CN107236155A - A kind of natural rubber chalcopyrite thermoelectric composite material and preparation method thereof - Google Patents

A kind of natural rubber chalcopyrite thermoelectric composite material and preparation method thereof Download PDF

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Publication number
CN107236155A
CN107236155A CN201710480768.7A CN201710480768A CN107236155A CN 107236155 A CN107236155 A CN 107236155A CN 201710480768 A CN201710480768 A CN 201710480768A CN 107236155 A CN107236155 A CN 107236155A
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natural rubber
chalcopyrite
composite material
thermoelectric composite
thermoelectric
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CN107236155B (en
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高佳华
张泽朋
申俊峰
彭山泖
庄官政
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China University of Geosciences Beijing
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China University of Geosciences Beijing
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L7/00Compositions of natural rubber
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C35/00Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
    • B29C35/02Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/30Sulfur-, selenium- or tellurium-containing compounds
    • C08K2003/3009Sulfides
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/02Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/03Polymer mixtures characterised by other features containing three or more polymers in a blend

Abstract

The invention discloses a kind of natural rubber chalcopyrite thermoelectric composite material and preparation method thereof, the preparation method is included after chalcopyrite is fully dried, it is compound with natural rubber according to a certain percentage, by the step, obtained natural rubber chalcopyrite thermoelectric composite material such as plasticating, kneading and vulcanize.This preparation method operating condition is simple and easy to control, raw material sources are extensive, it is with low cost, be conducive to the popularization of industrialization, obtained thermoelectric composite material, certain thermoelectric field can be inspired under certain temperature difference condition, thermoelectricity capability is excellent, suitably prepare the thermoelectric material of the other fields such as health care, medical thermoelectricity.

Description

A kind of natural rubber-chalcopyrite thermoelectric composite material and preparation method thereof
Technical field
The present invention relates to thermoelectric composite material field, more particularly to a kind of natural rubber-chalcopyrite thermoelectric composite material and Its preparation method.
Background technology
Thermoelectric material is a kind of can to realize the functional material that heat energy and electric energy are directly mutually converted, also known as thermoelectric material Material, is a kind of environment-friendly material of great wide application prospect.In recent years, with the increasingly in short supply and environment pressure of natural resources Power is continued to increase, and thermoelectric material is increasingly becoming the study hotspot of field of energy source materials.
Pyroelectricity refers to the powered property of semiconductor type MI heater, the general principle of mineral pyroelectricity be using metal or The pyroelectric effect that semiconductor mineral is produced under temperature difference condition.
It is generally believed that nature intrinsic semiconductor pyroelectricity is few for number, the pyroelecthc properties of most mineral are mainly Due to existing in mineral lattice caused by impurity element or lattice defect.Specifically refer to:Because impurity (is particularly transiens metal Ion) and fault of construction presence so that the structural order of nonideality is occurred in that inside mineral crystal, can also regard part as The non-grid system that particle (ion or atom of composition crystal) occurs sorts or grid system distorts, and (natural minerals crystal structure lacks Fall into, there is or crystallize after formation that radioactive particle radiation is caused around it when can be initial crystallization).
The most common non-grid system defect in the micro- domain of crystal is vacant, displacement and calking.When these defects are in wire or face In the presence of shape, as dislocation defects.In fact, the crystal boundary of generally existing is also a kind of planar defect in crystal.
Due to the presence of drawbacks described above, crystals partial charge is directly resulted in unbalance or there is potential removable electric charge (electronics or hole), also directly results in local be between the particle that non-grid system sorts in unstable high energy chemical combination shape State (because by contrast, the interior energy of ideal crystal is minimum).Therefore, the presence of defect to be provided with crystal potentially Removable mobile carriers (electronics or hole).This potential removable mobile carriers, swash once running into energy (heat, light, electricity, magnetic etc.) Hair can be activated, and then the realization movement under the driving of energy field.The essence of pyroelecthc properties is that heat energy has activated carrier, Carrier displacement under the driving of gradient temperature, and then show thermoelectric force (or electric current).
Chalcopyrite is a kind of reserves most abundant primary copper and iron sulfide mineral, accounts for copper reserves known to the world 70%, many secondary copper ores are all by it changes, often containing micro gold, silver etc..Its crystal phase, to rare, is tetrahedron Shape, in irregular granular or compact massive more than aggregate.Chalcopyrite is a kind of more typical copper mineral, mainly hydrothermal process and The product of contact metasomatism, can often form the mineral deposit of tool certain scale, place of production throughout world various regions.
Chalcopyrite has potential removable mobile carriers due to the presence of crystal defect, in its crystal, once run into heat, The energy excitations such as light, electricity, magnetic are to be activated, the generation thermoelectric force under the driving of gradient temperature, therefore, chalcopyrite tool There is excellent thermoelectricity capability.But at present, the primary raw material for being mainly used for industrially being used as copper metallurgy of chalcopyrite, its pyroelectricity Can it not be used widely.
The content of the invention
For the thermoelectricity capability of development and application chalcopyrite, the thermoelectricity as the other field such as health care, medical is made Material, the present invention is studied with keen determination, is as a result found:It is combined using a certain proportion of chalcopyrite and natural rubber, passes through modeling The steps such as refining, mixing and vulcanization, can prepare that pliability is good and that the thermoelectricity of thermoelectrical potential can be inspired under certain temperature difference is compound Material.This preparation method raw material sources is extensively, with low cost, and operating condition is simple and low to the demand of production equipment, so that complete Into the present invention.
In particular it is object of the present invention to provide following aspect:
In a first aspect, the present invention provides a kind of preparation method of natural rubber-chalcopyrite thermoelectric composite material, including it is following Step:
1), natural rubber is plasticated;
2) additive, is added into the system of step 1, is kneaded;
3) chalcopyrite and softening agent, are added into the system of step 2, continues to knead;
4) sulphur, is added into the system of step 3, is vulcanized, natural rubber-chalcopyrite thermoelectric composite material is made.
Second aspect, the present invention is also provided a kind of natural rubber-chalcopyrite thermoelectricity obtained using above-mentioned preparation method and answered Condensation material, the thermoelectric composite material includes the component of following weight proportion:
Preferably, the component of following weight proportion is included:
It is highly preferred that including the component of following weight proportion:
A kind of natural rubber-chalcopyrite thermoelectric composite material provided according to the present invention and preparation method thereof, with following Beneficial effect:
(1) in the present invention, in the whole preparation process of composite, produced without contaminant water and waste gas, green safety;
(2) in the present invention, natural rubber used, chalcopyrite and various additives wide material sources are cheap, use peace Entirely, production cost is low;
(3) preparation method of the invention is simple and easy to control, less demanding to production equipment, it is easy to operate, and is conducive to industrialization Promote;
(4) natural rubber obtained by preparation method in the present invention-chalcopyrite thermoelectric composite material, had both been maintained natural The pliability of rubber, presents the excellent pyroelectricity of chalcopyrite again.Obtained thermoelectric composite material, in the temperature difference between 30-70K When, it can realize the thermoelectricity capability of the material by regulating and controlling natural rubber and chalcopyrite material ratio, its thermoelectrical potential is between 0mV Between -15.82mV.
Brief description of the drawings
Fig. 1 is natural rubber-chalcopyrite thermoelectric composite material and comparative example 1,2 samples prepared by 1-3 of the embodiment of the present invention Thermoelectrical potential with difference variation curve map;
Fig. 2 is the XRD spectra of the sample of comparative example 2 of the present invention and mineral composition standard card;
Fig. 3 is natural rubber-chalcopyrite thermoelectric composite material and comparative example 1,2 samples prepared by 1-3 of the embodiment of the present invention XRD spectra;
Fig. 4 A are the SEM figures in natural rubber-chalcopyrite thermoelectric composite material section prepared by embodiment 1;
Fig. 4 B are the SEM figures in natural rubber-chalcopyrite thermoelectric composite material section prepared by embodiment 2;
Fig. 4 C are the SEM figures in natural rubber-chalcopyrite thermoelectric composite material section prepared by embodiment 3.
Embodiment
Below by drawings and examples, the present invention is described in more detail.Illustrated by these, the features of the present invention It will be become more apparent from clearly with advantage.
Special word " exemplary " is meant " being used as example, embodiment or illustrative " herein.Here as " exemplary " Illustrated any embodiment should not necessarily be construed as preferred or advantageous over other embodiments.Although each of embodiment is shown in the drawings In terms of kind, but unless otherwise indicated, it is not necessary to accompanying drawing drawn to scale.
The first aspect of the present invention there is provided a kind of preparation method of natural rubber-chalcopyrite thermoelectric composite material, including with Lower step:
Step 1, natural rubber is plasticated.
In the present invention, appropriate natural rubber is weighed, after cutting is uniform, is plasticated by opening rubber mixing machine.
The inventors discovered that, natural rubber is cut uniformly, is easy to processing to plasticate, is conducive to subsequent additive and chalcopyrite Addition with mixing.
In the present invention, after natural rubber cutting is uniform, roll temperature extremely provides preliminary roller 45 before and after adjustment opening rubber mixing machine ± 1 DEG C, 40 ± 1 DEG C of back roller.Roll spacing is adjusted to 3~6mm, preferably 4~5mm;Glue blob of viscose will be cut by main drive gear while connecting The continuous broken glue 3~6min, preferably 4~5min of input;Thin logical 10~13 times, the low once thin logical film by film, the 2nd torsion 90 ° of angles are added;10~12mm is modulated in roll spacing, and continuous left and right cutting after thin logical film bag roller is smash into conjunction 3~5 times, then cut Bottom sheet, parks 8~72h.
The inventors discovered that, the viscoplasticity of natural rubber is not only influenced by temperature, while also by the external force speed of action Influence.When shearing increase, to the viscoplasticity of natural rubber, equivalent to reduction temperature, make the intensity and bullet of natural rubber Property improve, be advantageously implemented elastic state bag roller.Therefore,, can also be by reducing roller in addition to roller temperature is reduced when there is roll release Solved away from, the method that revs up or carry high ratio.
Step 2, additive is added into the system of step 1, is kneaded.
In the present invention, the additive includes vulcanizing activator, vulcanization aid, antiscorching agent and accelerator.
In the present invention, the vulcanizing activator is metal oxide, preferably in zinc oxide, magnesia and silver oxide Any one or more, more preferably zinc oxide;The vulcanization aid is any one in stearic acid, nonox and white carbon Plant or a variety of, preferably stearic acid;The antiscorching agent is any one in phthalic anhydride, benzoic acid, salicylic acid and oleic acid Plant or a variety of, preferably salicylic acid;The accelerator be thiazoles, preferably any one in altax, captax or its Combination, more preferably its combination.
In the present invention, the weight ratio of each composition and natural rubber is in the additive, vulcanizing activator:Natural rubber Glue=(3~8):100, be preferably (4~6):100;Vulcanization aid:Natural rubber=(1~4):100, be preferably (1.5~ 2.5):100;Antiscorching agent:Natural rubber=(0.2~1):100, be preferably (0.3~0.6):100;Accelerator:Natural rubber= (1~3):100, be preferably (1.6~2.4):100.
In the present invention, when accelerator is the combination of altax and captax, the weight ratio of the two addition is 1:1.
The inventors discovered that, during mixing, additive is few due to consumption, and effect is big, to improve dispersion effect, needs More first add.
Step 3, chalcopyrite and softening agent are added into the system of step 2, continues to knead.
In the present invention, after the additive added in step 2 is evenly dispersed into natural rubber, size-reduced mistake is added The chalcopyrite of sieve continues to knead, while adding softening agent.
The inventors discovered that, during mixing, general to be added dose of softening agent adds again after being uniformly dispersed, because if Softening agent is first added, rubber overinflation can be made and influence the mechanical friction between xanthan molecule and filler to act on, reduction sizing material is mixed Speed is refined, while the scattered inequality of additive can be caused, or even conglomeration.
In the present invention, the chalcopyrite is the natural chalcopyrite dried at 100 DEG C, and 60~120 mesh are crossed after crushed Sieve, such as preferably 70~100 mesh sieves, 80 mesh sieves;The maximum particle diameter of natural chalcopyrite is less than 180 microns after crushing.
The inventors discovered that, size-reduced sieving, particle diameter are less than 180 microns of chalcopyrite, are preparing thermoelectric composite material During, can be more favourable evenly spread in natural rubber and is not likely to produce agglomeration.
In the present invention, the weight ratio of the chalcopyrite and natural rubber is (450~1350):100, be preferably (600~ 1200):100, more preferably (900~1200):100.
In the present invention, the softening agent is liquid softener, preferably any one in machine oil, white oil or its combination, The more preferably combination of machine oil and white oil.
In the present invention, the weight ratio of the addition of the liquid softener and natural rubber is (10~25):100, it is excellent Elect as (12~18):100.In the present invention, when the liquid softener of selection is the combination of machine oil and white oil, the two addition Weight ratio is 2:1, and during mixing, machine oil and white oil are alternately added.
Step 4, to step 3) system in add sulphur, vulcanized, be made natural rubber-chalcopyrite thermoelectricity composite wood Material.
In the present invention, after the softening agent added in step 3 and chalcopyrite are all dispersed in natural rubber, Sulphur is added, after sulphur is all uniformly blended into, takes appropriate elastomeric compound to load mould, vulcanizes in vulcanizing press, be made most End-product natural rubber-chalcopyrite thermoelectric composite material.
In the present invention, the weight ratio of the addition of the sulphur and natural rubber is (1.5~3.5):100, be preferably (1.8~2.8):100.
In the present invention, the temperature of the vulcanization is 135~150 DEG C, preferably 140~145 DEG C, such as 143 DEG C;Vulcanization Pressure is 13~17MPa, such as preferably 14~16MPa, 15MPa;Cure time is 15~25 minutes, preferably 20~25 points Clock.
In the present invention, the mold thickness is 0.1mm~0.3mm, preferably 0.15mm~0.25mm.
The natural rubber that step 4 of the present invention is obtained-chalcopyrite thermoelectric composite material, it generally comprises following weight proportion Component:
Preferably, natural rubber-chalcopyrite thermoelectric composite material is made according to the above method, in the temperature difference between 30-70K When, it is natural it is different with brass mineral content in the case of, its thermoelectrical potential is between 0mV and -15.82mV.
It is further preferred that the natural rubber according to made from the above method-chalcopyrite thermoelectric composite material, its crystal structure is in 2 θ There are (112), (220), (204), (312), (116) at respectively 29.47 °, 48.72 °, 49.11 °, 57.93 °, 58.65 ° Crystallographic plane diffraction peak is identical with the diffraction maximum position of natural chalcopyrite.
The second aspect of the present invention is there is provided a kind of natural rubber-chalcopyrite thermoelectric composite material, and it is according to above method system , the composite includes the component of following weight proportion:
Preferably, the component of following weight proportion is included:
It is highly preferred that including the component of following weight proportion:
The inventors discovered that, natural rubber tool has good wearability, very high elasticity, breaking strength and elongation, comprehensive Close better performances.And the molecular weight distribution of natural rubber is wider, suitable melting temperature wider range, at general temperature all Can bag roller well, mixing behavior is good.
In the present invention, the additive includes vulcanizing activator, vulcanization aid, antiscorching agent and accelerator.Wherein, it is described Vulcanizing activator is metal oxide, preferably any one or more in zinc oxide, magnesia and silver oxide, more preferably Zinc oxide;The vulcanization aid is any one or more in stearic acid, nonox and white carbon, preferably stearic acid; The antiscorching agent is any one or more in phthalic anhydride, benzoic acid, salicylic acid and oleic acid, preferably salicylic acid; The accelerator is thiazoles, preferably any one in altax, captax or its combination, more preferably its combination.
In the present invention, the weight ratio of each composition and natural rubber is as follows in the additive, vulcanizing activator:Naturally Rubber=(3~8):100, be preferably (4~6):100;Vulcanization aid:Natural rubber=(1~4):100, be preferably (1.5~ 2.5):100;Antiscorching agent:Natural rubber=(0.2~1):100, be preferably (0.3~0.6):100;Accelerator:Natural rubber= (1~3):100, be preferably (1.6~2.4):100.
In the present invention, the chalcopyrite is the natural chalcopyrite dried at 80~120 DEG C, preferably 90~110 DEG C The chalcopyrite of lower drying, crosses 60~120 mesh sieves, such as preferably 70~100 mesh sieves, 80 mesh sieves after crushed;It is natural after crushing The maximum particle diameter of chalcopyrite is less than 180 microns.
In the present invention, the weight ratio of the chalcopyrite and natural rubber is (450~1350):100, be preferably (600~ 1200):100, more preferably (900~1200):100.
In the present invention, the softening agent is liquid softener, preferably any one in machine oil, white oil or its combination, The more preferably combination of machine oil and white oil.The addition of the liquid softener and the weight ratio of natural rubber are (10~25): 100, be preferably (12~18):100.
In the present invention, using natural rubber obtained above-chalcopyrite thermoelectric composite material, in the temperature difference between 30-70K When, in the case where natural rubber is different with brass mineral content, its thermoelectrical potential is between 0mV and -15.82mV.
Embodiment
The present invention is further described below by way of instantiation, but these examples are only exemplary, not to this The protection domain of invention constitutes any limitation.
Embodiment 1
Step (1), weighs 100g natural rubbers, after cutting is uniform, and roll temperature is extremely provided before and after adjustment opening rubber mixing machine 45 ± 1 DEG C of preliminary roller, 40 ± 1 DEG C of back roller.Roll spacing is adjusted to 5mm;Glue blob of viscose will be cut, and by main drive gear, continuous input breaks glue on one side 5min;Thin logical 12 times, the low once thin logical film by film, 90 ° of angles of the 2nd torsion are added;11mm is modulated in roll spacing, will be thin logical Conjunction 4 times is smash in continuous left and right cutting after film bag roller, is then cut bottom sheet, is parked 48h;
Step (2), weighs 5g zinc oxide, 2.0g stearic acid, 0.5g salicylic acids, 1.0g altaxs, 1.0g captaxs and adds Enter and kneaded in the natural rubber after plasticating;
Step (3), after the additive added in step (2) is evenly spread in natural rubber, weighs 450g in 100 DEG C The natural chalcopyrite of lower drying, crosses 80 mesh sieves after crushing, then add in above-mentioned system and continue to knead, be alternately added simultaneously 10g10# machine oil and 5g white oils;
Step (4), after natural chalcopyrite is kneaded uniformly with machine oil, white oil in natural rubber, adds 2.5g sulphur, treats sulphur After sulphur is all mixed into, takes appropriate elastomeric compound to be fitted into the thick moulds of 0.2mm, vulcanize in vulcanizing press, curing temperature is 143 DEG C, pressure 15MPa, cure time 25 minutes.Vulcanization obtains natural rubber-chalcopyrite thermoelectric composite material after terminating.
Embodiment 2
The present embodiment method therefor is similar to the method therefor of embodiment 1, differs only in the natural Huang added in step (3) The amount of copper mine is 900g.
Embodiment 3
The present embodiment method therefor is similar to the method therefor of embodiment 1, differs only in the natural Huang added in step (3) The amount of copper mine is 1200g.
Comparative example
Comparative example 1
This comparative example specimen in use is the natural rubber material for not adding natural chalcopyrite.
Comparative example 2
This comparative example specimen in use is natural brass green ore particle.
Experimental example
The thermoelectrical potential measurement experiment of experimental example 1
The BHTE-06 type Seebeck coefficient measuring instruments developed using BJ University of Aeronautics & Astronautics, are measured under specified temp difference The thermoelectrical potential of thermoelectric composite material made from embodiment 1-3 and the specimen in use of comparative example 1 and 2, as a result as shown in table 1 and Fig. 1.
The thermoelectrical potential of the embodiment 1-3 of table 1 and the sample of comparative example 1 and 2 under certain temperature difference
From table 1 and Fig. 1, when the temperature difference is between 30-70K, the composite obtained by the present invention, in natural rubber and Huang In the case that copper mine content is different, its thermoelectrical potential is between 0mV and -15.82mV.Especially, when the temperature difference is 70K, thermoelectricity Composite is with the increase of brass mineral content, and its thermoelectrical potential increases to -15.82mV by -8.17mV;When chalcopyrite and natural rubber Weight ratio be 1200:When 100, as the temperature difference by 30K is increased to 70K, corresponding thermoelectrical potential increases to by -5.94mV - 15.82mV。
Furthermore it is also possible to draw to draw a conclusion:
(1) thermoelectric composite material made from embodiment 1-3 and the thermoelectrical potential measured by the natural brass green ore of comparative example 2 are equal For negative, illustrate that obtained natural rubber-chalcopyrite thermoelectric composite material belongs to N-type as natural brass green ore and led Body.
(2) the natural rubber sample of comparative example 1 is without pyroelectricity, and obtained natural rubber-chalcopyrite is combined in embodiment 1-3 Material all makes natural rubber-chalcopyrite composite have thermoelectricity capability because adding chalcopyrite, illustrates adding for brass green ore Enter to show thermoelectricity capability to sample and play a key effect.
(3) in same sample, embodiment 1-3 thermoelectrical potential is proportionate with the temperature difference, and thermoelectrical potential is with the liter of the temperature difference It is high and increase;Under same temperature difference condition, brass mineral content is proportionate with thermoelectrical potential in embodiment 1-3, and thermoelectrical potential is with brass The increase of mineral content and increase.
(4) natural rubber made from embodiment 1-3-chalcopyrite thermoelectric composite material and the brass green ore phase of comparative example 2 Than the thermoelectrical potential of sample is all higher than the thermoelectrical potential of sample in comparative example 2 in embodiment 1-3, illustrates that chalcopyrite is answered with natural rubber The thermoelectricity capability showed after conjunction is better than natural brass green ore, and natural rubber is conducive to natural brass green ore heat as matrix The raising of electrical property.
The X-ray diffraction of experimental example 2 is tested
Using German Bruker D8Advance types X-ray powder diffraction instrument (Cu targets KαRay), in λ=0.15406nm, To obtained thermoelectric composite material in embodiment 1-3 and right under the conditions of step width=0.02, operating voltage 40kV, operating current 40mA The sample of ratio 1 and comparative example 2 carries out XRD analysis, as a result as shown in Figures 2 and 3.
As shown in Figure 2, the crystal structure of the specimen in use of comparative example 22 θ be respectively 29.47 °, 48.72 °, 49.11 °, There is (112), (220), (204), (312), the crystallographic plane diffraction peak of (116) at 57.93 °, 58.65 °, with its standard card JCPDS#99-0029 is essentially identical, and it is chalcopyrite to illustrate the specimen in use main component of comparative example 2.
From the figure 3, it may be seen that crystalline substance of the crystal structure of embodiment 1-3 thermoelectric composite material and the sample of comparative example 2 at 2 θ Face diffraction maximum is essentially identical, illustrates that chalcopyrite still keeps original crystal structure in obtained thermoelectric composite material.
The sem test of experimental example 3 is tested
Using JEOL JSM-IT300 type SEM, operating voltage 15kV, to being made in embodiment 1-3 The section of natural rubber-chalcopyrite thermoelectric composite material carry out sem analysis, as a result such as Fig. 4 A, 4B and 4C, it can be seen that implement Monodispersed has chalcopyrite particle in thermoelectric composite material made from example 1-3.
In summary, natural rubber-chalcopyrite thermoelectric composite material prepared by the technical scheme that the present invention is provided, in the temperature difference During between 30-70K, in the case where natural rubber is different with brass mineral content, its thermoelectrical potential between 0mV and -15.82mV it Between.The crystal structure of composite 2 θ be respectively at 29.47 °, 48.72 °, 49.11 °, 57.93 °, 58.65 ° exist (112), (220), (204), (312), the crystallographic plane diffraction peak of (116).
The present invention is described in detail above in association with embodiment and exemplary example, but these explanations are simultaneously It is not considered as limiting the invention.It will be appreciated by those skilled in the art that without departing from the spirit and scope of the invention, A variety of equivalencings, modification can be carried out to technical solution of the present invention and embodiments thereof or is improved, these each fall within the present invention Protection domain in.Protection scope of the present invention is determined by the appended claims.

Claims (10)

1. the preparation method of a kind of natural rubber-chalcopyrite thermoelectric composite material, it is characterised in that comprise the following steps:
1), natural rubber is plasticated;
2) additive, is added into the system of step 1, is kneaded;
3) chalcopyrite and softening agent, are added into the system of step 2, continues to knead;
4) sulphur, is added into the system of step 3, is vulcanized, natural rubber-chalcopyrite thermoelectric composite material is made.
2. according to the method described in claim 1, it is characterised in that step 2), the additive includes vulcanizing activator, sulphur Change auxiliary agent, antiscorching agent and accelerator,
Preferably,
The vulcanizing activator is metal oxide, preferably any one or more in zinc oxide, magnesia and silver oxide, more Preferably zinc oxide;And/or
The vulcanization aid is any one or more in stearic acid, nonox and white carbon, preferably stearic acid;And/or
The antiscorching agent is any one or more in phthalic anhydride, benzoic acid, salicylic acid and oleic acid, preferably bigcatkin willow Acid;And/or
The accelerator is thiazoles, preferably any one in altax, captax or its combination, more preferably its group Close.
3. method according to claim 2, it is characterised in that step 2) in, the vulcanizing activator and natural rubber Weight ratio is (3~8):100, be preferably (4~6):100;And/or
The weight ratio of the vulcanization aid and natural rubber is (1~4):100, be preferably (1.5~2.5):100;And/or
The weight ratio of the antiscorching agent and natural rubber is (0.2~1):100, be preferably (0.3~0.6):100;And/or
The weight ratio of the accelerator and natural rubber is (1~3):100, be preferably (1.6~2.4):100.
4. according to the method described in claim 1, it is characterised in that step 3), in addition to chalcopyrite pulverized and sieved, it is described It was 60~120 mesh sieves to sieve, and was preferably 70~100 mesh sieves, such as 80 mesh sieves;The maximum particle diameter of chalcopyrite is less than after crushing 180 microns;And/or
The chalcopyrite is the natural chalcopyrite dried at 80~120 DEG C, is preferably the brass dried at 90~110 DEG C Ore deposit.
5. according to the method described in claim 1, it is characterised in that step 3), the weight of the chalcopyrite and natural rubber Than for (450~1350):100, be preferably (600~1200):100, more preferably (900~1200):100.
6. according to the method described in claim 1, it is characterised in that step 3), the softening agent is liquid softener, preferably For any one in machine oil, white oil or its combination, the more preferably combination of machine oil and white oil.
7. according to the method described in claim 1, it is characterised in that step 4), the weight for adding sulphur and natural rubber Amount is than being (1.5~3.5):100, be preferably (1.8~2.8):100;And/or
The temperature of the vulcanization is 135~150 DEG C, preferably 140~145 DEG C, such as 143 DEG C;And/or
The pressure of the vulcanization is 13~17MPa, such as preferably 14~16MPa, 15MPa;And/or
The cure time is 15~25 minutes, preferably 20~25 minutes.
8. the method according to claim 3 or 6, it is characterised in that step 2) in, the accelerator is altax and rush When entering agent M combination, the weight ratio of the two is 1:1;
Step 3) in, when the softening agent is the combination of machine oil and white oil, the weight ratio of the two is 2:1.
9. according to the method described in claim 1, it is characterised in that step 4), obtained natural rubber-chalcopyrite thermoelectricity is answered Condensation material is formed by the component of following weight proportion:
Preferably, it is when the temperature difference is between 30-70K, in the case where natural rubber is different with brass mineral content, thermoelectrical potential between Between 0 and -15.82mV.
10. a kind of natural rubber-chalcopyrite thermoelectric composite material, the method according to one of claim 1 to 9 is made, its It is characterised by, the thermoelectric composite material includes the component of following weight proportion:
Preferably, the component of following weight proportion is included:
It is highly preferred that including the component of following weight proportion:
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