CN103214860A - Smoke-suppression compound modified asphalt and preparation method thereof - Google Patents
Smoke-suppression compound modified asphalt and preparation method thereof Download PDFInfo
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Abstract
The invention discloses smoke-suppression compound modified asphalt and a preparation method of the smoke-suppression compound modified asphalt. The smoke-suppression compound modified asphalt comprises the following components: 92.3% of No. 70 Grade A matrix asphalt, 1% of expanded graphite, 2.7% of SBS4402 (styrene-butadiene-styrene) modifier, and 4% of epoxidized soybean oil. According to the smoke-suppression compound modified asphalt and the preparation method, high-performance and environment-friendly compound smoke-suppression asphalt based on hot-mix modified asphalt and a modified asphalt mixture is developed by combining practical situations of an expressway pavement, in particular a long and large tunnel asphalt pavement in China, and by deeply and systematically researching modified asphalt smoke generation, smoke suppression and flame retarding mechanisms under high temperature conditions for technical problems of smoke suppression and flame retarding during construction of a high-performance hot-mix asphalt pavement; the emission of asphalt smoke and harmful gas at a high temperature is reduced under the condition of ensuring the pavement performance and the quality of the asphalt pavement; the hazard level of asphalt mixture combustion in case of pavement fire is reduced; and energy conservation, emission reduction and environmental protection of road construction are facilitated.
Description
Technical field
The present invention relates to the modified asphalt technology field, in particular a kind of cigarette composite modified asphalt and preparation method thereof that presses down.
Background technology
Current, construction temperature height, the heat that pavement performance is good are mixed hot petrolize road surface and are still technology and the pattern that high grade highway pavement is mated formation and extensively adopted, polymers of excellent properties Modified Bitumen Pavement wherein, because construction temperature is higher, cause the harmful smog emission contaminate environment of pitch then even more serious, the injury that human body is caused is bigger.Though to the poisonous characteristic and the existing comparatively deep understanding of hazardness of glance coal, the industrial method of administering glance coal at present all mainly concentrates in the pitch production of oil, chemical industry, the course of processing both at home and abroad.The method of the glance coal of petrochemical iy produced department processing both at home and abroad has following several usually:
1) combustion method
Combustion method is exactly that hydro carbons in the flue gas and flammable charcoal dirt are burnt, and generates H2O and CO2.When temperature is controlled between 800 ℃～1000 ℃, the oxygen supply abundance, combustion time, it is very complete that hydrocarbons is that incendivity gets about 0.5s, and other impurity also can thoroughly burn.This method is handled energy consumption under low concentration pitch smoke too high, and expense is high and uneconomical.When temperature of combustion was too high simultaneously, the part glance coal formed particle easily, discharged with flue gas with dust form, formed secondary pollution.The U.S. and Canada have just brought into use combustion method as far back as 1972, Japan and Germany also adopt method in succession, and China begins to adopt in a eighties of last century introduction nineties day present technique.
2) electric fishing method
Utilize the principle and the electrostatic dust collection principle of static capture glance coal basic identical, be after glance coal enters electric field, in the time of between by negative electrode and anode, by means of corona discharge, make the glance coal particulate charged and drive, reach pitch smog purpose separated from the gas to pole plate.Be current the most widely used tar capturing device, according to foreign data, accounting at present the glance coal that 85% roasting produces in the world all is to adopt the electric fishing method to administer.The shortcoming of this method is: one-time investment is big, temperature requirement to cigarette is higher, generally is controlled at 70 ℃～80 ℃, and the dry type electric fishing is almost nil to the gaseous component collection efficiency, though and wet type electric fishing device can trapping gaseous pitch, has increased the secondary pollution that sewage disposal brings.
3) WATER-WASHING METHOD
WATER-WASHING METHOD is to wash earlier with clear water, again the method for asphalt flue gas purifying.Germany KHO company is exactly the induced-draft fan that the flue gas of bituminous cigarette is extracted into an inner water spray, makes it preliminary cleaning. and then enter gas separator.This separator has many intensive " S " type steel sheets of being made by stainless steel arranged side by side, flue gas flows from top to bottom, water is spray from top to bottom also, cause on the long-pending stainless plate of large contact surface the foam layer is arranged, coal-tar middle oil droplet of flue gas and mixture are attached to face down on the foam in the groove that flows to the bottom, overflow is at aggregate groove again.In aggregate groove, need to add specialist additive. the surface tension of tar-charcoal dirt compound particles is increased, because charcoal dirt particulate is than great and heavy people's bottom land in the mixture, precipitation and going out, tar drips and then floats over the aggregate groove surface, scrapes off and reaches the purification purpose with oil wiper.
4) absorption method
It is little that absorption method adopts coke grain, slag, rhombspar, flyash or talcum powder etc. to have a particle diameter, porous, and material than bigger serface is arranged as sorbent material, glance coal is carried out physical adsorption.The selected of concrete sorbent material should be selected fixed bed for use and carry bed etc. in conjunction with the source situation of nature of production and sorbent material, can decide according to condition such as the character of the concentration of glance coal, sorbent material, purification standard.The sorbent material that this method adopts need not be regenerated, and can be directly used in production, and this method technology is simple, the purification efficiency height, and less investment, systematic running cost is low, non-secondary pollution, but systemic resistance is bigger.
5) absorption process
Absorption process adopts organic class I liquid Is such as gasoline, diesel oil to make sorbent material, makes the gas mixture of glance coal fully contact and wash with the absorption agent adverse current, removes poisonous component, reaches the purpose of purification.These class methods are used for coke-oven plant, coating factory and petroleum chemical plant more.This method equipment is simple, easy to maintenance, and systemic resistance is little, and energy consumption is low, but inflammable, and purification efficiency is not high, also is difficult for adopting.
From the above, these punishment technology and method need fixed equipment and technology mostly, be applicable to that asphalt smoke concentration is quite high, and production process comparatively fixed occasion and factory etc., be not suitable for the inhibition that construction process of asphalt pavement medium pitch cigarette inorganization discharges situation.
At present, it mainly is from reducing the angle of construction temperature that domestic and international transportation industry presses down cigarette to asphalt, promptly based on warm mix asphalt technologies, by reducing the discharging that construction temperature reduces glance coal.This technology at first originates from Europe [i], and subsequently, states such as Japan, Europe, Australia begin to use in a large number Warm-Mix Bitumen Mixture, and the U.S. began to introduce temperature in 2003 and mixes technology.At present, mix working mechanism according to temperature abroad and mix the different of technical approach, will press down the cigarette Warm-Mix Bitumen Mixture and be divided into following three classes with the realization temperature:
1) asphalt foaming method
The ultimate principle of this method be compound mix and stir in the process or pitch enter mix and stir the pot (tube) import water before, bring out asphalt foaming, the asphalt membrane structure that forms by foaming realizes under the lesser temps to wrapping of gathering materials, to reduce the asphalt service temperature.The green twin-roll of WAM-Foam, Aspha-Min, LEA and Astec etc. all can be included into this type of.According to the difference of foaming method, can be divided into the trickle foaming of the process of mixing and stirring again and mix and stir two types of preceding mechanical foamings.But because the asphalt foaming method relates to fairly large equipment and batching plant transformation and technical know-how, The Application of Technology is not extensive.
2) agglutinate viscosity reduction method
The construction working of hot-mix asphalt mixture depends on the bituminous high-temperature viscosity, and its non-deformability and the pitch viscosity under summer road surface use temperature condition is relevant.Be added with organic additive, make the asphalt high-temperature viscosity degradation but simultaneously under the summer temp viscosity do not change even improve, thereby the realization temperature mix, this technological line is the most representative to be SASOBIT.
The problem of pitch viscosity reduction technology maximum is from the contradiction of viscosity reduction additive amount, consumption is difficult to reach the obvious cooling effect less, and consumption increases, though the cooling-down effect that can obtain, but excessive to the change of agglutinate material character, mixture performance is tended to produce adverse influence.
3) tensio-active agent
The characteristics of tensio-active agent technology are that a spot of surfactant additive (0.5%～1%), water and heated bitumen acting in conjunction in the process of mixing and stirring realize merging each other by the powerful dispersive ability of mixing and stirring.Tensio-active agent is enriched in residual minim water and bituminous interface, and three's acting in conjunction temporarily forms comparatively stable structure moisture film in agglutinate inside.Because the moisture film lubrication is temperature influence not, when temperature descended, the moisture film lubrication can largely be offset the effect that asphalt viscosity increases, thereby the realization temperature is mixed effect.The main products of this technology is Evotherm at present.
In the temperature technology of mixing is that each side has separately, ins and outs still are in the secret stage, the cost height, complex manufacturing, so technology popularization is difficulty comparatively, simultaneously, the Warm-Mix Bitumen Mixture performance is because construction temperature is lower, influence pitch and wrapping of gathering materials to a certain extent, whether performance of asphalt mixture can reach the hot-mix asphalt mixture level, how its long-term pavement performance is still needed and will further be observed and study, some temperature is mixed Technology Need and is improved equipment or add new preparation of construction in addition, this has increased investment with regard to corresponding, and operational procedure is relative complex also, if gather materials oven dry fully, lower production temperature can cause the possibility of compound damage by water evil to increase, and influences performance of asphalt mixture.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of cigarette composite modified asphalt and preparation method thereof that presses down at the deficiencies in the prior art.
Technical scheme of the present invention is as follows:
A kind of preparation method who presses down the cigarette composite modified asphalt, material is formed and ratio is: No. 70 A grade matrix pitches 92.3%, expanded graphite 1%, SBS 4402 properties-correcting agent 2.7%, epoxy soybean oil 4%; The preparation method is: the A1 swelling stage: at first matrix pitch is heated to 160～170 ℃, constant temperature, in proportion SBS4402 properties-correcting agent is incorporated in the matrix pitch that has heated, rotating speed with 300～400 commentaries on classics/min stirs at a slow speed, the thickness that swims in asphalt surface by range estimation SBS4402 properties-correcting agent is adjusted swelling time, and swelling time remains 60-70min;
The A2 shear stage: just expanded graphite and epoxy soybean oil slowly evenly mix the SBS modifying asphalt simultaneously, carry out high speed shear processing to pressing down the cigarette composite modified asphalt, and rotating speed is 4000 commentaries on classics/min, and temperature is 180～185 ℃; Shear time is 60-70min;
The A3 etap: after high speed shear is finished,, adopt high-power adjustable speed automatic stirrer to stir frequently simultaneously with the slow speed of revolution with pressing down the following 60min of placement of constant temperature that the cigarette composite modified asphalt is placed on 180 ℃.
The present invention is in conjunction with China's express highway pavement tunnel sheet pavement reality of especially growing up; at smoke suppression in high-performance hot asphalt (modifying asphalt) asphalt pavement construction and flame-retarded technology problem; by going deep into; modifying asphalt smog produces and smoke-inhibiting flame retardant mechanism under the systematic research hot conditions; the high-performance of modifying asphalt and modified asphalt mixture is mixed in exploitation based on heat; the compound cigarette pitch that presses down of environment-friendly type; under the condition of guaranteeing bituminous pavement pavement performance and quality; pitch smog and discharge of harmful gases when reducing high temperature; asphalt incendiary hazard level when reducing the road surface presence of fire; promote road construction energy-saving and emission-reduction and environment protection; realization hommization construction; the protection people's life security; for building resource-conserving; environmentally friendly traffic provides technical support, has important significance for theories and using value.
Description of drawings
Fig. 1 is a sample A infrared spectra; A-former state expanded graphite;
Fig. 2 is a sample B infrared spectra, the expanded graphite that sample B-trieline soaked;
Fig. 3 is a sample C infrared spectra, and sample C-adopts the trieline expanded graphite that wash-out goes out from expanded graphite modified pitch;
Fig. 4 is that sample A, B, C infrared spectra compare;
Fig. 5 is a sample D infrared spectrum, the expanded graphite that sample D-kerosene soaked;
Fig. 6 is a sample E infrared spectra, and sample E-adopts the kerosene expanded graphite that wash-out goes out from expanded graphite modified pitch;
Fig. 7 is that sample A, D, E infrared spectra compare;
Fig. 8 is sample A, B, C, D, the comparison of E infrared spectra;
Fig. 9 is graphite XRD figure spectrum (θ is the Bragg diffraction angle);
Figure 10 is expanded graphite XRD figure spectrum;
Figure 11 is middle extra large 70# pitch XRD figure spectrum;
Figure 12 is western petrochemical industry 70# pitch XRD figure spectrum;
Figure 13 is 2% an expanded graphite pitch XRD figure spectrum;
Figure 14 is 10% an expanded graphite pitch XRD figure spectrum;
Figure 15 is the calculating XRD figure spectrum of anthracene;
Figure 16 is the SEM pattern (550X) of sample A, sample A-former state expanded graphite
Figure 17 is the SEM pattern (500X) of sample B, the expanded graphite that sample B-trieline soaked;
Figure 18 is the SEM pattern (3.00KX) of sample B;
Figure 19 is the SEM pattern (500X) of sample C; Sample C-adopts the trieline expanded graphite that wash-out goes out from expanded graphite modified pitch
Figure 20 is the SEM pattern (1.00KX) (1) of sample C;
Figure 21 is the SEM pattern (1.00KX) (2) of sample C;
Figure 22 is the SEM pattern (5.00KX) of sample C;
Figure 23 is the TG-DSC of sample B, C;
Figure 24 is the smoke density grade.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in detail.
Embodiment 1
A kind of cigarette composite modified asphalt that presses down, when heat is mixed the asphalt pavement construction of heat shop, guaranteeing that pavement performance satisfies under the prerequisite of existing asphalt pavement construction technical specifications, compare with matrix pitch, pitch smog and discharge of harmful gases in the time of can effectively reducing high temperature, asphalt incendiary hazard level when reducing the road surface presence of fire.Promote the environment protection of road construction joint, realize the hommization construction, the protection people's life security.
Table 1 presses down the cigarette composite modified asphalt material and forms
Table 2 presses down the requirement of cigarette composite modified asphalt reference technique
(proposing) based on the JTG F40-2004 of the Ministry of Communications asphalt highway construction technique normalizing
The prepared in laboratory method:
1. swelling stage: at first extra large 70# matrix pitch among 1.5～2.0kg is heated to 160～170 ℃, constant temperature, SBS4402 properties-correcting agent (Balin Branch Corp. SINOPEC) is incorporated in the middle extra large 70# matrix pitch (China National Offshore Oil Corporation (CNOOC)) that has heated by table 1 design proportion, adopt 1 high-power adjustable speed automatic stirrer to stir at a slow speed with the rotating speed of 300～400 commentaries on classics/min, the thickness that swims in asphalt surface by range estimation SBS4402 properties-correcting agent is adjusted swelling time, and swelling time remains 60min; This stage mainly is to make SBS4402 properties-correcting agent at high temperature quicken to do thermal motion, allows the molecular chain of SBS4402 properties-correcting agent can unrestricted flow, segment launches, and promotes SBS4402 properties-correcting agent to disperse in matrix pitch;
2. shear stage: just expanded graphite (Shanghai shines graphite company limited) and epoxy soybean oil (Tianjin recovery fine chemistry industry institute) slowly evenly mix the SBS modifying asphalt simultaneously, adopt high-speed shearing machine to carry out high speed shear processing to pressing down the cigarette composite modified asphalt, rotating speed is 4000 commentaries on classics/min, and temperature is 180～185 ℃; For preventing ageing of asphalt, can stir at a slow speed with the slow speed of revolution by available aside high-power adjustable speed automatic stirrer; Shear time is 60min;
3. etap: after high speed shear is finished, the following 60min of placement of constant temperature that the cigarette composite modified asphalt is placed on 180 ℃ will be pressed down, adopt high-power adjustable speed automatic stirrer to stir frequently simultaneously with the slow speed of revolution, this stage mainly is for expanded graphite and SBS4402 properties-correcting agent evenly, stably are scattered in the pitch, also make the recovery of SBS4402 properties-correcting agent segment, grafting, in pitch, form reticulated structure.
4. preparation is finished presses down cigarette composite modified asphalt standby (table 3, table 4) to be measured.
Table 3
Table 4
| Asphalt type | Penetration degree (0.1mm) | 5 ℃ of ductilities (cm) | Softening temperature (℃) |
| Press down the cigarette composite modified asphalt | 72.7 | 26.0 | 55.3 |
Because expanded graphite has the premium properties and the characteristics of very easily adsorbing oils, organic molecule and lyophobic dust, can not produce secondary pollution again, and is harmless, therefore, in waste water, waste gas pollution control and treatment field, obtained using widely and research.SBS properties-correcting agent is a kind of thermoplastic elastomer, with vinylbenzene and 1-3 divinyl is monomer, the end of each butadiene block chain all connects a styrene block, several divinyl segment couplings then form linear or star block copolymer, it has the performance of rubber and plastics concurrently, can improve performances such as bituminous high temperature, low temperature, antifatigue preferably simultaneously, be the most widely used properties-correcting agent in the bitumen for road use modification at present.
The present invention adopts the scientific experiment method of design based on " homogeneous design ", select SBS4402 properties-correcting agent and expanded graphite to press down the important materials of cigarette composite modified asphalt as exploitation, with control glance coal burst size and assurance agglutinate performance is target, with epoxy soybean oil as the environment-friendly type softening agent, finally develop based on expanded graphite, SBS properties-correcting agent and epoxy soybean oil composite modified press down the cigarette composite modified asphalt, it is proportional to have proposed the material best group; And proved that the cigarette composite modified asphalt of developing that presses down has good glance coal rejection, satisfies the requirement of bituminous cements pavement performance.
Infrared spectra test (FT-IR), X-ray diffraction test (XRD), scanning electronic microscope (SEM) test and comprehensive heat are analyzed (TG-DSC) and be studies confirm that expansible black lead mixes pitch, mix in the process in hot conditions and long-time heat, produce demi-inflation, the graphite synusia is mainly by pitch light component swelling, and cleavage is the thin layer gauffer, and specific surface increases, adsorptive capacity increases; The light component such as polycyclic aromatic hydrocarbons that discharged in the pitch are adsorbed on the expanded graphite surface or part is inserted between the expanded graphite synusia and the forming core crystal growth, and the constraint of Van der Waals force and lattice energy has effectively suppressed its effusion of mixing in the process in heat and discharged.
On microtexture, expanded graphite and graphite belong to same crystallographic system, are by being made of numerous graphite microcrystals, having identical unit cell parameters; On macroscopic view, because expanded graphite is loose porous and be imbued with flexibility, therefore, expanded graphite is stronger than graphite to the adsorptive power of polycyclic aromatic hydrocarbons and long chain alkane.The present invention adopts Fourier to change infrared spectra test (FT-IR), X-ray diffraction test (XRD), scanning electron microscope (SEM) test and comprehensive thermal analyzer (TG-DSC) test to wait the microanalysis methods to pressing down the analysis and the research that mechanism has been carried out system that improves of cigarette composite modified asphalt inhibition glance coal release.
2.1 test sample preparation
1. infrared spectra test, scanning electron microscopy test and comprehensive thermal analysis test specimen preparation
The infrared spectra test, in electronic scanning microscopic test and the comprehensive thermal analysis test, the sample that is used to study has 5 kinds:
1) sample A: former state expanded graphite; The preparation method is as follows:
Accurately take by weighing the former state graphite of certain mass, behind 180 ℃ of heat tracing 3h, standby behind the cooling drying;
2) sample B: the expanded graphite that trieline soaked; The preparation method is as follows:
Start the low speed automatic stirrer, expanded graphite divided evenly mix in the trieline 2～3 times, mix finish after, start low speed automatic stirrer and high speed shear mulser (rotating speed 4 000r/min) simultaneously, stir 1h, with filter paper and funnel expanded graphite is filtered, after the expanded graphite drying that leaches, behind 180 ℃ of heat tracing 3h, standby behind the cooling drying.
3) sample C: adopt the trieline expanded graphite that wash-out goes out from expanded graphite modified pitch; The preparation method is as follows:
(1) in container, adds the 500g matrix pitch, be heated to 120 ℃ of constant temperature, the complete heat of matrix pitch is melted; (2) start the low speed automatic stirrer, in matrix pitch, the 25g expanded graphite divided in the middle of 2～3 even doped matrix pitch; (3) after expanded graphite mixes and finishes, slowly be warming up to 180 ℃, start low speed automatic stirrer and high speed shear mulser (rotating speed 4 000r/min) simultaneously, stir 1h, stirring at low speed 2h makes expanded graphite modified pitch again; (4) behind the expanded graphite modified pitch naturally cooling that preparation is finished, adopt trieline to clean, modifying asphalt is filtered (wash-out) with filter paper and funnel, after the expanded graphite drying that leaches, standby;
4) sample D: the expanded graphite that kerosene soaked; Preparation method and sample B are identical, and just solvent has been changed to kerosene by trieline;
5) sample E: adopt the kerosene expanded graphite that wash-out goes out from expanded graphite modified pitch; Preparation method and sample C are identical, and just clean-out system has been changed to expanded graphite by trieline;
Trieline, kerosene are excellent solvent and extraction agent, be widely used in the asphalt extraction test in highway system, be used for thorough separate bitumen and mineral aggregate as solvent, this paper adopts trieline, kerosene that the expanded graphite in the expanded graphite modified pitch is filtered out, the expanded graphite that soaked with former state expanded graphite, trieline, the expanded graphite pitch that kerosene soaked are done reference respectively, press down the research of cigarette mechanism.
2. X-ray diffraction (XRD) test sample preparation
The diffraction experiment sample comprises:
1) pure former state graphite:
Accurately take by weighing the former state graphite of certain mass, dry back is standby;
2) the pure expanded graphite after heating:
Accurately take by weighing the former state graphite of certain mass, behind 180 ℃ of heat tracing 4h, standby behind the cooling drying;
3) expanded graphite and the bituminous blend that extracts in the expanded graphite pitch (expanded graphite volume 2% is mixed outward);
4) expanded graphite and the bituminous blend that extracts in the expanded graphite pitch (expanded graphite volume 10% is mixed outward);
5) 2 kinds of No. 70 matrix pitches:
The middle extra large 70# pitch that adopts in test is, the western petrochemical industry 70# pitch of adding is as comparison.Directly sample preparation after pitch is heated to 110 ℃.
The preparation method of expanded graphite and bituminous blend sample is: the expanded graphite and the middle sea base matter pitch that will design volume are even at 110 ℃ of stirring 60min thorough mixing, (preceding 2h stirs 1 time every 1h in 180 ℃ of insulation 3h, back 1 hour for leaving standstill, make the expanded graphite precipitation), make the abundant swelling of graphite, topple over while hot and upper strata pitch, only keep the more precipitation of lower floor's graphite, adopt thin stainless steel filtering net filtering and sampling, the compressing tablet sample preparation;
2.2 infrared spectra (FT-IR) is analyzed
The Fourier infrared spectrograph Spectrum 100 that adopts U.S. PerkinElmer company to produce, the sample preparation of KBr pressed disc method, wavelength region 400～4000cm
-1, scanning times is 3 times, and sample A, B, C, D, E are tested, the infrared spectra image that obtains sample is seen Fig. 1～shown in Figure 8:
In former state expanded graphite infrared spectrogram (Fig. 1), at high frequency region 3400cm
-1Near absorption peak belongs to water molecules O-H stretching vibration peak, 3200cm
-1Near slightly Long Feng be graphite oxide hydroxyl O-H stretching vibration peak.3000-3700cm
-1The spectrum peak widthization, reason is that the sample water absorbability is stronger, the water molecules association causes.2 930,2 850cm
-1Near the position absorption peak is corresponding CH respectively
2Unsymmetrically and symmetrical stretching vibration.
Intermediate frequency zone 1 740
-1(seeing arrow indication among Fig. 1) more weak absorption peak is the C=O stretching vibration of graphite flake layer edge carbonyl.1 639cm
-1Locate corresponding O-H flexural vibration absorption peak.1580cm
-1Belong to the C=C key that forms with sp2 hydridization between the carbon atom and adjacent carbons in the graphite flake layer structure.1399cm
-1C-H symmetric vibration peak for stable hydrocarbon.1 200～1100cm
-1About be the stretching vibration peak of C-O-C, C-O-H.In addition, because graphite has certain infrared attenuating performance, so some is mixed and disorderly and not obvious for the absorption peak in the infrared spectrogram.
Fig. 2 (the expanded graphite infrared spectra that trieline soaked), Fig. 3 (the expanded graphite infrared spectra that adopts trieline wash-out from expanded graphite modified pitch to go out) compare with Fig. 1 (former state expanded graphite infrared spectra), at 3 400cm
-1The O-H stretching vibration peak has the part blue shift, wherein 2346cm in Fig. 2
-1Absorption peak has appearred in the place, near 3 000cm
-1Near absorption peak is strengthened to some extent, and is particularly comparatively obvious in Fig. 3, at 2 918cm
-1, 2 854cm
-1Tell two spikes, be the C-H stretching vibration peak of stable hydrocarbon
Fig. 5 (the expanded graphite infrared spectra that kerosene soaked), Fig. 6 (the expanded graphite infrared spectra that adopts kerosene wash-out from expanded graphite modified pitch to go out) compare with Fig. 1 (former state expanded graphite infrared spectra), also have extremely similarly situation, at 3 400cm
-1The part blue shift appears in the O-H stretching vibration peak, near 3000cm
-1Near absorption peak is strengthened to some extent, and is particularly comparatively obvious in Fig. 6, at 2 918cm
-1, 2 848cm
-1Tell two spikes, be the C-H stretching vibration peak of stable hydrocarbon.Through bituminous-treated expanded graphite intermediate frequency zone 1740
-1(seeing arrow indication among Fig. 1) more weak absorption peak grow in Fig. 6 shows the aggravation of graphite oxidation degree.
Above research and analysis prove, the test-results that adopts different solvents to obtain has consistence, promptly pass through trieline, after kerosene extracts expanded graphite modified bituminous brute force, still there is hydrocarbons in the expanded graphite residue, can produce stronger absorption when this has proved expanded graphite and asphalt grouting, the lightweight component in the pitch is adsorbed in expanded graphite surface or the interlayer structure, thereby reach the effect that presses down cigarette.
2.3 X-ray diffraction (XRD) is analyzed
Adopt day LabX XRD-6000 type X-ray diffractometer of island proper Tianjin (Shimadzu) company production to carry out the X-ray diffraction test, voltage, current stability: ± 0.03%, radiator tube voltage 40kV, tube current 30mA, 2 °～50 ° of diffraction angle scopes, the Cu target, continuous recording scanning, 4 °/min of sweep velocity.
According to the data that the XRD diffraction experiment obtains, Prague (Bragg) equation 2dsin θ=(λ is the X ray wavelength to n λ in employing; N is any positive integer, claims diffraction progression again; θ is for plunderring the angle, i.e. the complementary angle of input angle) can calculation sample spacing d, be used for x ray structure analysis; Each sample XRD figure spectrum is as Fig. 9～shown in Figure 14:
Fig. 9, Figure 10 are respectively the XRD figure of graphite and expanded graphite sample, and two figure are being highest peak to occur about 26.6 ° at 2 θ all; Figure 11, Figure 12 are the XRD figure of middle extra large 70# matrix pitch that adopts in the research and the western petrochemical industry 70# matrix pitch sample that is used to compare, two figure peak position difference are very little, the amorphous peak is obvious, and it is about 19 ° that highest peak is positioned at 2 θ, is speculated as part sheet bituminous matter near orderly stacked structure; Peak position 2 θ are about 9 ° and 2 θ are that all there is small and weak diffraction peak in two kinds of pitches about 29 °.Show that the pitch principal phase is a non-crystalline state, but have the crystallisate of trace that what be speculated as bituminous matter or crystallizable wax piles up part in order, but still can not confirm.
Figure 13, Figure 14 are respectively the XRD figure of mixing the sample of 2% and 10% expansible black lead, at first visible is that diffraction peak strengthens significantly, except that 2 θ are graphite diffraction peak about 26.6 °, 2 θ in the former matrix pitch are that 9 °, 19 °, 29 ° three peaks significantly strengthen, the conclusion that can draw is: after the graphite of ordering mixes pitch, produced the heterogeneous nucleation effect, make in the pitch to climb near orderly component and be born in the capable nucleus growth of graphite surface, the part increase of ordered crystalline strengthens diffraction in the sample; Two-dimension plane structure based on graphite, the component that crystallization increases in the pitch should be the plane ring-type polycyclic aromatic hydrocarbons similar to graphite-structure, comprise regular relatively colloid of part-structure and bituminous matter synusia, the ordering part-structure of these increases is regular inadequately, thereby pile up loose, 9 ° of left and right sides peak positions (promptly than megacryst identity distance direction, d
001=0.906nm) produced stronger peak value to increase.
For proving conclusively 9.8 ° of 2 θ ≈, 19 °, the source at 29 ° of three peaks, introduce the Theoretical Calculation XRD diffraction peak of anthracene molecular crystal, see shown in Figure 15, anthracene is a kind of condensed-nuclei aromatics, its three strong diffraction peaks are respectively 9 ° of peak positions, 19 °, about 29 °, just in time with Figure 13, among Figure 14 9 °, 19 °, three peaks of 29 ° are identical substantially, and it is completely different with the diffraction peak (the 2 θ angles at the strong peak of diffraction mainly are distributed in about 18 °～25 °) of saturated alkane (paraffin), this explanation is under the nucleogenesis of graphite, in possibility crystalline paraffin and two species of condensed-nuclei aromatics, the species that actual crystallization goes out are condensed-nuclei aromatics in the pitch.
By Fig. 9, Figure 10 as seen, the d of expanded graphite and graphite
0012 θ of the characteristic peak correspondence of crystal face are 26.6 °, and (2d sin θ=n λ) can calculate d by Bragg equation
001Spacing is respectively 0.34nm, by Figure 13, Figure 14 as seen, after adding expanded graphite, bituminous XRD spectra and raw material expanded graphite are very different: particularly in 9.8 ° of diffraction peaks of locating of 2 θ ≈, calculate according to Bragg equation (2d sin θ=n λ), this part lamella graphite spacing is about 0.9nm behind the intercalation, this explanation may exist part asphaltene molecule chain to enter the expanded graphite interlayer, enlarged interlamellar spacing, can insert the sheet interlayer of expanded graphite if can prove the component in the pitch, form the nanostructure of intercal type, the expanded graphite that adding then more can be described at high temperature has the intensive adsorptive power to lightweight component in the pitch, therefore, next step need will adopt other microanalysis methods to do further research.
In addition, contrast Figure 13, the XRD figure spectrum of two different expanded graphite volumes of Figure 14, the graphite peaks that obviously visible peak position is about 26.9 ° is powerful little relevant with the expanded graphite volume, 2% expanded graphite volume is to 9 ° of bituminous, 19 °, the enhancing at 29 ° of three peaks is more obvious than 10% expanded graphite volume, can infer when the graphite volume is higher, because the nucleator specific surface area increases severely, the certain crystallizable species of content are adsorbed between expanded graphite sheet surfaces or interposed layer, limited behind the forming core owing to content, crystal can not be grown up and be caused diffraction peak to descend by force, therefore, add the structure that 2% expanded graphite is easier to form intercal type.
The XRD analysis proof is mixed expanded graphite can make the crystallization phases in the pitch increase, because deleterious volatilizable component is based on polycyclic aromatic hydrocarbons in the pitch, its structure is similar to the two-dimensional layer chip architecture of graphite, after mixing expanded graphite, polycyclic aromatic hydrocarbons can pile up to climb in order is born in graphite surface, after forming crystal, cause intermolecular reactive force to increase, and the restrained possibility of expanded graphite interlayer is inserted in existence, therefore, unordered release to asphalt component produces stronger restraining effect, promptly suppressed based on polycyclic aromatic hydrocarbons the gasification of the harmful volatilizable component of pitch volatilize.
2.4 scanning electronic microscope (SEM) is analyzed
The KYKY 2800B type scanning electron microscope (resolving power: 4.5nm that adopts BeiJing ZhongKe instrument limited-liability company of section to produce, magnification: 15X～250 000X, acceleration voltage: 0.1kV～30kV), with magnifications such as 0.2K, 0.5K, 1.2K, 3K, 5K, 10K, as reference sample, sample C (adopt trieline the expanded graphite that wash-out goes out from expanded graphite modified pitch) is carried out the scanning electron microscope experimental study, the image of collection is seen Figure 16～shown in Figure 22 with sample A (former state expanded graphite), sample B (expanded graphite that trieline cleaned):
Contrast Figure 16, Figure 17, Figure 18 and Figure 19～Figure 22 are as seen, object of reference sample A (former state expanded graphite), sample B (expanded graphite that trieline soaked) are obvious with sample C (expanded graphite that adopts trieline to clean out from expanded graphite modified pitch) pattern difference, sample B is at process trieline wash-out, experience 180 ℃ again, after 3h cures, be the stacked in layers structure, can clear resolution cleavage layer, bed thickness is bigger, compare with sample A, the laminate structure of expanded graphite does not change, and proves that the cleaning of trieline does not exert an influence to its structure.
Sample C is the expanded graphite sample that cleans out from pitch by trieline, then is that rhythmo structure is loose.The visible graphite of Figure 21 edge part is loose and still have part to keep thicker laminated structure; Figure 22 is the part of loose part; Figure 19 and Figure 20 are complete loose part, and the graphite synusia has been the tulle shape and fold curls, and which floor whether graphite synusia thickness estimation between tens of layers, wherein exist single-layer graphene film to remain further to be studied and checking at.Can infer in addition, may have same thin layer graphite in the eluted pitch, also have single-layer graphene film.
Loose, the fold mechanism of expanded graphite lamella is in pitch: light component in the pitch such as aromatic hydrocarbons, naphthenic hydrocarbon and fractional saturation hydrocarbons, the similar expanded graphite of chemical structure had swelling action, in 180 ℃ of experience, 3h mixing process, the expansible black lead demi-inflation, the pitch light component has at first diffused between the graphite synusia in the moment of expanding, there is model ylid bloom action between each component of unfolded graphite synusia and bituminous and produces absorption, what stop the expanded graphite synusia piles up reunion again, thereby the expanded graphite synusia begins to launch loose from the edge.When the expanded graphite synusia was thin, because result of random thermal motion produces fold, after trichloroethylene solvent cleaned sampling, synusia was reunited to a certain extent again, but the fold part has kept original state substantially.
Because the expansion of graphite synusia, the specific surface area of graphite further increases, and absorption and further enhancing of crystallization nucleation (seeing XRD analysis) effect to polycyclic aromatic hydrocarbons have restricted the release of harmful polycyclic aromatic hydrocarbons in the process of mixing and stirring and overflowed.The conclusion that X-ray diffraction (XRD) analysis of experiments obtains has been confirmed in research.
2.5 comprehensive heat is analyzed (TG-DSC) and is analyzed
Material be heated or process of cooling in, when reaching a certain temperature, tend to melt, solidify, physics or chemical transformation such as crystal conversion, decomposition, chemical combination, absorption, desorption, and be attended by the change of enthalpy, thereby the generation heat effect, it shows as between material and the environment (sample and reference substance) temperature head.Comprehensive thermal analysis system is combined as a whole thermogravimetric analysis TG and differential scanning calorimetric DSC exactly, is utilizing same sample to obtain thermogravimetric and differential thermal information synchronously in once measuring.Determine a kind of heat analysis method of material physicochemical property.This method is subjected to physics or chemical transformation in the thermal process by measuring material, inquire into composition, structural transformation and the chemical reaction of material, the calcining system of expert evidence and definite product, measure thermodynamical coordinate (as, specific heat capacity and heat content etc.) and degree of crystallinity, judgement material thermostability, volatile component carried out the research of quantitative analysis and reaction kinetics aspect etc.Factors such as it can be eliminated and weigh, sample homogeneity, temperature correspondence are to the influence of test, better than independent TG and DTA/DSC curve correspondence, more help to differentiate the pairing materializing procedure of heat effect (as distinguishing melting peak, peak crystallization, phase transformation peak and decomposition peak, oxidation peak etc.), more help the accurate calculating of reaction enthalpy, the information of more exosyndrome material thermal property can be provided.This paper adopts the simultaneous thermal analysis method to press down cigarette in performance from energy variation angle investigation expanded graphite and does the time spent, the micro-variations of its internal composition, phase structure in temperature changing process.
Prepare sample by aforementioned requirement, the comprehensive thermal analyzer of the STA449C (temperature measurement range :-120～1650 ℃ that adopts Germany anti-speeding (NETZSCH) company to produce, the specific heat measurement temperature range: room temperature-1400 ℃, the specific heat measurement scope: 0.1-5.0J/gK), temperature rise rate is 10 ℃/min; , sample C (adopting the trieline expanded graphite that wash-out goes out from expanded graphite modified pitch) is tested and analyzes and researches as with reference to sample with sample B (expanded graphite that trieline soaked), comprehensive hot analytical results is seen shown in Figure 23:
Analyze Figure 23 as can be known, the thermal weight loss Tg of sample C is shown as 21.09%, and the thermal weight loss Tg that is higher than the sample B of reference is 17.27%; Exothermic peak in the DSC curve of sample C almost disappears, and visible obviously exothermic peak in the DSC curve of sample B is positioned near 340 ℃.
Because adopting starting material is expansible black lead, about 400 ℃ of its maximum swelling temperature.May there be a spot of expansion reaction in sample B when curing for 180 ℃, obviously not complete expansion, and near the exothermic peak in the DSC curve of sample B 340 ℃ is graphite expansion and the heat release of following oxidizing reaction; Exothermic peak disappears substantially in the DSC curve of sample C, shows the thermopositive reaction that there is no obvious expansion oxidation.In view of the above deducibility sample E 180 ℃ with pitch mixing process in, swelling agent with oxidation activity spreads to pitch, and with pitch oxidizing reaction (be similar to bituminous short term thermal aging) has taken place, and because oxygenizement causes pitch to produce deterioration by oxidation, cause expanded graphite modified bituminous low temperature brittleness to increase, cause the reduction of bitumen ductility after the modification.Whether under different hot conditionss, this type of variation all can take place in expanded graphite modified pitch, and can adopt other method of modifying and material not to allow swelling agent in pitch, spread with oxidation activity, the deterioration of pitch low-temperature performance after the prevention modification, increase the low temperature strain that presses down the cigarette composite modified asphalt mixture, all be worth further checking and continue research.
From the TG curve, the value that sample C weightlessness exceeds object of reference sample B weightlessness is 3.82%, and this part is the asphalt component that is adsorbed, and may comprise polycyclic aromatic hydrocarbons, reach bituminous matter and colloid.Initial weightlessness is about 220 ℃, is mainly the desorption of residual solvent from graphite surface; The weightlessness that is positioned near sample B 280 ℃ is that the swelling agent gasification is weightless, and apparently higher than sample C, corresponding DSC exothermic peak is positioned at 340 ℃, is because the temperature compensation that the 10K/min heat-up rate causes lags behind.Be higher than 300 ℃ of asphalt component pyrolysis of adsorbing for graphite later on, so temperature is higher than the weightlessness of sample C after 370 ℃ apparently higher than object of reference sample B.The contrast of the TG curve of two samples is proof also: one since the swelling agent of expansible black lead in pitch the part diffusion consume, cause the sample C heat release of in thermoanalytical pyroprocess, almost not expanding, DSC does not have obvious exothermic peak; Its two because the demi-inflation of expansible black lead in pitch increased specific surface area, and adsorbed asphalt component, cause its TG weightlessness to be higher than reference sample, this has also confirmed the conclusion that the SEM morphology analysis obtains.
2.6 microscopic test is analyzed conclusion
The result that comprehensive FT-IR, XRD, 4 kinds of study on characterization of SEM, TG-DSC are analyzed, as can be known, expansible black lead mixes pitch, under 180 ℃ hot conditions, long-time heat is mixed in the process, produces demi-inflation, and the graphite synusia is mainly by pitch light component swelling, and cleavage is the thin layer gauffer, and specific surface increases, adsorptive capacity increases; Asphalt components such as polycyclic aromatic hydrocarbons are adsorbed on the expanded graphite surface or part is inserted between the expanded graphite synusia and the forming core crystal growth, and the constraint of Van der Waals force and lattice energy has effectively suppressed its effusion of mixing in the process in heat and discharged; The oxidisability swelling agent of expansible black lead can diffuse in the pitch in the process of mixing and stirring, make pitch oxidized to a certain extent (wearing out), cause the plasticity of modifying asphalt to weaken, show as the modifying asphalt ductility and reduce, and may influence the modifying asphalt softening temperature, it is raise to some extent.
Above-mentioned microcosmic Mechanism Analysis research provides theoretical foundation for disclosing the smoke suppressing that presses down the cigarette composite modified asphalt, for follow-up the systematic study that presses down cigarette composite modified asphalt agglutinate and compound is laid a good foundation.
Adopt the test method of combination of dynamic and static to carry out comprehensively systematically research with performance that presses down the cigarette composite modified asphalt mixture and kinetic characteristic to pressing down the cigarette composite modified asphalt under the differing temps, proof presses down the every performance of cigarette composite modified asphalt and is better than matrix pitch, and is approaching with the SBS modifying asphalt.Data are more: see Appendix " pressing down cigarette composite modified asphalt and mixture performance data analysis "
With matrix pitch, SBS modifying asphalt as the research reference, do not have the constraint combustion test and the constraint combustion test studies have shown that by test of agglutinate oxygen concn combustion test, smoke density and compound, press down cigarette composite modified asphalt and asphalt and have good flame retardancy; When judging presence of fire, but the destruction that cigarette composite modified asphalt pavement structure is subjected to is little, can bring into play the effect of blocking-up bituminous pavement incendiary.
When bituminous pavement runs into the road fire, pitch can produce the mixed firing phenomenon with combustible material (as the big petrol that leaks), cause polycyclic aromatic hydrocarbons organism such as anthracene in the pitch, phenanthrene, pyrene to discharge, very harmful to human body, particularly in air-tight environment such as tunnel, when the traffic accident fire took place, pitch burnt and produces a large amount of obnoxious flavoures if can not get timely discharging, not only can cause great physiology injury to the related personnel, even can threaten personnel safety.And adopt antiflaming asphalt mixture can effectively shorten the flame time, reduce the thermolysis of pitch in combustion processes, thereby reduce the generation of obnoxious flavour, the protection people's life security.By to the flame retardant properties test that presses down cigarette composite modified asphalt and asphalt with to the analysis of fire retardant mechanism, prove exploitation but the cigarette composite modified asphalt has flame retardant properties preferably.
2.7 the oxygen concn combustion test is analyzed
At present, China's GB mainly concentrates on materials such as plastics, glass fibre, rubber, textiles and insulating liquid about the testing standard of oxygen index, the every profession and trade standard is variant slightly at aspects such as test material preparation, test conditions and experimental data processing, but the principle and the method basically identical that adopt, all be under certain oxygen nitrogen concentration, to light sample, observe combustion phenomena, record sustained combustion time or sample quantity combusted compare with prescribed value again.It is generally acknowledged that when OI is an inflammable material less than 21% the time, OI was a combustible matl at 21%～27% o'clock, OI was greater than 27% o'clock, and material can be from horizontal blanking in burning.Using for reference GB T 2406.2-2009 " plastics are measured the burning behavior second section with oxygen index method: the room temperature experiment " limiting oxygen index(LOI) (OI) method in the research estimates in the flame retardant properties under the different oxygen concentrations pressing down the cigarette composite modified asphalt.
Because bituminous character differs greatly with general textiles, fiber, plastic or other material, even increasing oxygen concn, still be difficult to light pitch at normal temperatures, therefore, must make certain adjustment to the test method in the existing rules, could finish the oxygen concn combustion test that presses down the cigarette composite modified asphalt smoothly.Test is spun on the M606B digital display limiting oxygen index determination instrument on homemade mountain and is carried out, and the asphalt sample fixed mass is 3g, and the dry cotton yarn that adopts the 0.6g quality evenly spreads upon asphalt sample on the cotton yarn as carcass, at normal temperatures, controls different oxygen concentrations and tests.3 kinds of asphalt sample are 19% to begin to light pitch from primary oxygen concentration, and the pilot-gas flow is 9.3L/min, and concrete data are shown in Table 5:
Table 5 pitch combustion time
Analyze above data as can be known, common matrix pitch can just fire when oxygen concn 19%, just can burn the long period when oxygen concn 27%, does not therefore improve oxygen concn again and proceeds test; The SBS modifying asphalt then reaches at 40% o'clock at oxygen concn and could just fire, more need oxygen concn is brought up to ability combustion just in 45% o'clock and press down the cigarette composite modified asphalt, simultaneously, in 40%～85% oxygen concn scope, obviously be less than the SBS modifying asphalt combustion time of pressing down the cigarette composite modified asphalt,, can think far below matrix pitch combustion time, compare with matrix pitch and SBS modifying asphalt, press down the cigarette composite modified asphalt and have good flame retardancy.
2.8 the glance coal density test is analyzed
The test of material of construction smoke density is by meeting " burning of GB/T 8627--2007 material of construction or the smoke density test method of decomposing " requirement, be under standard test condition, measure the test method of material of construction static smoke-producing amount under the test conditions of burning or decomposition by the loss of optical throughput in the testing experiment smoke box.Its principle is by measuring solid dust in the flue gas that material combustion produces reflection of light to be caused the loss of optical throughput, and SDR estimates smoke-producing amount with the smoke density grade.The smoke density grade has been represented the total smoke-producing amount in (0～4) min, and the smoke density grade is high more, represents the material producing smoke amount big more.Do reference with SBS modifying asphalt and plain asphalt, adopt material smoke density test evaluation to press down the cigarette composite modified asphalt may discharge cigarette under burning and decomposition condition degree, test is finished on the Z801 building materials smoke density determinator that the imitative Instr Ltd. of Qingdao Mount produces, data are seen shown in Figure 24, Figure 24 shows, the smoke density grade that presses down the cigarette composite modified asphalt mixture is between SBS modifying asphalt smoke density grade and plain asphalt compound smoke density grade, but need to prove, according to regulation and stipulation, in the test, adopt the propane flame of the lighter for ignition generation of 276kPa to light measured material, and the pressure of lighting the propane flame that presses down the cigarette asphalt must be higher than standard pressure and could be lighted, this side light press down the cigarette composite modified asphalt flame retardant resistance be higher than SBS modifying asphalt and 70# matrix pitch.
2.9 there is not the analysis of constraint combustion test
Vehicle is presence of fire in road, all with liquid fuel catch fire relevant, thereby liquid fuel is very easily by the spark ignition presence of fire that produces when getting into an accident.By in the laboratory situation of liquid fuel combustion initiation fire being simulated, and then research presses down the flame retardant properties of cigarette composite modified asphalt mixture for the road fire.Concrete testing sequence is as follows: 1. will press down cigarette composite modified asphalt mixture, matrix pitch compound, SBS modified asphalt mixture and prepare 2 groups respectively, totally 6 groups of standard marshal pieces; 2. in 3 kinds of compounds, respectively get 1 group of marshal piece, carry out combustion simulation test, test specimen is taken by weighing quality after, put into and take out behind the 93# gasoline 10s and light test specimen, after horizontal blanking, note combustion time at test specimen flame.Test specimen after the burning is put into 60 ℃ baking oven 5h dry and take by weighing quality, and measure mass loss; 3. marshal piece and unburned marshal piece after the burning are carried out Marshall stability test.Data are shown in Table 6:
Table 6 does not have constraint combustion test data
Analytical table 6 data retrain in the combustion test in nothing as can be known, and the combustion time of pressing down the cigarette composite modified asphalt mixture is the shortest, and the mass loss minimum illustrates that the flame retardant properties that presses down the cigarette composite modified asphalt is better than matrix pitch and SBS modifying asphalt; But mass loss, the Marshall stability difference and little of 3 kinds of asphalts before and after burning, explanation is not having the constraint combustion test, because it is less to add amount of gasoline, the cause of heat rapid diffusion, test specimen can not reach the temperature of combustion of asphalt and cause compound perfect combustion, burning does not cause the asphalt structure deteriorate, and this has bigger difference with the bituminous concrete pavement incendiary practical situation with certain intensity and certain space structural level.Therefore, designed the constraint combustion test, further research presses down the flame retardant properties of cigarette composite modified asphalt.
2.10 constraint combustion test analysis
Marshal piece is placed in the environmental cabinet keeps 20 ℃, 2h takes out, keep all specimen test initial temperature unanimities, then test specimen is contained in the diameter 30cm container (constraint condition), effect of contraction when simulating the burning of actual road surface around the combustion zone, still adopt the test method of directly adding gasoline combustion, add 100ml gasoline every 1min, design adds 10 times continuously, the total consumption of gasoline is 1000ml, in the process of the test: 1. measure the test specimen surface combustion temperature, measure the test specimen surface temperature during when fray-out of flame every 2min; 2. the test specimen configuration of surface changes in the special survey combustion processes, and the time when occurring caving in phenomenon with test specimen simultaneously, is measured test specimen surface temperature when caving in as sustained combustion time (off-test condition); 3. measure test specimen burning front and back quality change, the calculated mass rate of loss.Testing data is shown in Table 7:
Table 7 constraint combustion test data
Test shows that along with the rising of temperature of combustion, test specimen is softening gradually, and asphalt can lose structural strength because of softening after the stagnation point that reaches a high temperature, cave in.In the test, 3 kinds of asphalts all do not reach the total consumption of design gasoline and the phenomenon of caving in promptly occurred, but but the combustion processes of cigarette composite modified asphalt mixture test specimen has following characteristics:
1. before test specimen caved in, the sustained combustion time was the longest, and than the long 70s of matrix pitch compound test specimen, than the long 40s of SBS modified asphalt mixture test specimen, proving needs the longer structure deteriorate that just can cause compound combustion time;
Surface temperature was the highest when 2. test specimen caved in, and is higher 16.2 ℃ than matrix pitch compound test specimen, higher 12.2 ℃ than SBS modified asphalt mixture test specimen, and proving needs higher temperature of combustion just can cause the structure deteriorate that presses down the cigarette composite modified asphalt mixture;
When 3. test specimen caves in, the gasoline consumption is maximum, used 200ml gasoline than matrix pitch compound test specimen more, used 100ml gasoline than SBS modified asphalt mixture test specimen more, proving needs more high temperature heat just can cause the structure deteriorate that presses down the cigarette composite modified asphalt mixture.
When 4. burning finishes, the mass loss minimum, mass loss rate is littler by 19.2% than matrix pitch compound test specimen, and is littler by 12.1% than SBS modified asphalt mixture test specimen, proves under the equal combustion conditions, presses down the destruction minimum that cigarette composite modified asphalt mixture structure is subjected to.
More than analyze explanation, compare with matrix pitch, SBS modifying asphalt, the cigarette composite modified asphalt that presses down of exploitation has good flame retardancy, when the presence of fire of road surface, has the effect of the bituminous pavement of delay incendiary.
Should be understood that, for those of ordinary skills, can be improved according to the above description or conversion, and all these improvement and conversion all should belong to the protection domain of claims of the present invention.
Claims (2)
1. a preparation method who presses down the cigarette composite modified asphalt is characterized in that, material is formed and ratio is: No. 70 A grade matrix pitches 92.3%, expanded graphite 1%, SBS 4402 properties-correcting agent 2.7%, epoxy soybean oil 4%; The preparation method is: the A1 swelling stage: at first matrix pitch is heated to 160～170 ℃, constant temperature, in proportion SBS4402 properties-correcting agent is incorporated in the matrix pitch that has heated, rotating speed with 300～400 commentaries on classics/min stirs at a slow speed, the thickness that swims in asphalt surface by range estimation SBS4402 properties-correcting agent is adjusted swelling time, and swelling time remains 60-70min;
The A2 shear stage: just expanded graphite and epoxy soybean oil slowly evenly mix the SBS modifying asphalt simultaneously, carry out high speed shear processing to pressing down the cigarette composite modified asphalt, and rotating speed is 4000 commentaries on classics/min, and temperature is 180～185 ℃; Shear time is 60-70min;
The A3 etap: after high speed shear is finished,, adopt high-power adjustable speed automatic stirrer to stir frequently simultaneously with the slow speed of revolution with pressing down the following 60min of placement of constant temperature that the cigarette composite modified asphalt is placed on 180 ℃.
2. preparation method according to claim 1 preparation press down the cigarette composite modified asphalt.
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| CN113720703A (en) * | 2021-09-15 | 2021-11-30 | 南京林业大学 | Method for researching mechanism of graphene for enhancing mechanical properties of asphalt |
| CN113848130A (en) * | 2021-09-15 | 2021-12-28 | 南京林业大学 | Method for researching mechanism of improving asphalt toughness by graphene |
| CN114507451A (en) * | 2022-03-29 | 2022-05-17 | 邯郸市交通运输局公路工程管理处 | VOCs composite inhibition type asphalt and preparation method thereof |
| CN114507451B (en) * | 2022-03-29 | 2022-11-29 | 邯郸市交通运输局公路工程管理处 | VOCs composite inhibition type asphalt and preparation method thereof |
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