample is composed entirely.It can see from full spectrogram is scanned, there are mainly five types of peaks, i.e. two main peaks in figure: C (284.6eV) and O (532.0eV)；Three secondary peaks: Si (99.5eV), Cl (199.8eV) and Ca (347eV).Carbon fibre precursor Surface basic element be carbon and oxygen, a small amount of silicon, chlorine and the calcium that detected are introducings during the experiment.VCF and I20S2.0The specific chemical element content situation of carbon fiber surface that group recycling obtains is shown in Table 7.2.
Table 7.2VCF and I20S2.0The carbon fiber surface constituent content (%) that group recycling obtains
See from table, the carbon content on carbon fibre precursor surface is up to 79.3%, and oxygen content 20.7% does not detect Other elements content.It is all to recycle the obtained carbon contents of carbon fiber surface all relatively, under general compared to carbon fibre precursor 10% is dropped, oxygen content then has to be risen to a certain degree；From the point of view of carbon ratio, the carbon fiber recycled is much higher than carbon fibre precursor 0.2610, in three kinds of HNO3In concentration gradient, H3Carbon ratio highest, followed by H5, minimum is H1, illustrate H3Be region most Good concentration can introduce more oxygen, obtain bigger surface-active, the chemical bonds ability of enhancing and inorganic rouge.From chlorine From the point of view of content, HNO3Concentration increase can improve carbon fiber surface chlorinity.All carbon fiber sample surfaces all introduce a certain amount of Calcium, this may be residual of the cement-based material in carbon fiber surface.In addition, I20S2.0H1Carbon fiber surface detects 3.4% Silicone content.Using software XPSPeak4.1, the narrow spectrum of C1s high-resolution can be divided into following six kinds of chemical bond peaks according to combination and carried out Gauss long-range navigation thatch fitting: graphite state C~C (284.4eV), amorphous state C~C (284.8eV), C=O (285.5eV), C~O (286.2eV), C~Cl (287.2) and O~C=O (288.4eV).The right column of Fig. 5 .15 are shown in the fitting of C1s swarming, it should be pointed out that Be that the C1s of carbon fibre precursor is bimodal, and does not have area after 288eV peak position, thus fitting obtain the results show that carbon Fiber precursor surface is free of O~C=O key, other carbon carbon and oxidation of coal key peak position deviate, and shows carbon fibre precursor table Face activity is bad.And C~Cl the linkage content for recycling obtained carbon fiber surface is zero, illustrates the carbon fiber surface that recycling obtains Chlorine exists with adsorbed state, not with chemical bonds.Obtained carbon fiber surface functional group content is specifically recycled to be shown in Table 7.3。
Table 7.3VCF and I20S2.0The carbon fiber surface functional group content (%) that group recycling obtains
It is found from table, the graphite state and amorphous state C~C key total amount on carbon fibre precursor surface are 51.1%, I20S2.0H1 Carbon~carbon linkage content slightly rise to 52.8%, I20S2.0H3And I20S2.0H5Then decline, respectively 49.4% He 48.4%.In terms of carbon-oxygen bond, there is sharp fall in C~O key of the carbon fiber recycled, and slippage sorts from large to small Are as follows: H3>H5>H1；Then there is decline by a small margin in the C=O key for the carbon fiber that recycling obtains, in strongly hydrophilic functional group O~C=O On linkage content, the content compared to carbon fibre precursor is zero, and the content of the carbon fiber recycled is very high, and H3>H5>H1.It is above-mentioned Situation shows that carbon fiber experienced a degree of oxidation in removal process, and content of surface oxygen increases, and improves surface-active, And O~C=O key occurs, and greatly improves the chemical bonds ability of carbon fiber Yu inorganic rouge；The carbon fiber obtained from recycling Carbon ratio and functional group content from the point of view of, HNO3When concentration is 1.0g/L, carbon fiber degree of oxidation is too low, works as HNO3Concentration is When 3.0g/L, carbon fiber degree of oxidation is best, increases HNO3Concentration only increases carbon fiber surface C=O key.
7.4XRD
With reference to Figure 18 A and Figure 18 B of attached drawing of the present invention, main presentation I20 series and I40 series are in different temperatures ladder The XRD spectrum of recycled carbon fiber is spent, wherein only one strong diffraction maximum of the XRD spectrum of all recycling carbon fibers, peak position is 2 It near θ=26 °, is mutually retrieved by object, is determined as C, show that, in electrochemistry removal process, carbon fiber surface does not introduce other Crystal structure compound.
It is noted that can further look at discovery from figure, XRD spectrum is in that temperature is higher, and characteristic peak spreads out substantially It is higher to penetrate intensity, the further sharp trend in peak shows that recovered temperature is higher, carbon fiber crystallinity is better, and crystal grain is smaller. Papirer E's studies have shown that carbon fiber surface crystal grain is smaller, the unsaturated C atom at surface corner angle and edge the more, surface Activity is higher, can improve the adhesive property of carbon fiber and resin to a certain extent, and improve the tensile strength of carbon fiber. I20 series carbon fiber is better than I40 series of features peak, and it is smaller to show that low current effect influences the graphite block structure of carbon fiber, It is more advantageous to the mechanical property of recycling carbon fiber.
Example 8: influence of the temperature to electrochemistry recycling carbon fiber
Similar to other chemical reactions, it is suitable anti-that the chemical reaction process of electrochemical process recycling carbon fiber should also be as it Answer condition.The present invention determines the suitable temperature of electrochemistry recovery method of the present invention by following experimental results.Similarly, multiple groups Sample (as shown in following table 6.1) is used in testing for suitable reactions temperature, wherein the current strength being selected be respectively 20mA and 40mA, NaCl concentration are 2.0 (%), HNO3Dosage is 3.0g/L, and temperature gradient is to eliminate the too low extreme temperature (pole of yield It is low, such as 0 DEG C hereinafter, with 100 DEG C of temperatures above) four temperature gradients, totally 6 groups.Sample number is dense by action current, NaCl Degree, catalyst HNO3Concentration and temperature gradient determine jointly, such as sample number " I20S2.0H3T40", first part " I20 " is The electric current for referring to that sample applies is 20mA, second part " S2.0" refer to that NaCl concentration is 2.0% in electrolyte, Part III " H3” Refer to the catalyst HNO added in electrolyte3Concentration is 3.0g/L.Part IV " T40" refer to the temperature of electrolyte in experimentation Degree is maintained at 40 DEG C.Detailed experimental group and experiment parameter are shown in Table 8.1.
The grouping of 8.1 experiment sample of table and parameter
This part Experimentation An electrochemical return period is 4 days, after recycling, and composite material carries out hardness test.Then it goes Except the cement base colloid of composite material, carbon fiber is taken out.The carbon fiber cleaning, drying that obtained recycling obtains, then carry out various surveys Examination.It is detected, the carbon fiber recycled still maintains tow shape, and length is about 100mm, recycles length one with sample substantially It causes, surface illustrates the damage very littles such as oxidation and the corrosion that carbon fiber is subject in removal process rich in gloss.
8.1 Carbon Fiber Reinforced Cement Composites samples and carbon fiber yield
From table 8.2, it can be seen that, Carbon Fiber Reinforced Cement Composites sample is after 4 days return periods, under hardness Very big, far smaller than 9B hardness level, I20S drop2.0H3T75The cohesional failure depth of sample reaches 1.88mm, close to carbon fiber Layer is tieed up, illustrates that temperature plays tremendous influence in Carbon Fiber Reinforced Cement Composites softening, it is short to compensate for return period Influence.Simultaneously from composite material cohesional failure depth it can be found that, temperature is bigger, and the softening degree of composite material is more serious.
8.2 composite material sample hardness of table and cohesional failure depth
Note: the hardness of pencil hardometer is from low to high successively are as follows: and 9B~8B~7B~6B~5B~4B~3B~2B~ 1B~HB~F~H~2H~3H~4H~5H~6H~7H~8H~9H
See from table 8.3 and Figure 12, from low to high trend is presented with the raising of temperature in carbon fiber yield, is T in temperature40 When (40 DEG C), carbon fiber yield is maximum, I20S2.0H3T40Yield is 772mg, reaches the 91.8% of carbon fibre precursor.High temperature Although state only room temperature (T lower return period0, 25 DEG C) half, but the yield of carbon fiber is higher, and reason should be carbon The electrochemical oxidation process time that fiber is subject to is shorter, and degradation is lower, and the lousiness of generation is fewer, thus the amount that recycling obtains It is more.The carbon fiber yield of I20 serial sample is obviously higher than I40 series, especially in hot stage, take out in carbon fiber and Cleaning process discovery, the lousiness of I40 series carbon fiber is more, not only more to be sticked on cement base gel, and a part is with water Stream washes away, and it is more serious to show that high current is deteriorated caused by carbon fiber.
Carbon fiber correlated performance under 8.3 different temperatures gradient condition of table
Note: 1) DB: expression failure mode is inorganic rouge layer stripping damage
2) CB: indicate that failure mode is carbon fiber and inorganic rouge interface delaminating damage
The detection of 8.2 sample voltages
See from Figure 13, each group sample voltage is lower, and the sample voltage difference value very little of different parameters condition shows in height Under the conditions of temperature, the system resistance value of sample is very small.The voltage of all samples is in electrochemistry kept stable return period, I20 Serial sample voltage fluctuation is within 0.15V, and I40 serial sample voltage fluctuation is within 0.1V.The sample of identical temperature condition Voltage is close, T2The voltage of serial sample is minimum, shows that its electric conductivity is very good with this condition, the deterioration journey of carbon fiber It spends very low.
The carbon mono-filaments tensile strength detection that 8.3 recycling obtain
It is found from table 8.4,7 μm of carbon fiber diameter holding is constant, shows the electricity being subject in electrochemistry removal process carbon fiber Chemical oxidation and acid corrosion the effects of lesser extent, carbon fiber surface substantially without lamella peel off.Recycle obtained carbon fiber In, I20S2.0H3T3Monofilament tensile strength be up to 3214MPa, reach the 89.58% of carbon fibre precursor；I40S2.0H3T1's The minimum 2881MPa of tensile strength is the 80.30% of carbon fibre precursor.The filament stretch for the carbon fiber that other recycling obtain is strong Degree is intended to low compared to carbon fibre precursor, and the relationship of more intuitive monofilament tensile strength and temperature gradient is shown in Figure 14.
Recycling carbon fiber tensile strength (ISO11566) under 8.4 different temperatures gradient condition of table
It is obvious that elder generation is presented in the monofilament tensile strength for the carbon fiber that recycling obtains as the temperature increases from Figure 14 Then trend that decline slowly rises always.It may be noted that in room temperature T0Under the conditions of (25 DEG C), the return period of carbon fiber is 8 The effects of it, under hot conditions, shorten to 4 days return period, oxidation and corrosion that carbon fiber is subject to is weaker, therefore damages Relatively small, the tensile strength of carbon fiber wants higher naturally.However, being T in temperature1When (40 DEG C), the stretching of carbon fiber is strong Degree but compares T0When it is low, it should be at this temperature carbon fiber receive certain seed type it is even more serious deterioration damage.I20 series sample This tensile strength is higher than I40 series, and as temperature increases, the two difference is continued to increase, it may be possible under the high temperature conditions, greatly Electric current accelerates the oxidizing reaction rate of sample.
The carbon fiber interface shearing performance evaluation that 8.4 recycling obtain
It can see from table 8.5, in addition to I40S in the carbon fiber recycled2.0H3T2Failure mode be CB, other samples This failure mode is DB.I20S2.0H3T2Interface shear strength be up to 28.45MPa, be carbon fibre precursor 105.02%, there is different degrees of decline compared to carbon fibre precursor in the interface shear strength of other samples.
Recycling carbon fiber interface shear strength under 8.5 different temperatures gradient condition of table
Note: 1) DB: expression failure mode is epoxy resin layer stripping damage
2) CB: indicate that failure mode is carbon fiber and epoxy resin interface stripping damage
It is found from Figure 15, the interface shear strength of the carbon fiber recycled is increased with temperature, occurs falling before then increasing High downward trend again, high temperature sample high shear strength is than room temperature T0Sample, reason may be only with the return period of high temperature sample Room temperature sample half, the surface fine structure degree for being oxidized etching is lower, and roughness is lower related.It can from Figure 16 A and Figure 16 B To see, I20S2.0H3T1And I40S2.0H3T1Destruction interface be smooth inorganic rouge layer, shear strength is lower, respectively 22.78MPa and 23.51MPa is the 84.09% and 86.78% of carbon fibre precursor.See from Figure 16 C and Figure 16 D, I20S2.0H3T2And I40S2.0H3T2Failure mode be respectively DB and CB, destroy interfacial adhesion have it is many acicular elongated inorganic Rouge, these needle-shaped resins have been capable of increasing the surface area destroyed, play the role of similar reinforcing bar Rib Reinforced, machinery is greatly improved and stings With joint efforts, so the shear strength of sample is improved, the 105.02% and 98.74% of carbon fibre precursor is respectively reached.In Figure 16 E In Figure 16 F, I20S2.0H3T3And I40S2.0H3T3Failure mode be DB, inorganic rouge layer destroys, destroy interface can To observe a small amount of needle inorganic rouge, interface shear strength is higher, respectively the 92.69% of carbon fibre precursor and 89.66%.
8.5SEM Scanning Detction
As seen from Figure 17, the carbon fiber recycled is very clean, and cement gel particle, carbon fiber are not adhered in surface Dimension table face does not find the defects of crackle crack and pit, compared to identical parameters sample in room temperature T0Condition lower surface has crackle to split The effects of stitching, showing oxidation and acid corrosion that the carbon fiber that recycling obtains is subject to degree is smaller, and shortening return period can have Effect reduces the deterioration that carbon fiber is subject to, therefore the carbon fiber tensile strength that the recycling under hot conditions obtains is higher.
8.6AFM Scanning Detction
Table 8.6 recycles the roughness of obtained carbon fiber
The AFM test result for recycling obtained carbon fiber is shown in Table 8.6 and Figure 18 respectively.In T1Obtained carbon fiber is recycled to maintain The longitudinal groove structure of column Figure 18 A to Figure 18 D, the oxide etch lesser extent of removal process, carbon fiber surface are shallower, protrusion knot Structure size is probably between 20 μm~50 μm, I20S2.0H3T1And I40S2.0H3T1The roughness being calculated be respectively 134nm and 149nm is not much different with the roughness 144nm of carbon fibre precursor, therefore recycles the interface shear strength of obtained carbon fiber not It is high.When temperature continues to increase, there is deeper longitudinal groove structure in the carbon fiber series surface Figure 18 E to Figure 18 H, I40, and width is more Greatly, I40S2.0H3T2Gather bulge-structure on surface, the size of these bulge-structures probably between 100nm~300nm, I20S2.0H3T2And I40S2.0H3T2Roughness is respectively 168nm and 169nm, and longitudinal groove and bulge-structure improve carbon fiber Mechanical snap power, increasing specific surface area improves wellability, therefore in T2The failure by shear interface of series carbon fiber can be bonding with Acicular resin greatly improves the interface shear strength of carbon fiber.When temperature rises to T3When, from Figure 18 I to Figure 18 L It arrives, the expansion protrusion of larger size occurs in carbon fiber surface, and there are also discontinuous groove structure, I20S2.0H3T3With I40S2.0H3T3Roughness is respectively 184nm and 192nm, these structures increase specific surface area, increases the model of infiltration absorption resin De Huali, however roughness crosses the cementitiousness that conference reduces carbon fiber and resin, and the class formation is unfavorable for mechanical snap Effect, interface shear strength are less high.
8.7XPS Scanning Detction
It is detected, the scanning of the carbon fiber recycled is composed entirely and the narrow spectrum of C1s high-resolution is shown in that Figure 19 A to Figure 19 F, left column are The scanning of sample is composed entirely, and right column are then the narrow spectrum of its corresponding C1s high-resolution and its swarming fitted figure.It can from full spectrogram is scanned It arrives, mainly there is six kinds of peaks, i.e. two main peaks: C (284.6eV) and O (532.0eV) in figure；Four secondary peaks: Si (99.5eV), Cl (199.8eV), Ca (347eV) and N (399.5eV).The surface basic element of carbon fibre precursor is carbon and oxygen, be detected A small amount of silicon, chlorine, calcium and calcium are introducings during the experiment.The carbon fiber surface chemistry member that the recycling of different temperatures gradient obtains Cellulose content situation is shown in Table 8.7.
Table 8.7 recycles obtained carbon fiber surface constituent content (%)
It can be seen that, the carbon fiber recycled compares carbon fibre precursor, and C element content has a degree of from table Decline, and oxygen element content appearance rises by a relatively large margin, from the point of view of carbon ratio, carbon fibre precursor is only 0.2610, and carbon ratio Minimum I20S2.0H3T3Also reach 0.4066, be 1.5 times or more of carbon fibre precursor, illustrate the carbon fiber surface that recycling obtains More oxygen is introduced, greater activity is obtained.In three temperature gradient samples, I20S2.0H3T2Carbon ratio be up to 0.4281, I20S2.0H3T1It is more slightly lower, carbon ratio 0.4252, I20S2.0H3T3It is then minimum, know from experiment above I20S2.0H3T0Carbon ratio be 0.3859, although show return period shorten cause carbon fiber oxidization time to shorten, high temperature Condition makes the oxygen introduction volume of carbon fiber surface bigger instead, is T in temperature2When, carbon fiber surface carbon ratio is maximum, then begins to Decline.In removal process, carbon fiber surface introduces chlorine element, and chlorinity increases with temperature and declined.In addition, I20S2.0H3T2And I20S2.0H3T3Carbon fiber surface also introduces a small amount of nitrogen, silicon and calcium constituent.
According to document and what is carried out research and analyse, using software XPSPeak4.1, by the narrow spectrum foundation of C1s high-resolution Gauss long-range navigation thatch fitting: graphite state C~C (284.4eV), amorphous state C~C is carried out in conjunction with following six kinds of chemical bond peaks can be divided into (284.8eV), C=O (285.5eV), C~O (286.2eV), C~Cl (287.2) and O~C=O (288.4eV).C1s swarming The right column of Fig. 6 .9 are shown in fitting, specifically recycle obtained carbon fiber surface functional group content and are shown in Table 8.8.
Table 8.8 recycles obtained carbon fiber surface functional group content (%)
To see from table, the graphite state and amorphous state C~C key total amount compared to carbon fibre precursor surface are 51.1%, I20S2.0H3T1And I20S2.0H3T2Decline, is 44.9%, and I20S2.0H3T3Then slightly rise to 51.4%；Due to returning There is sharp fall in C~O key of the electrochemical oxidation of receipts process, the carbon fiber recycled；And in C=O key, I20S2.0H3T1Content decline, I20S2.0H3T2And I20S2.0H3T3Content then slightly rises；In strongly hydrophilic group O~C=O key In, the carbon fiber content that the lower recycling of temperature obtains is higher, this is that may be because O~C=O key is easier to give birth at high temperature At carbon dioxide and water[34], the above-mentioned carbon fiber reaction temperature for showing that recycling obtains is lower, and surface oxidation degree is higher, with The chemical bonding ability of inorganic rouge is stronger, however due to I20S2.0H3T1C~Cl linkage content on surface is up to 8.2%, illustrates carbon fiber Dimension receives more serious chlorination, causes tensile strength and interface shear strength to decline, corresponding I20S2.0H3T2With I20S2.0H3T3The chlorine on surface exists not with chemical bonds with adsorbed state.
8.8XRD analysis
Can see from Figure 20 A and Figure 20 B, recycle only one strong diffraction maximum of the XRD spectrum of carbon fiber, peak position 2 θ= It near 26 °, is mutually retrieved by object, is determined as C, shown in electrochemistry removal process, carbon fiber surface does not introduce other crystalline substances Body structural compounds.
Further, it can be seen that the crystallinity of recycling carbon fiber is all poor.H1The diffraction of series recycling carbon fiber Peak intensity is lower, and when concentration of nitric acid increases to 3g/L, diffraction peak intensity increases, and peak becomes more sharper, when concentration of nitric acid after Continuous when increasing to 5g/L, the intensity decline of diffraction maximum, peak portion becomes round and smooth, shows H3The carbon fiber crystallinity of series is relatively Good, too high or too low concentration of nitric acid makes the graphite block structure of carbon fiber be affected what removal process was subject to.
It is noted that continuing to be powered in the experiment recycled above-mentioned, used electrolysis unit can be ability Various electrolytic cells, electrolytic cell etc. known to domain.
As the chemistry mixed in the above-mentioned electrolysis unit of returnable equipped with the recovery catalyst and catalyst that are pre-designed Solution, can effectively invade the cement-based gelling material of the Carbon Fiber Reinforced Cement Composites to be recycled, and break Its bad chemical bond, promotes cement-based gelling material to decompose.The chemical solution includes but is not limited to water, HNO3(nitric acid), liquid Body ethyl alcohol, liquid glycol, various acid solution (including but not limited to H2Si3(metasilicic acid), HCN (hydrogen cyanide), H2C3(carbon Acid), HF (hydrofluoric acid), C3COOH (also makees C2H4O2Acetic acid is called acetic acid), H2S (hydrosulphuric acid), HClO (hypochlorous acid), HNO2It is (sub- Nitric acid), all organic acids, H2S3(sulfurous acid) etc.), various alkaline solutions (including but not limited to potassium hydroxide solution, hydrogen Sodium hydroxide solution etc.), various chloro ion-containing solutions (including but not limited to sodium chloride solution, liquor zinci chloridi etc.).Above-mentionedization The feature for learning liquid is the mixed solution that can be above-mentioned various solution, and the concentration of various solution is 0.001%-99.9%,
According to this preferred embodiment of the invention, during the energization, the carbon fiber reinforced cement base to be recycled is multiple Carbon fibre material in condensation material is connected using the anode of known method and power supply, to ensure that circuit is steady in removal process Fixed operation.The method that the anode of the fibrous material and power supply is attached includes but is not limited to dissolving resin, grinds off resin Deng to expose internal fiber material, convenient for circuit connection.
According to this preferred embodiment of the invention, the cathode material in galvanization is well known conductive material, including but It is not limited to steel, iron, various metals, various forms graphite material.
In the galvanization, current density size be characterized in that under the collective effect of above-mentioned chemical solution, can be with Promote the cement-based gelling material solution in the Carbon Fiber Reinforced Cement Composites to be recycled, while not influencing to recycle carbon The various mechanical properties of fiber, electric conductivity, the adhesive property with organic (epoxy resin) and inorganic (cement base) cementitious material And cycling processability.The size of the current density is according to carbon fiber in the carbon fiber reinforced inorganic (cement base) composite material The surface area size that material is soaked in the electrolyte is calculated, and range is 3333.3~6666.7mA/m2。
In the galvanization, conduction time be characterized in under the collective effect of above-mentioned chemical solution and electric current, can To promote the cement-based gelling material in the Carbon Fiber Reinforced Cement Composites to be recycled to decompose, while not influencing back Receive the various mechanical properties of carbon fiber, electric conductivity, bonding with organic (epoxy resin) and inorganic (cement base) cementitious material Performance and cycling processability.The conduction time is 0.5~200 hour, preferably 2-120 hours, more preferably 4-48 hours.
In the galvanization, resin aging method known to the various industry can be used and accelerate recycling speed, such as is purple Outside line is strengthened, is ultrasound-enhanced, microwave reinforced.
It is described from Carbon Fiber Reinforced Cement Composites recycle carbon fiber method in, reaction temperature be 25 DEG C~ 75 DEG C, preferably 40 DEG C~75 DEG C, more preferably 60 DEG C~75 DEG C.
Pressure in the returnable is adjusted to default size, common with above-mentioned chemical solution, electric current and temperature Under effect, the cement-based gelling material in the Carbon Fiber Reinforced Cement Composites to be recycled is promoted to expand and divide Solution, while not influencing to recycle the various mechanical properties of carbon fiber, electric conductivity, adhesive property and re-workability with resin material Energy.Its pressure limit is 0.5~20 atmospheric pressure, and pressing time is 0.5~200 hour.
In the electrochemistry recovery method, between anode and cathode material distance to recovering effect, recycling speed and recycling at Originally have an impact, preferably 1mm~1000mm, more preferably 20mm~60mm.
In addition, saving after taking out carbon fiber in the electrochemistry recovery method, reproduction can be put into.The taking-up Method is various known methods, including and be not limited to the combination of ultrasound, dry, heating etc. and various methods.
The length for recycling obtained carbon fiber is a key factor of its recycle value.The carbon fiber that recycling is obtained Dimension, is straightened, it can be seen that the length of carbon fiber is about between 80mm~100mm, and the sample recoverer of experimental design Dividing length is 100mm, it is contemplated that the loss of the length existing for the carbon fiber that clip recycles, it is known that being recycled in electrochemistry The length of process carbon fiber is not lost substantially, shows in entire removal process, the damage such as electrochemical oxidation that carbon fiber is subjected to It is very slight.
According to this preferred embodiment of the invention, in the side for recycling carbon fiber from Carbon Fiber Reinforced Cement Composites In method, the electrolyte contains the catalyst B of 1g/L~5g/L, and wherein catalyst B is soluble acid, can be but not limited to It is HNO3.As shown in Fig. 4 and Fig. 6 of Figure of description, different grouping Carbon Fiber Reinforced Cement Composites sample is recycled The amount of the carbon fiber arrived is different, and carbon fiber yield is with HNO3Concentration increase, which is presented, first increases the trend that drops afterwards, HNO3Concentration is When 3g/L, carbon fiber yield is maximum.In HNO3Concentration is in 1g/L grouping, and carbon fiber yield is substantially reduced, and is recycled The monofilament tensile strength of the carbon fiber arrived is with HNO3Concentration increase and it is on a declining curve, in the HNO of 0~3 (g/L)3Concentration ranges, The tensile strength fall of carbon fiber is smaller, the HNO of 3~5 (g/L)3Concentration ranges, the carbon fiber tensile strength recycled Sharply decline.Therefore, HNO3Concentration control it is more excellent at 1~3 (g/L), when being more preferably controlled in 3g/L, can get reason The recovering effect thought.
It is to this hair that those skilled in the art, which would appreciate that the embodiment of the present invention shown in the drawings and described above only, Bright example rather than limit.
It can thus be seen that the object of the invention can be efficiently accomplished sufficiently.It is used to explain the present invention function and structure principle The embodiment is absolutely proved and is described, and the present invention is not limited by based on the change on these embodiment basis. Therefore, the present invention includes all modifications covered within appended claims claimed range and spirit.

Claims (10)

1. a kind of method for recycling high-performance carbon fibre from inorganic coagulation material comprising following step:
(A) carbon fiber reinforced inorganic composite material is placed in electrolyte, wherein the electrolyte contain weight ratio be 0.5%~ The catalyst of 3% NaCl and 1.0g/L~5g/L；；
(B) it is powered to the carbon fiber reinforced inorganic composite material placed in the electrolytic solution, wherein the carbon fiber reinforced inorganic is compound Material is connected with the anode of power supply, and controlling current density is 3333.3~6666.7mA/m2；With
(C) it is powered after reaction 0.5-200 hours, carbon fiber regenerant is taken out from the electrolyte.
2. the method according to claim 1, wherein further comprising following step:
(D) after carbon fiber regenerant surface receptacle, water flow rinse, to remove cement base inorganic glue, wherein pitch of holes be greater than 0.1mm, water flow hydraulic pressure are higher than 0.1MPa, and washing time is no less than 3 seconds.
3. the method according to claim 1, wherein the electrolyte is further containing the catalysis of 1.0g/L~5g/L Agent, wherein the catalyst system is selected from by hydrogen cyanide, carbonic acid, hydrofluoric acid, hydrosulphuric acid, hypochlorous acid, nitrous acid, nitrous acid, metasilicic acid With the group of soluble organic acid composition.
4. according to the method described in claim 2, it is characterized in that, the electrolyte is further containing the catalysis of 1.0g/L~5g/L Agent, wherein the catalyst system is selected from by hydrogen cyanide, carbonic acid, hydrofluoric acid, hydrosulphuric acid, hypochlorous acid, nitrous acid, nitrous acid, metasilicic acid With the group of soluble organic acid composition.
5. according to claim 1 to any method in 4, which is characterized in that reaction temperature is 25 DEG C~75 DEG C.
6. according to the method described in claim 5, it is characterized in that, reaction temperature is 60 DEG C~75 DEG C.
7. the method according to claim 1, wherein the electrolyte contains the solubility that weight ratio is 0.5~3% The catalyst of hydrochloride and 1.0g/L~5g/L, wherein the catalyst system is selected from by hydrogen cyanide, carbonic acid, hydrofluoric acid, hydrosulphuric acid, secondary The group of chloric acid, nitrous acid, nitrous acid, metasilicic acid and soluble organic acid composition, reaction temperature are controlled as 25 DEG C~75 DEG C.
8. the method according to claim 1, wherein the electrolyte contain weight ratio be 0.5%~3% it is solvable Property hydrochloride and 1.0g/L~5g/L catalyst, wherein the catalyst system be selected from by hydrogen cyanide, carbonic acid, hydrofluoric acid, hydrosulphuric acid, The group of hypochlorous acid, nitrous acid, nitrous acid, metasilicic acid and soluble organic acid composition, reaction temperature are controlled as 60 DEG C~75 ℃。
9. a kind of for recycling the electrolyte of high-performance carbon fibre from inorganic coagulation material, which is characterized in that it at least contains:
The soluble-salt hydrochlorate that weight ratio is 0.5%~3%；
The catalyst of 1.0g/L~5g/L, wherein the catalyst system is selected from by hydrogen cyanide, carbonic acid, hydrofluoric acid, hydrosulphuric acid, secondary chlorine The group of acid, nitrous acid, nitrous acid, metasilicic acid and soluble organic acid composition；With
80%~98% water.
10. electrolyte according to claim 9, which is characterized in that preferably comprise the catalyst of 3g/L.
CN201880000082.6A 2018-02-09 2018-02-09 The method of high-performance carbon fibre is recycled from inorganic coagulation material Pending CN109153051A (en)

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