A kind of carbon carbon/rubber composite material preparation method
Technical field:
The invention belongs to rubber wet method mixing technology fields, and in particular to a kind of carbon carbon/rubber composite material preparation method,
Using carbon carbon latex predispersion with wet method rubber compound drying process be combined realize carbon carbon in latex it is evenly dispersed with point
Cloth, the aggregation after anti-blocking carbon dispersion, is made carbon carbon and is evenly distributed and well dispersed, good mechanical performance, comprehensive mechanical property
Carbon carbon/the rubber composite material significantly improved with dynamic mechanical.
Background technology:
With science and technology the sustainable development being constantly progressive with material subject, the material that the mankind use also update and into
Step, high molecular material and its product have captured every field, industry-by-industry and each department in life, fly to space flight greatly
Some component of machine, small to one screw are likely to use high molecular material;Rubber is as a kind of important strategic object
Money, is widely used in the fields such as national economy, new and high technology and defence and military, but since rubbery intensity is low, modulus is low, wear-resisting
Property and fatigue resistance it is poor, without practicability, so most rubber are required for packing strengthening agent.In the prior art, carbon black
It is widely used in rubber product as main reinforcing agent with white carbon, including graphene, carbon nanotube and carbon carbon composite wood
The preparation and application of emerging filler/rubber composite material of material etc. also become research hotspot.
The process of rubber composite material preparation process most critical is to be kneaded, and the essence of compounding procedure is exactly by various compounding agents
It is mixed into raw rubber, the mixing and dispersion process of the process and rubber of the rubber compound of uniform quality with various compounding agents is made;
It can be said that it is first and a most important procedure in rubber product process to be kneaded, the quality of mix quality is straight
Connect the quality, performance and its service life for influencing rubber product;Currently, to mostly use mixer more for the mixing of China's rubber industry
Segmentation mixing method is resulted in the process that mixing process is a continuous heat heating, is anti-due to the high-elastic characteristic of high polymer
Only sizing material incipient scorch destroys the performance of sizing material and achievees the purpose that compounding agent is evenly dispersed, and mixing process has to be repeated, right
The performance of rubber product produces irreversible influence;In order to improve melting efficiency, new mixing method and process layer go out not
Thoroughly, including low-temperature primary method, tandem is kneaded and continuous mixing etc., these new mixing technologies are in melting efficiency and mixing
Upper to have good portfolio effect, still, the dispersion grade of the filler in these mechanically milling technologies cannot reach the journey of setting
Degree, even if extending mixing time, the mixing of sizing material will not be greatly improved.It is preferably kneaded matter in order to obtain
Amount, people attempt, to break the aggregation of filler, to improve in the new energy injection to mixing process such as ultrasonic wave and Solid dry ice
Compounding rubber quality finds that these new technological means only improve the microcosmic dispersion of filler to a certain extent by research
Degree, but with the requirement of high-end rubber product there are still a certain distance, the preparation for carbon carbon/rubber composite material, machine
The technological means that tool is kneaded cannot be satisfied the demand of filler dispersion;Carbon/carbon compound material is carbon fiber and its carbon of fabric enhancing
Matrix composite, have low-density (<2.0g/cm3), high intensity, high ratio modulus, high-termal conductivity, low-expansion coefficient, frictional property
Nowadays the advantages that good and thermal shock resistance of energy is good, dimensional stability is high is in the alternative materials of minority of 1650 DEG C of use above
Material, highest theoretical temperatures are more up to 2600 DEG C, it is considered to be one of most promising high-temperature material.
Currently, the wet method of rubber nano composite material is prepared mainly using chemical method processing brand-new material and latex breast
Nano filling is dispersed in latex by liquid in the way of stirring, then flocculates and wet method rubber compound is made, this method and
Chemical reagent is added in technique, and very big influence is produced on properties of rubber, reduces the quality and service life of rubber product;
Such as the preparation method of wet process mixed natural rubber material disclosed in Chinese patent 201110064299.3, to traditional mixing technology
It is improved, acetic acid flocculation is added in the latex solution produced, glue and dehydration, then the drying in drying box are washed through rubber washing machine
4-6h can be obtained the glue stuff compounding of natural rubber after dry.There is the defect being difficult to avoid that in strong acid flocculation, can not only influence to grasp
Make the health of personnel, etching apparatus, the long time drying after flocculation easy tos produce the sour gas for influencing environment, if by force
Sour do not wash clean clearly can also influence subsequent vulcanization time, and curing time lag can be led to by vulcanizing under acidic environment.Therefore, it researches and develops
A kind of carbon carbon/rubber composite material preparation method improving carbon carbon degree of scatter in wet method mixing process, it is flocculated using anacidity
Method, the reunion after preventing carbon carbon from disperseing shorten the production cycle, improve the performance and intensity of rubber, have very much science and apply valence
Property, it may have good society and application prospect.
Invention content:
It is an object of the invention to overcome disadvantage of the existing technology, solves the carbon carbon difficulty in wet method mixing process and disperse
The problem of with easy reunion, while solving in wet method mixing process by adding properties of rubber caused by acid ingredient flocculation rubber compound
The problems such as variation, R & D design a kind of new wet method mixing method and technique are broken by the rapid temperature of carbon carbon emulsion droplet predispersion
Technology realizes that carbon carbon is evenly dispersed in lotion, reaches the microcosmic degree of scatter of nanoscale of carbon carbon, passes through high temperature expansion drying
Technology realizes that the rapid draing of wet method rubber compound, the microcosmic aggregation of prevention carbon carbon are to prepare high performance wet method rubber compound
High-performance tire, preparing for high-end rubber product provide practicable approach.
It includes preparing rubber master batch mixed liquor, system that carbon carbon/rubber composite material preparation method of the present invention, which obtains technical process,
For rubber master batch and prepare composite material totally three steps:
(1) rubber master batch mixed liquor is prepared:
Carbon carbon composite aqueous solution is prepared first:In temperature it is 25-100 DEG C and work(by carbon carbon composite powder and water
Carbon carbon composite aqueous solution is made in rate ultrasound 15min-12h under conditions of 500-1500W;
Then carbon black slurry is prepared:The water for setting mass fraction and carbon black are mixed, high speed dispersor is used in combination to handle
The black slurry that finely dispersed mass percent concentration is 20-30% is obtained, at omnidirectional planetary ball mill
Reason black slurry 4-6h obtains carbon black slurry;
Finally prepare rubber master batch mixed liquor:Carbon carbon composite aqueous solution and 200g natural emulsions are added in carbon black slurry
The mechanical agitation processing for carrying out 5-30min, obtains rubber master batch mixed liquor, completes the preparation of rubber master batch mixed liquor;
(2), rubber master batch is prepared:The surface temperature of high temperature plate is adjusted to 150 DEG C, the jet velocity of nozzle is adjusted to 15m/s,
The ejection flow of nozzle is adjusted to 3L/h, and the horizontal distance of nozzle distance high temperature plate is adjusted to 100mm, and rubber master batch mixed liquor is from spraying
The emulsion droplet that device is ejected into high temperature plate surface realizes microcosmic dispersion, the black slurry in rubber master batch mixed liquor by explosion and splashing
It is handled by the broken dispersing technology of rapid temperature and makes the moment under the high temperature positice ground effect of high temperature plate of the moisture in black slurry
It evaporates, high temperature plate shows to form rubber master batch, completes the preparation of rubber master batch;
(3) composite material is prepared:Rubber master batch is scraped to be placed on open mill with scraper plate and is plasticated, the mother of sheet is obtained
Sheet rubber master batch is cut into the blocky rubber master batch being sized by glue, will in favor of being kneaded and preventing the excessive damage machine of rubber master batch stress
The antioxidant 4020 of SAD, 1.8g of ZnO, 1.8g of 1.8g and the accelerant CZ of 1.24g are made into small powder, by the initial of mixer
Temperature is adjusted to 90 °, and initial speed is adjusted to 90r/min, and the 2/3,40s of rubber master batch prepared by step (2) is added in mixer
Mixer is added in small powder and remaining 1/3 rubber master batch afterwards, mixed material is obtained, bolt 2s, the temperature rise of mixed material is put forward after 40s
To after 120 °, bolt 2s is carried after the rotating speed of mixer is increased to 100r/min operatings 140s, the rotating speed of mixer is down to 90r/
Min, the temperature rise of mixed material to refining glue 1min after 145 °, the temperature rise of mixed material are obtained to dumping is carried out after 147 °
Total time to rubber compound, mixing is less than 6min, and the S of the rubber compound of 165g, the accelerant CZ of 1.29g and 1.1g is put into gap
It is adjusted to beat triangle bag in the open mill after packet roller 4 times, the rubber compound tabletting after triangle bag will be played at the thickness of setting and in room
16h is stood under warm environment, completes the preparation of composite material.
It is respectively 100,35,5,2,0.7 and 2.25 that carbon carbon/rubber composite material prepared by the present invention, which includes mass fraction,
Natural emulsion, carbon black N330, ZnO, SAD, accelerant CZ and S, the compound derivative material of carbon carbon is variable;Heveatex is Thailand's production
The natural emulsion that mass percent concentration is 60%;White carbon is the white carbon of Qingdao Rhodia Ltd production;ZnO
Additive amount with SAD is the 0.3-2% of natural emulsion quality;Antioxidant 4020, accelerant CZ and S are commercially available technical grade
Product.
Compared with prior art, the present invention being stirred first to filler and the technological means of ultrasonic atomizatio pre-processes to be formed
Then filler slurry uses filler predispersion warm crushing technology suddenly, filler slurry is sprayed filler slurry by gas high pressure
Go out, is ejected into high temp objects surface, heat is broken suddenly for filler emulsion droplet, quick-fried after holding up drop due to the steam cushion on high temperature surface
It is broken, further break the network structure of filler and filler in the blasting process of emulsion droplet, realizes filler in rubber matrix
Twice dispersing, improve the microcosmic dispersion grade of filler, then use high temperature expansion drying technology, will be suddenly warm through filler predispersion
The wet method rubber compound prepared after broken dispersion is placed in moisture flash evapn therein in hot environment, and solidification filler is in rubber-based
Good dispersion in body finally prepares filler/rubber composite material using conventional mixer;Its scientific in principle is reliable, practical letter
Just, preparation efficiency is high, has a extensive future, and use environment is friendly.
Description of the drawings:
Fig. 1 be carbon carbon composite additive amount of the present invention be respectively 0 part, 5 parts and 10 parts carbon carbon/rubber it is compound
Material tire dynamic mechanical correlation curve schematic diagram.
Fig. 2 be carbon carbon composite additive amount of the present invention be respectively 0 part, 5 parts and 10 parts carbon carbon/rubber it is compound
Material tire wet-sliding resistant performance compares column schematic diagram.
Fig. 3 be carbon carbon composite additive amount of the present invention be respectively 0 part, 5 parts and 10 parts carbon carbon/rubber it is compound
Material tire rolling resistance performance comparison column schematic diagram.
Fig. 4 be carbon carbon composite additive amount of the present invention be respectively 0 part, 5 parts and 10 parts carbon carbon/rubber it is compound
The scanning electron microscope (SEM) photograph of material tire (wherein, the additive amount of a is 0 part, and the additive amount of b is 5 parts, and the additive amount of c is 10 parts).
Specific implementation mode:
The present invention is described further by way of example and in conjunction with the accompanying drawings.
Embodiment 1:
Carbon carbon/rubber composite material preparation method that the present embodiment is related to is also referred to as atomization drying method, technical process packet
It includes and prepares rubber master batch mixed liquor, prepare rubber master batch and prepare composite material totally three steps:
(1) rubber master batch mixed liquor is prepared:
Carbon carbon composite aqueous solution is prepared first:In temperature it is 25-100 DEG C and work(by carbon carbon composite powder and water
Carbon carbon composite aqueous solution is made in rate ultrasound 15min-12h under conditions of 500-1500W;
Then carbon black slurry is prepared:The water for setting mass fraction and carbon black are mixed, high speed dispersor is used in combination to handle
The black slurry that finely dispersed mass percent concentration is 20-30% is obtained, at omnidirectional planetary ball mill
Reason black slurry 4-6h obtains carbon black slurry;
Finally prepare rubber master batch mixed liquor:Carbon carbon composite aqueous solution and 200g natural emulsions are added in carbon black slurry
The mechanical agitation processing for carrying out 5-30min, obtains rubber master batch mixed liquor, completes the preparation of rubber master batch mixed liquor;
(2), rubber master batch is prepared:The surface temperature of high temperature plate is adjusted to 150 DEG C, the jet velocity of nozzle is adjusted to 15m/s,
The ejection flow of nozzle is adjusted to 3L/h, and the horizontal distance of nozzle distance high temperature plate is adjusted to 100mm, and rubber master batch mixed liquor is from spraying
The emulsion droplet that device is ejected into high temperature plate surface realizes microcosmic dispersion, the black slurry in rubber master batch mixed liquor by explosion and splashing
It is handled by the broken dispersing technology of rapid temperature and makes the moment under the high temperature positice ground effect of high temperature plate of the moisture in black slurry
It evaporates, high temperature plate shows to form rubber master batch, completes the preparation of rubber master batch;
The evaporation curable of moisture in the black slurry microcosmic dispersion of carbon black and natural emulsion, it is therefore prevented that carbon black
Coacervation process, the alkaline components volatilization in natural emulsion under high temperature action, avoids sizing material quality caused by sour flucculation process
The problem of variation;
(3) composite material is prepared:Rubber master batch is scraped to be placed on open mill with scraper plate and is plasticated, the mother of sheet is obtained
Sheet rubber master batch is cut into the blocky rubber master batch being sized by glue, will in favor of being kneaded and preventing the excessive damage machine of rubber master batch stress
The ZnO (zinc oxide) of 1.8g, SAD (stearic acid), the antioxidant 4020 of 1.8g and the accelerant CZ of 1.24g of 1.8g are made into small
Material, 90 ° are adjusted to by the initial temperature of mixer, and initial speed is adjusted to 90r/min, and step (2) is added in mixer and makes
Mixer is added in small powder and remaining 1/3 rubber master batch after 2/3,40s of standby rubber master batch, mixed material is obtained, bolt 2s is carried after 40s,
The temperature rise of mixed material carries bolt 2s to after 120 ° after the rotating speed of mixer is increased to 100r/min operatings 140s, will be close
The rotating speed of mill is down to 90r/min, and the temperature rise of mixed material to refining glue 1min after 145 °, the temperature rise of mixed material arrives
Dumping is carried out after 147 °, obtains rubber compound, the total time of mixing is less than 6min, by the rubber compound of 165g, the accelerant CZ of 1.29g
It is put into the open mill after gap is adjusted to packet roller with the S (sulphur) of 1.1g and beats triangle bag 4 times, the mixing glue laminated after triangle bag will be beaten
Piece at setting thickness and stand 16h under room temperature environment, complete the preparation of composite material.
It is respectively 100,35,5,2,0.7 and 2.25 that carbon carbon/rubber composite material manufactured in the present embodiment, which includes mass fraction,
Natural emulsion, carbon black N330, ZnO, SAD, accelerant CZ and S, the compound derivative material of carbon carbon is variable;Heveatex produces for Thailand
Mass percent concentration be 60% natural emulsion;White carbon is the white carbon of Qingdao Rhodia Ltd production;
The additive amount of ZnO and SAD is the 0.3-2% of natural emulsion quality;Antioxidant 4020, accelerant CZ and S are commercially available work
Industry grade product.
It is respectively that 0 part, 5 parts and 10 parts carbon carbon is compound when carbon carbon/rubber composite material testing inspection manufactured in the present embodiment
Material, which is added in carbon carbon/rubber composite material tire, tests tire, and the dynamic mechanical of tire is using Germany
The DMA (full-automatic Dynamic Mechanical Analyzer) of GABO companies is tested, and test condition is as follows:Frequency is 10HZ, and static strain is
5%, static stress 70N, dynamic strain 0.25%, dynamic stress 60N, temperature range are -65 to 65 DEG C, temperature rise rate
For 2 DEG C/min, using stretch mode;Carbon carbon composite additive amount is respectively 0 part, 5 parts and 10 parts of carbon carbon/rubber composite wood
Material wheel tire dynamic mechanical correlation curve is as shown in Figure 1:The rolling resistance of tire, anti-slippery, wear-resisting property three, which exist, to be write
Devil's triangle relation of name improves any one of three performance, and how together will necessarily influence both remaining has the tendency that variation,
Tri- performances of Shi Tigao are always the objective of the struggle of people, are formulated for fixed, and good calendering process then can be a certain in promotion
While kind or two kinds of performances so that the downward trend of another performance minimizes;The dynamic mechanical of tread mix
Can there are apparent correlativity, the wet-sliding resistant performance of tire to characterize using 0 DEG C of Tan δ with the performance of finished tire,
Tan δ are bigger, and wet-sliding resistant performance is better, and rolling resistance performance is using 60 DEG C of Tan δ characterizations, and Tan δ are smaller, and rolling resistance is lower:
Carbon carbon composite additive amount is respectively 0 part, 5 parts and 10 parts of carbon carbon/rubber composite material tire wet-sliding resistant performance comparison column
Shape figure is as shown in Fig. 2, carbon carbon composite additive amount is respectively 0 part, 5 parts and 10 parts of carbon carbon/rubber composite material tire rolling
Performance comparison block diagram is hindered as shown in figure 3, being learnt by Fig. 2 and 3, and with the increase of carbon carbon composite number, carbon carbon/rubber is multiple
The anti-slippery ability of condensation material tire significantly improves, and in the case where carbon carbon composite additive amount is 5 parts, carbon carbon/rubber is multiple
The rolling resistance of condensation material tire increases few;Carbon carbon composite additive amount is respectively that 0 part, 5 parts and 10 parts of carbon carbon/rubber is compound
The scanning electron microscope (SEM) photograph of material tire is as shown in Figure 4, wherein the additive amount of a is 0 part, and the additive amount of b is 5 parts, and the additive amount of c is
10 parts, the brittle failure face for carbon carbon/rubber composite material tire that carbon carbon composite additive amount is 0 part is more regular, only exists one
A little rough textures, this is because caused by firmly uneven in brittle failure, carbon that carbon carbon composite additive amount is 5 parts
The surface of carbon/rubber composite material tire is relatively smooth, the dispersion of carbon fiber in carbon carbon composite it is relatively uniform and
Orientation is more regular, can preferably be combined with rubber matrix, and the mechanical property for enhancing carbon carbon/rubber composite material tire is contributed to
Can, carbon carbon composite additive amount be 10 parts carbon carbon/rubber composite material tire with carbon carbon composite dosage increasing
More, there is agglomeration in carbon fiber in carbon carbon composite, has also appeared some cellular eyelets on brittle failure surface, this is carbon
Pyrolytic carbon in carbon composite produces aggregation, and in brittle failure, particle falls off from section generates gap, secondly, on brittle failure surface
Some circular holes are showed, the reason is that causing binding force small because carbon fiber and rubber matrix binding ability decline during brittle failure
In the breaking tenacity of carbon fiber, and then carbon fiber pulls out generation circular hole from brittle failure face;Carbon carbon composite additive amount is respectively 0
Part, carbon carbon/rubber composite materials of 5 parts and 10 parts is to the influence such as following table of natural rubber (NR) composite material heat conductivility:
For composite material, thermal conductivity takes mainly certainly in the collective effect of rubber and conductive filler, and filler is at it
In occupy leading role, interaction has been begun with as loading increases, between filler grain, has been formd in system similar
Netted and chain form, referred to as heat conduction network chain, as seen from the above table, with increasing for carbon carbon composite additive amount, naturally
The trend risen is presented in the thermal conductivity of rubber composite material, and reason has two:First, pyrolytic carbon itself has in carbon carbon composite
Excellent electric conductivity, second is that increasing with carbon carbon composite additive amount, pyrolytic carbon and carbon fiber, which contact with each other, becomes more, carbon
More heat conduction network chain is formed between carbon composite and carbon carbon composite, to form passage of heat, natural rubber is compound
The thermal conductivity of material is significantly promoted.