Aramid self-reinforced composite material prepared by surface dissolution method and application thereof
Technical Field
The invention belongs to the technical field of aramid fiber composite materials, and particularly relates to an aramid fiber self-reinforced composite material with super-strong mechanical strength in the transverse direction and the longitudinal direction, and a preparation method and application thereof.
Background
In recent years, a new class of "all-polymer composites" or "self-reinforced composites" based on similar or identical materials as the matrix and the reinforcement have attracted much attention in the industry due to their advantages in processing and recycling. Also, the matrix and the reinforcement have good interfacial effects because they are of the same chemical composition, and thus have advantages over conventional reinforced composites. Self-reinforced polymer composites are the fastest growing field in the field of engineering polymers. But at present these materials are mainly thermoplastic fibres with mild properties. Conventional methods of making self-reinforced composites include film stacking, powder impregnation, solution injection, hot pressing, and co-extrusion methods. Especially the last two have been quite successful and commercial products have been obtained.
The Propex textile company produced a novel thermoplastic composite material, Curv, using a hot pressing process. Selectively melting partial polymer surface by finely controlling processing temperature, and rapidly fusing the polymer surface by a hot pressing process; after a subsequent cooling process, the originally melted fiber fraction is bound back to the matrix by recrystallization to obtain a self-reinforcing material. Commercial PUREs produced by lank-hoster composites, netherlands, are obtained based on a coextrusion technique, exhibiting excellent mechanical properties and recyclability. In this way, a coextruded tape can be obtained having a "shell-core" structure with a large difference in melting points.
Since the last sixties years of the century since the development of Dupont corporation, aramid fiber is a high-tech synthetic fiber which is the most widely applied of three high-performance fibers in the world, and has high attention in various countries in the world due to its excellent properties such as high temperature resistance, organic solvent resistance, high strength, high modulus and the like, and is the first organic fiber with sufficient tensile strength and modulus to be applied to advanced composite materials. The PPTA and PPDA aramid fibers are applied to tires, rubber tubes, bulletproof materials, thermal protection materials, engineering plastics and composite materials due to the excellent performance. In particular, in the aspect of mechanics, the high tensile strength and tensile modulus are possessed at very low density; in thermal property, the flame retardant property is good, and the thermal decomposition temperature is high.
The preparation of the aramid self-reinforced composite material is rarely reported. Because aramid fiber has high flame retardance and high temperature resistance and has excellent mechanical property and difficult deformation, the aramid fiber self-reinforcing material is difficult to prepare by using the traditional methods such as film stacking, powder impregnation, solution injection, hot pressing, co-extrusion and the like.
Disclosure of Invention
In order to overcome the defects and shortcomings of the prior art, the invention mainly aims to provide a preparation method of a high-strength aramid self-reinforced composite material. The aramid fiber self-reinforced composite material is prepared by adopting a surface dissolving method, the method is simple and efficient, the preparation condition is mild, and the prepared composite material has high strength and very excellent performance.
The invention also aims to provide the aramid self-reinforced composite material prepared by the method. The composite material has high temperature resistance, excellent mechanical property and better strength in the transverse and longitudinal directions.
The invention further aims to provide application of the aramid self-reinforced composite material. The aramid self-reinforced composite material is applied to the fields of national defense, aerospace, high-speed trains and electrical insulation, and is based on lasting thermal stability, outstanding flame retardance, excellent electrical insulation, outstanding chemical stability, excellent mechanical property and super-strong radiation resistance.
The purpose of the invention is realized by the following technical scheme:
a preparation method of an aramid self-reinforced composite material comprises the following specific steps:
partially dissolving aramid fiber in an organic solvent, strong base and an auxiliary agent at a certain temperature, taking out undissolved aramid fiber, and soaking the undissolved aramid fiber in water to partially cure the aramid fiber; and then carrying out stable curing in a near-vacuum low-pressure environment, and carrying out subsequent treatment to obtain the aramid self-reinforced composite material.
When the undissolved aramid fiber is taken out, the surface of the undissolved aramid fiber has partially dissolved aramid fiber and undissolved aramid fiber.
The organic solvent is a strong polar organic solvent.
Preferably, the organic solvent is at least one of N, N-dimethylformamide (DMAc), dimethyl sulfoxide (DMSO), and N, N-Dimethylacetamide (DMF).
The auxiliary agent is at least one of alkali metal salt or alkaline earth metal salt.
Preferably, the auxiliary agent is at least one of lithium chloride and calcium chloride.
The strong base is at least one of inorganic base and organic base.
Preferably, the strong base is at least one of sodium hydroxide, potassium tert-butoxide and sodium ethoxide.
The aramid fiber is promoted to be dissolved by utilizing the interaction of strong base and an auxiliary agent, and good dissolution is the first condition for promoting the surface of the aramid fiber to be quickly separated from the aramid fiber matrix.
The certain temperature is 30-90 ℃.
The partial dissolution time, namely the infiltration dissolution time, is 0.5h to 2h, and is preferably 1 h. The specific dissolving time can be determined according to actual conditions. The dissolving time is too long, and the longitudinal performance of the aramid fiber can be influenced by excessive dissolving; the time is too short, and the strength of the formed transverse fibers cannot meet the application requirements.
The mass ratio of the aramid fiber to the strong base to the auxiliary agent is (5-10): (5-10): (0-10).
The addition amount of the organic solvent is preferably just submerging the aramid fiber body.
The aramid fiber is soaked in water for curing for 0.5-1.5 min, preferably 0.8-1.2 min, and more preferably 1 min. The water solidification is more efficient because the aramid fiber solution or the solution can be immediately coagulated into solid when meeting water, and the low-pressure solidification plays a role in stabilizing and shaping at the later stage.
The low-pressure environment refers to an environment with the pressure of 3-10 kpa.
The stable curing time is 5-15 min.
The subsequent treatment refers to soaking, cleaning and drying the product.
The cleaning is to sequentially clean the glass by ethanol and normal hexane or sequentially clean the glass by ethanol and cyclohexane.
The drying is vacuum drying.
The aramid self-reinforced composite material is prepared by the method. The aramid self-reinforced composite material has high temperature resistance, excellent mechanical property and better strength in the transverse and longitudinal directions.
The aramid self-reinforced composite material is applied to the fields of national defense, aerospace, high-speed trains and electrical insulation.
The mechanism of the invention is as follows:
the aromatic polyamide has excellent properties of high temperature resistance, solvent resistance, high modulus and the like due to the rigidity of a special molecular structure and strong hydrogen bonding action among molecules, and is widely applied to the technical fields of national defense, papermaking, automobile manufacturing, textile and the like. Aramid fiber can be slowly dissolved in a strong base, an organic solvent and an auxiliary agent system at a certain temperature, after part of the aramid fiber is dissolved, when the undissolved aramid fiber is taken out, the surface of the undissolved aramid fiber can be partially dissolved with the aramid fiber and the aramid fiber which is not completely dissolved; after the aramid fiber is immersed in water, the aramid fiber surface is partially cured (the aramid fiber matrix (undissolved aramid fiber) and the aramid fiber self-reinforcing part are recombined to initially form transverse fibers) after the aramid fiber is immersed for a short time; and performing stable curing in a near-vacuum low-pressure environment, further generating and shaping the transverse fibers on the surface of the aramid fiber, and cleaning to remove impurities to obtain the aramid fiber self-reinforced composite material.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the aramid self-reinforced composite material prepared by the invention has the advantages of high temperature resistance, solvent resistance, high modulus, excellent mechanical property and better strength in the transverse and longitudinal directions, and the aramid fiber prepared by the composite material disclosed by the invention is more widely applied; the all-aramid polymer obtained by the invention has new characteristics on the basis of keeping the original excellent characteristics of aramid: the transverse Young modulus can reach 152-226MPa at room temperature, the tensile strength can reach 6.8-8.6MPa, and new transverse mechanical strength (originally zero) is endowed;
(2) the preparation method is simple, the reagent is easy to obtain and control, the cost is low, and the industrial production is easy to realize; and has ductility guidance for the self-reinforcing preparation of carbon fiber polymers and other aramid fiber polymers.
Detailed Description
The present invention is described in further detail below with reference to examples, but the embodiments of the present invention are not limited thereto.
Example 1
The preparation method of the aramid self-reinforced composite fiber material comprises the following steps:
(1) soaking 10 parts by mass of an aramid fiber belt with a binding size of 10cm into 200 parts by mass of dimethyl sulfoxide, adding 5 parts by mass of potassium tert-butoxide and 3 parts by mass of lithium chloride, and continuously heating and soaking at 50 ℃ for 1h to dissolve part of the surface of the aramid fiber belt;
(2) taking out an undissolved aramid fiber belt (an aramid fiber body, attached dissolved aramid fibers and a partially dissolved system (undissolved aramid fibers) adhered on the aramid fiber body), and immersing the belt in water for 1min to partially solidify the belt (primarily form transverse fibers); then carrying out stable curing for 10min under the low-pressure environment of near vacuum 5kpa (the process of generating and shaping transverse fibers);
(3) and finally, soaking the cured aramid fiber belt into ethanol for 6h, then adding n-hexane for 6h, removing the auxiliary agent, and drying at 20 ℃ in vacuum for 48h to obtain the aramid self-reinforced composite fiber material.
Example 2
The preparation method of the aramid self-reinforced composite fiber material comprises the following steps:
(1) soaking 10 parts by mass of an aramid fiber belt with a binding size of 10cm into 200 parts by mass of dimethyl sulfoxide, adding 5 parts by mass of sodium hydroxide and 3 parts by mass of lithium chloride, and continuously heating and soaking at 50 ℃ for 1 hour to dissolve part of the surface of the aramid fiber belt;
(2) taking out an undissolved aramid fiber belt (an aramid fiber body, attached dissolved aramid fibers and a partially dissolved system (undissolved aramid fibers) adhered on the aramid fiber body), and immersing the belt in water for 1min to partially solidify the belt (primarily form transverse fibers); then carrying out stable curing for 10min under the low-pressure environment of near vacuum 5kpa (the process of generating and shaping transverse fibers);
(3) and finally, soaking the cured aramid fiber belt into ethanol for 6 hours, then adding cyclohexane for 6 hours, removing the auxiliary agent, and drying at 20 ℃ in vacuum for 48 hours to obtain the aramid self-reinforced composite fiber material.
Example 3
The preparation method of the aramid self-reinforced composite fiber material comprises the following steps:
(1) soaking 10 parts by mass of an aramid fiber belt with a binding size of 10cm into 200 parts by mass of dimethyl sulfoxide, adding 5 parts by mass of sodium ethoxide and 3 parts by mass of lithium chloride, and continuously heating and soaking at 50 ℃ for 1 hour to dissolve the surface part of the aramid fiber belt;
(2) taking out an undissolved aramid fiber belt (an aramid fiber body, attached dissolved aramid fibers and a partially dissolved system (undissolved aramid fibers) adhered on the aramid fiber body), and immersing the belt in water for 1min to partially solidify the belt (primarily form transverse fibers); then carrying out stable curing for 10min under the low-pressure environment of near vacuum 5kpa (the process of generating and shaping transverse fibers);
(3) and finally, soaking the cured aramid fiber belt into ethanol for 6h, then adding cyclohexane (or normal hexane) for 6h, removing the auxiliary agent, and drying at 20 ℃ in vacuum for 48h to obtain the aramid self-reinforced composite fiber material.
Example 4
The preparation method of the aramid self-reinforced composite fiber material comprises the following steps:
(1) soaking 10 parts by mass of an aramid fiber belt with a binding size of 10cm into 200 parts by mass of dimethyl sulfoxide, adding 10 parts by mass of potassium tert-butoxide and 3 parts by mass of lithium chloride, and continuously heating and soaking at 50 ℃ for 1h to dissolve part of the surface of the aramid fiber belt;
(2) taking out an undissolved aramid fiber belt (an aramid fiber body, attached dissolved aramid fibers and a partially dissolved system (undissolved aramid fibers) adhered on the aramid fiber body), and immersing the belt in water for 1min to partially solidify the belt (primarily form transverse fibers); then carrying out stable curing for 10min under the low-pressure environment of near vacuum 5kpa (the process of generating and shaping transverse fibers);
(3) and finally, soaking the cured aramid fiber belt into ethanol for 6 hours, then adding cyclohexane for 6 hours, removing the auxiliary agent, and drying at 20 ℃ in vacuum for 48 hours to obtain the aramid self-reinforced composite fiber material.
Example 5
The preparation method of the aramid self-reinforced composite fiber material comprises the following steps:
(1) soaking 10 parts by mass of an aramid fiber belt with a binding size of 10cm into 200 parts by mass of dimethyl sulfoxide, adding 5 parts by mass of potassium tert-butoxide and 3 parts by mass of calcium chloride, and continuously heating and soaking at 50 ℃ for 1h to dissolve part of the surface of the aramid fiber belt;
(2) taking out an undissolved aramid fiber belt (an aramid fiber body, attached dissolved aramid fibers and a partially dissolved system (undissolved aramid fibers) adhered on the aramid fiber body), and immersing the belt in water for 1min to partially solidify the belt (primarily form transverse fibers); then carrying out stable curing for 10min under the low-pressure environment of near vacuum 5kpa (the process of generating and shaping transverse fibers);
(3) and finally, soaking the cured aramid fiber belt into ethanol for 6h, then adding n-hexane for 6h, removing the auxiliary agent, and drying at 20 ℃ in vacuum for 48h to obtain the aramid self-reinforced composite fiber material.
Example 6
The preparation method of the aramid self-reinforced composite fiber material comprises the following steps:
(1) soaking 5 parts by mass of an aramid fiber belt with a binding size of 10cm into 200 parts by mass of dimethyl sulfoxide, adding 5 parts by mass of potassium tert-butoxide and 3 parts by mass of lithium chloride, and continuously heating and soaking at 50 ℃ for 1h to dissolve part of the surface of the aramid fiber belt;
(2) taking out an undissolved aramid fiber belt (an aramid fiber body, attached dissolved aramid fibers and a partially dissolved system (undissolved aramid fibers) adhered on the aramid fiber body), and immersing the belt in water for 1min to partially solidify the belt (primarily form transverse fibers); then carrying out stable curing for 10min under the low-pressure environment of near vacuum 5kpa (the process of generating and shaping transverse fibers);
(3) and finally, soaking the cured aramid fiber belt into ethanol for 6h, then adding n-hexane for 6h, removing the auxiliary agent, and drying at 20 ℃ in vacuum for 48h to obtain the aramid self-reinforced composite fiber material.
Example 7
The preparation method of the aramid self-reinforced composite fiber material comprises the following steps:
(1) soaking 10 parts by mass of an aramid fiber belt with a binding size of 10cm into 200 parts by mass of dimethyl sulfoxide, adding 5 parts by mass of potassium tert-butoxide and 0 part by mass of lithium chloride, and continuously heating and soaking at 50 ℃ for 1h to dissolve part of the surface of the aramid fiber belt;
(2) taking out an undissolved aramid fiber belt (an aramid fiber body, attached dissolved aramid fibers and a partially dissolved system (undissolved aramid fibers) adhered on the aramid fiber body), and immersing the belt in water for 1min to partially solidify the belt (primarily form transverse fibers); then carrying out stable curing for 10min under the low-pressure environment of near vacuum 5kpa (the process of generating and shaping transverse fibers);
(3) and finally, soaking the cured aramid fiber belt into ethanol for 6 hours, then adding cyclohexane for 6 hours, removing the auxiliary agent, and drying at 20 ℃ in vacuum for 48 hours to obtain the aramid self-reinforced composite fiber material.
Example 8
The preparation method of the aramid self-reinforced composite fiber material comprises the following steps:
(1) soaking 10 parts by mass of an aramid fiber belt with a binding size of 10cm into 200 parts by mass of dimethyl sulfoxide, adding 5 parts by mass of potassium tert-butoxide and 10 parts by mass of lithium chloride, and continuously heating and soaking at 50 ℃ for 1h to dissolve part of the surface of the aramid fiber belt;
(2) taking out an undissolved aramid fiber belt (an aramid fiber body, attached dissolved aramid fibers and a partially dissolved system (undissolved aramid fibers) adhered on the aramid fiber body), and immersing the belt in water for 1min to partially solidify the belt (primarily form transverse fibers); then carrying out stable curing for 10min under the low-pressure environment of near vacuum 5kpa (the process of generating and shaping transverse fibers);
(3) and finally, soaking the cured aramid fiber belt into ethanol for 6 hours, then adding cyclohexane for 6 hours, removing the auxiliary agent, and drying at 20 ℃ in vacuum for 48 hours to obtain the aramid self-reinforced composite fiber material.
Example 9
The preparation method of the aramid self-reinforced composite fiber material comprises the following steps:
(1) soaking 10 parts by mass of an aramid fiber belt with a binding size of 10cm into 200 parts by mass of N, N-dimethylformamide, adding 5 parts by mass of potassium tert-butoxide and 10 parts by mass of lithium chloride, and continuously heating and soaking at 50 ℃ for 1h to dissolve part of the surface of the aramid fiber belt;
(2) taking out an undissolved aramid fiber belt (an aramid fiber body, attached dissolved aramid fibers and a partially dissolved system (undissolved aramid fibers) adhered on the aramid fiber body), and immersing the belt in water for 1min to partially solidify the belt (primarily form transverse fibers); then carrying out stable curing for 10min under the low-pressure environment of near vacuum 5kpa (the process of generating and shaping transverse fibers);
(3) and finally, soaking the cured aramid fiber belt into ethanol for 6 hours, then adding cyclohexane for 6 hours, removing the auxiliary agent, and drying at 20 ℃ in vacuum for 48 hours to obtain the aramid self-reinforced composite fiber material.
Example 10
The preparation method of the aramid self-reinforced composite fiber material comprises the following steps:
(1) soaking 10 parts by mass of an aramid fiber belt with a binding size of 10cm into 200 parts by mass of N, N-dimethylacetamide, adding 5 parts by mass of potassium tert-butoxide and 10 parts by mass of lithium chloride, and continuously heating and soaking at 50 ℃ for 1h to dissolve part of the surface of the aramid fiber belt;
(2) taking out an undissolved aramid fiber belt (an aramid fiber body, attached dissolved aramid fibers and a partially dissolved system (undissolved aramid fibers) adhered on the aramid fiber body), and immersing the belt in water for 1min to partially solidify the belt (primarily form transverse fibers); then carrying out stable curing for 10min under the low-pressure environment of near vacuum 5kpa (the process of generating and shaping transverse fibers);
(3) and finally, soaking the cured aramid fiber belt into ethanol for 6 hours, then adding cyclohexane for 6 hours, removing the auxiliary agent, and drying at 20 ℃ in vacuum for 48 hours to obtain the aramid self-reinforced composite fiber material.
And (3) performance testing:
the composite materials prepared in examples 1 to 10 were subjected to performance tests, and the test results are shown in table 1:
the mechanical parameters of the all-aramid self-reinforced composite fiber material prepared in the examples 1 to 10 are as follows, and are compared with pure aramid fibers:
TABLE 1 mechanical parameters of all-aramid self-reinforced composite fiber materials
(examples 1, 2 and 3 influence on the type of strong base, examples 1 and 4 influence on the addition of strong base, examples 1 and 5 influence on the type of assistant, examples 1 and 6 influence on the addition of aramid fiber in bulk (changing the weaving density of aramid fiber), examples 1, 7 and 8 influence on the addition of assistant, examples 8, 9 and 10 influence on the type of organic solvent, and it is found that the difference between examples 1 and 6 is the largest, that is, the influence on the addition of aramid fiber is the largest, the smaller the addition of aramid fiber is, the better the aramid fiber is in full contact with a dissolving system, and the better the strength of the obtained transverse fiber is.)
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents and are included in the scope of the present invention.