Preparation method of non-woven fabric for X and gamma ray protection
Technical Field
The application relates to the field of radiation protection, in particular to a preparation method of non-woven fabric for X and gamma ray protection.
Background
In recent years, with the rapid development of national defense research, radiology and atomic energy industries, the use of various rays is increasingly widespread. X and gamma rays are one of the important types. The long-term exposure to X and gamma rays can cause damage to gonads, mammary glands, hematopoietic bone marrow and the like, and the exceeding dosage can even cause cancer, thereby bringing serious threat to human bodies. Therefore, according to the properties of X and gamma rays and the action mechanism of the X and gamma rays and substances, corresponding materials are selected and prepared for protection.
The first used for shielding X and gamma rays are metal materials such as lead plates and iron plates, and later products such as lead-containing glass, organic glass and rubber are developed and processed into various protective clothing, helmets, protective gloves and the like. However, these protective articles are poorly breathable, bulky, uncomfortable to wear, and lead presents a serious hazard to both the human body and the environment.
The method comprises the steps of coating the surface of a quartz fiber monofilament by using a surface treating agent containing a flame retardant, drawing and winding the quartz fiber monofilament into a quartz fiber precursor by a drawing machine head in a high-speed rotating manner, and producing the quartz fiber with the flame retardant coating after silk drying, untwisting, primary twisting and cabling; the Chinese invention patent 'a preparation method of X-ray-proof rare earth/polypropylene composite fiber' (CN 104532381B) discloses a preparation method of X-ray-proof rare earth/polypropylene composite fiber, which comprises the steps of firstly mixing and granulating rare earth element oxide particles and polypropylene particles to obtain rare earth/polypropylene particles, then carrying out melt spinning to obtain nascent fiber, shearing the nascent fiber into fibers with the length of 3-5 cm, uniformly paving the fibers layer by layer, and preparing non-woven fabric with the thickness of 4-8mm by means of a film pressing machine under pressure; the invention discloses a preparation method of an X-ray radiation resistant cellulose fiber (CN 102704023A). The method comprises the steps of preparing barium sulfate powder with the particle size of less than or equal to 3 mu m into barium sulfate emulsion slurry in an organic dispersion medium mutually soluble with water, adding the barium sulfate emulsion slurry into a viscose solution after yellowing and dissolution according to the weight percentage of the barium sulfate content to 10-30% of alpha cellulose, uniformly mixing, and then carrying out spinning and coagulating bath spinning forming, drafting and post-treatment to obtain the X-ray radiation resistant cellulose fiber. The disadvantages are that the addition amount of the functional powder in the polymer is low due to the compatibility problem of the functional powder and the polymer, so that the X-ray shielding rate is low, and the durability is poor when the X-ray radiation-blocking agent is coated on the surface of the fiber.
Disclosure of Invention
In view of this, the embodiments of the present application provide a method for preparing a non-woven fabric for X and γ ray protection, so as to solve the problems of poor durability caused by the X ray shielding rate and the application of an X ray radiation blocking agent on the surface of a fiber in the prior art.
The embodiment of the application adopts the following technical scheme:
the embodiment of the application provides a preparation method of non-woven fabric for X and gamma ray protection, which comprises the following steps:
preparing graphene oxide containing interlayer water;
preparing first graphene oxide powder of intercalated bismuth tungstate according to the graphene oxide containing interlayer water;
preparing second graphene oxide powder of intercalated europium oxide, samarium oxide, gadolinium oxide and barium oxide according to the first graphene oxide powder;
preparing lead-free powder with an X-ray radiation protection function according to the first graphene oxide powder and the second graphene oxide powder;
and preparing the non-woven fabric for X and gamma ray protection according to the lead-free powder with the X-ray radiation protection function.
Preferably, in the method for preparing a nonwoven fabric for X-ray and γ -ray protection, the preparing of graphene oxide containing interlayer water includes:
mixing expanded graphite and concentrated sulfuric acid according to a certain proportion, and fully stirring in an ice-water bath;
adding potassium permanganate until the potassium permanganate completely reacts;
adding deionized water, mechanically stirring, uniformly mixing, and adding hydrogen peroxide to obtain a first mixed solution;
washing the first mixed solution to be neutral by using a second mixed solution containing hydrochloric acid and deionized water under a centrifugal dispersion condition to obtain graphene oxide;
and carrying out ultrasonic treatment on the graphene oxide in a hydrothermal reaction kettle at a first temperature for a first preset time to obtain the graphene oxide containing interlayer water.
Preferably, in the preparation method of the non-woven fabric for protecting against X and gamma rays, the mass ratio of the expanded graphite to concentrated sulfuric acid is 1: 30-1: 40, the mass ratio of the expanded graphite to potassium permanganate is 1: 1-1: 6, the mass ratio of the expanded graphite to hydrogen peroxide is 1: 3-1: 10, and the volume ratio of hydrochloric acid to deionized water in the second mixed solution is 1: 5-1: 10;
the first temperature is 100-250 ℃, and the first preset time is 1-10 hours.
Preferably, in the above method for preparing a non-woven fabric for X-ray and γ -ray protection, the step of preparing the first graphene oxide powder of intercalated bismuth tungstate from the graphene oxide containing interlayer water includes:
dissolving bismuth nitrate in dilute nitric acid, and slowly adding the obtained silver nitrate solution into an aqueous solution of sodium tungstate under vigorous stirring;
adding a graphene oxide solution to obtain a third mixed solution;
adding an alkaline solution to adjust the pH value of the third mixed solution to 5-5.5;
adding hexadecyl trimethyl ammonium bromide and polyethylene glycol, and stirring for a second preset time to obtain gel;
and then treating the gel under a first pretreatment condition to obtain the first graphene oxide powder.
Preferably, in the preparation method of the non-woven fabric for protecting against X and gamma rays, the mass ratio of bismuth nitrate to dilute nitric acid is 1: 2-1: 5, the mass ratio of bismuth nitrate to sodium tungstate is 3:1-5:1, the mass ratio of bismuth nitrate to graphene oxide is 1: 2-1: 5, the concentration of hexadecyl trimethyl ammonium bromide is 0.01M-0.1M, and the mass ratio of bismuth nitrate to polyethylene glycol is 1: 3-1: 5;
the alkaline solution comprises a sodium hydroxide solution;
the second preset time is 6-10 hours;
the first pre-treatment conditions include: washing with ethanol, drying at 40-60 ℃, and calcining at 300-500 ℃.
Preferably, in the above method for preparing a non-woven fabric for X and γ ray protection, the step of preparing a second graphene oxide powder of intercalated europium oxide, samarium oxide, gadolinium oxide, and barium oxide from the first graphene oxide powder includes:
adding a mixed solution of europium nitrate, gadolinium nitrate, samarium nitrate and barium sulfate into a graphene oxide solution, adding ammonia water, performing ultrasonic treatment for a third preset time, transferring to a hydrothermal reaction kettle, and performing hydrothermal reaction at a second temperature for a fourth preset time to obtain a fourth mixed solution;
and treating the fourth mixed solution under a second pretreatment condition to obtain the second graphene oxide powder.
Preferably, in the above method for preparing a nonwoven fabric for X-and γ -ray protection, the mass component ratio of europium nitrate in the mixed solution of europium nitrate, gadolinium nitrate, samarium nitrate and barium sulfate is: 30% -40%; the mass component ratio of the gadolinium nitrate is 30-40%; the mass component ratio of the samarium nitrate is 10-20 percent; the mass component ratio of the barium sulfate is 10-20%;
1: 3-1: 5 of the mixed solution of europium nitrate, gadolinium nitrate, samarium nitrate and barium sulfate and graphene oxide, wherein the mass ratio of the mixed solution of europium nitrate, gadolinium nitrate, samarium nitrate and barium sulfate to ammonia water is 1: 3-1: 6;
the second temperature is 100-300 ℃, and the third preset time is 2-4 hours; the fourth preset time is 1-48 hours;
the second pretreatment condition is as follows: washing with ethanol, drying at 40-60 ℃, and calcining at 900-1200 ℃.
Preferably, in the method for preparing a non-woven fabric for X-and γ -ray protection, the preparation of the lead-free powder having an X-ray radiation protection function from the first graphene oxide powder and the second graphene oxide powder includes:
mixing the first graphene oxide powder and the second graphene oxide powder according to a ratio of 3:1-5:1, and then uniformly mixing to obtain the lead-free powder with the X-ray radiation protection function.
Preferably, in the method for producing a nonwoven fabric for X-and gamma-ray protection, the production of a nonwoven fabric for X-and gamma-ray protection from the lead-free powder having an X-ray radiation protection function includes:
uniformly mixing the lead-free powder with the X-ray radiation protection function and a silane coupling agent, dropwise adding a small amount of water, mechanically stirring for 1-1.5 hours, adding a hyperbranched polymer, and continuously stirring for 1-2 hours to obtain modified lead-free powder with the X-ray radiation protection function;
the non-woven fabric for X-ray and gamma-ray protection is prepared by taking the PE component and the PP component added with the modified lead-free powder with the X-ray radiation protection function as an adhesive fiber and a carrier fiber respectively.
Preferably, in the above method for preparing a nonwoven fabric for X and γ ray protection, the sheath of the PE fiber has a relative viscosity of 2.5 to 45.0, the core of the PP fiber has an intrinsic viscosity of not less than 0.64, the mass ratio of the powder in the PP is 20 to 40%, the mass ratio of the powder in the PE is 20 to 40%, and the fiber components are: 15-85% of PP and 85-15% of PE;
when the non-woven fabric for X-ray and gamma-ray protection is prepared, PE is at 200-230 ℃ and 5.0-35.0 MPa, and PP is at 235-265 ℃ and 15-35.0 MPa; the temperature, humidity and speed of the cooling air are respectively 15-28 ℃, 75-100% and 0.8-2.5 m/s; spinning speed is 400-1000 m/min; the water bath stretching temperature is 70-80 ℃, the water bath drafting multiple is 3.5-4.5, and then the water bath is subjected to steam drafting at the temperature of 90-110 ℃, and the steam drafting multiple is 1.1-1.5.
The embodiment of the application adopts at least one technical scheme which can achieve the following beneficial effects: the X-ray and gamma-ray shielding agent-nano powder is modified by the silane coupling agent and the hyperbranched polymer and then is added into the spinning polymer, so that the problems of poor dispersibility and agglomeration of the functional powder existing in the prior art when the functional powder is directly added into the spinning solution are effectively solved, the compatibility of the powder and the polymer is improved after modification treatment, the addition amount of the functional powder in the polymer is improved, and the prepared lead-free sheath-core fiber has good physical and mechanical properties, textile processing performance and usability, has the advantages of high X-ray and gamma-ray shielding rate and good durability, can be widely applied to the industries of clothing and non-woven fabrics of workers who are in contact with X and gamma rays for a long time, and has good economic and social benefits.
Drawings
The accompanying drawings, which are included to provide a further understanding of the application and are incorporated in and constitute a part of this application, illustrate embodiment(s) of the application and together with the description serve to explain the application and not to limit the application. In the drawings:
fig. 1 is a flowchart of a method for preparing a nonwoven fabric for X-ray and gamma-ray protection according to an embodiment of the present application.
Detailed Description
In order to make the objects, technical solutions and advantages of the present application more apparent, the technical solutions of the present application will be described in detail and completely with reference to the following specific embodiments of the present application and the accompanying drawings. It should be apparent that the described embodiments are only some of the embodiments of the present application, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
The technical solutions provided by the embodiments of the present application are described in detail below with reference to the accompanying drawings.
Fig. 1 is a schematic flow chart of a method for preparing a nonwoven fabric for X-ray and gamma-ray protection according to an embodiment of the present disclosure. The method may be as follows. The method comprises the following steps: preparing graphene oxide containing interlayer water as shown in step S101 in fig. 1; preparing first graphene oxide powder of intercalated bismuth tungstate according to the graphene oxide containing interlayer water, as shown in step S103 in figure 1; preparing second graphene oxide powder of intercalated europium oxide, samarium oxide, gadolinium oxide and barium oxide according to the first graphene oxide powder as shown in step S105 in FIG. 1; preparing lead-free powder with X-ray radiation protection function according to the first graphene oxide powder and the second graphene oxide powder, as shown in step S107 in the figure 1; and preparing a non-woven fabric for X-ray and gamma-ray protection from the lead-free powder having the X-ray radiation protection function, as shown in step S109 in FIG. 1.
Step S101, preparing graphene oxide containing interlayer water.
Specifically, firstly, the expanded graphite and the concentrated sulfuric acid are mixed according to a certain proportion and fully stirred in an ice-water bath. The mass ratio of the expanded graphite to the concentrated sulfuric acid is 1: 30-1: 40.
And then, adding potassium permanganate until the potassium permanganate completely reacts, wherein the mass ratio of the expanded graphite to the potassium permanganate is 1: 1-1: 6.
And then, adding deionized water, mechanically stirring, uniformly mixing, and adding hydrogen peroxide to obtain a first mixed solution, wherein the mass ratio of the expanded graphite to the hydrogen peroxide is 1: 3-1: 10.
And washing the first mixed solution to be neutral by using a second mixed solution containing hydrochloric acid and deionized water under a centrifugal dispersion condition to obtain the graphene oxide. Wherein the volume ratio of the hydrochloric acid to the deionized water in the second mixed solution is 1: 5-1: 10.
And carrying out ultrasonic treatment on the graphene oxide in a hydrothermal reaction kettle at a first temperature for a first preset time to obtain the graphene oxide containing interlayer water. Wherein the first temperature is 100-250 ℃, and the first preset time is 1-10 hours.
And S103, preparing first graphene oxide powder of intercalated bismuth tungstate according to the graphene oxide containing interlayer water.
Specifically, bismuth nitrate is dissolved in dilute nitric acid, and the obtained nitrate solution is slowly added into an aqueous solution of sodium tungstate under vigorous stirring, wherein the mass ratio of bismuth nitrate to dilute nitric acid is 1: 2-1: 5, and the mass ratio of bismuth nitrate to sodium tungstate is 3:1-5: 1.
And adding a graphene oxide solution to obtain a third mixed solution, wherein the mass ratio of the bismuth nitrate to the graphene oxide is 1: 2-1: 5.
And adding an alkaline solution to adjust the pH value of the third mixed solution to 5-5.5, wherein the alkaline solution comprises but is not limited to a sodium hydroxide solution.
And adding hexadecyl trimethyl ammonium bromide and polyethylene glycol, and stirring for a second preset time to obtain the gel. The concentration of the hexadecyl trimethyl ammonium bromide is 0.01-0.1M, the mass ratio of the bismuth nitrate to the polyethylene glycol is 1: 3-1: 5, and the second preset time is 6-10 hours.
And then treating the gel under a first pretreatment condition to obtain the first graphene oxide powder. The first pre-treatment conditions include: washing with ethanol, drying at 40-60 ℃, and calcining at 300-500 ℃.
And S105, preparing second graphene oxide powder of intercalated europium oxide, samarium oxide, gadolinium oxide and barium oxide according to the first graphene oxide powder.
Specifically, a mixed solution of europium nitrate, gadolinium nitrate, samarium nitrate and barium sulfate is added into a graphene oxide solution, ammonia water is added for ultrasonic treatment for a third preset time, the mixture is transferred to a hydrothermal reaction kettle, and hydrothermal reaction is carried out for a fourth preset time at a second temperature, so that a fourth mixed solution is obtained. The mass component ratio of europium nitrate in the mixed solution of europium nitrate, gadolinium nitrate, samarium nitrate and barium sulfate is as follows: 30% -40%; the mass component ratio of the gadolinium nitrate is 30-40%; the mass component ratio of the samarium nitrate is 10-20 percent; the mass component ratio of the barium sulfate is 10% -20%, the second temperature is 100-300 ℃, and the third preset time is 2-4 hours; the fourth preset time is 1-48 hours.
And treating the fourth mixed solution under a second pretreatment condition to obtain the second graphene oxide powder. The second pretreatment condition is as follows: washing with ethanol, drying at 40-60 ℃, and calcining at 900-1200 ℃.
And S107, preparing the lead-free powder with the X-ray radiation protection function according to the first graphene oxide powder and the second graphene oxide powder.
Specifically, the first graphene oxide powder and the second graphene oxide powder are mixed according to a ratio of 3:1-5:1, and then uniformly mixing to obtain the lead-free powder with the X-ray radiation protection function.
And step S109, preparing the non-woven fabric for X-ray and gamma-ray protection according to the lead-free powder with the X-ray radiation protection function.
Specifically, uniformly mixing the lead-free powder with the X-ray radiation protection function and a silane coupling agent, dropwise adding a small amount of water, mechanically stirring for 1-1.5 hours, adding a hyperbranched polymer, and continuously stirring for 1-2 hours to obtain modified lead-free powder with the X-ray radiation protection function;
the non-woven fabric for X-ray and gamma-ray protection is prepared by taking the PE component and the PP component added with the modified lead-free powder with the X-ray radiation protection function as an adhesive fiber and a carrier fiber respectively.
Wherein the relative viscosity of the sheath of the PE fiber is 2.5-45.0, the intrinsic viscosity of the core of the PP fiber is not lower than 0.64, the mass ratio of the powder in the PP is 20-40%, the mass ratio of the powder in the PE is 20-40%, and the fiber components comprise: 15-85% of PP and 85-15% of PE;
when the non-woven fabric for X-ray and gamma-ray protection is prepared, PE is at 200-230 ℃ and 5.0-35.0 MPa, and PP is at 235-265 ℃ and 15-35.0 MPa; the temperature, humidity and speed of the cooling air are respectively 15-28 ℃, 75-100% and 0.8-2.5 m/s; spinning speed is 400-1000 m/min; the water bath stretching temperature is 70-80 ℃, the water bath drafting multiple is 3.5-4.5, and then the water bath is subjected to steam drafting at the temperature of 90-110 ℃, and the steam drafting multiple is 1.1-1.5.
Next, a description will be given of a specific example.
Firstly, putting a certain amount of expanded graphite and a proper amount of concentrated sulfuric acid into a glass container, and fully stirring in an ice-water bath; slowly adding a certain amount of potassium permanganate until the potassium permanganate completely reacts, then adding a certain amount of deionized water, mechanically stirring at a certain temperature, uniformly mixing, then adding a certain amount of hydrogen peroxide, and changing the solution from brown black to bright yellow; and (3) washing the solution to be neutral under the condition of centrifugal dispersion of hydrochloric acid and deionized water to obtain the graphene oxide.
Secondly, placing the prepared graphene oxide in a hydrothermal reaction kettle, and carrying out ultrasonic treatment under a certain temperature condition to obtain the graphene oxide containing interlayer water.
Then, dissolving a certain amount of bismuth nitrate pentahydrate in a certain amount of dilute nitric acid, slowly adding a nitrate solution into a certain amount of aqueous solution of sodium tungstate under vigorous stirring, then adding a certain amount of graphene oxide solution, adding a sodium hydroxide solution to adjust the pH value to 5-5.5, adding polyethylene glycol, stirring for 6-10 hours, washing the obtained gel with ethanol, drying at 40-60 ℃, and calcining at 300-500 ℃ to obtain first graphene oxide powder of intercalated bismuth tungstate.
And then, adding a certain amount of mixed solution of europium nitrate, gadolinium nitrate, samarium nitrate and barium sulfate into a certain amount of graphene oxide solution, adding a certain amount of ammonia water for 2-4 hours of strong ultrasound, transferring the mixture into a hydrothermal reaction kettle for hydrothermal reaction at the temperature of 100-300 ℃ for 1-48 hours, washing the obtained solution with ethanol, drying at the temperature of 40-60 ℃, and calcining at the temperature of 900-1200 ℃ to obtain second graphene oxide powder of intercalated europium oxide, samarium oxide, gadolinium oxide and barium oxide.
Then, mixing the first graphene oxide powder and the second graphene oxide powder according to the ratio of 3:1-5:1, and then evenly mixing to obtain the powder with the X-ray radiation protection function.
And then, uniformly mixing the X-ray radiation protection functional powder with a silane coupling agent, dropwise adding a small amount of water, mechanically stirring for 1-1.5 hours, adding a hyperbranched polymer, and continuously stirring for 1-2 hours to obtain the modified X-ray radiation protection functional powder.
Finally, the PE component and the PP component added with the modified X-ray radiation protection functional powder are respectively used as an adhesive fiber and a carrier fiber to prepare the PE/PP sheath-core composite fiber.
In the preparation method of the non-woven fabric for X and gamma ray protection provided by the embodiment of the application, expanded graphite is used as a raw material to prepare a graphene oxide solution; taking bismuth nitrate pentahydrate and sodium tungstate as raw materials, generating bismuth tungstate in situ between graphene oxide lamella to obtain graphene oxide of intercalated bismuth tungstate, and washing, drying and calcining to obtain first graphene oxide powder of intercalated bismuth tungstate; preparing second graphene oxide powder of intercalated europium oxide, samarium oxide, gadolinium oxide and barium oxide by using europium nitrate, gadolinium nitrate, samarium nitrate and barium sulfate as raw materials; and mixing the first graphene oxide powder and the second graphene oxide powder, modifying by using a silane coupling agent and a hyperbranched polymer, and adding the modified mixture into the PE component and the PP component to prepare the PE/PP skin-core composite fiber with the X-ray and gamma-ray radiation prevention function. The addition amount of the functional powder in the prepared PE/PP sheath-core composite fiber is improved, and the fiber not only has good physical and mechanical properties, textile processing properties and wearability, but also has the advantages of high shielding rate of X and gamma rays, good durability, lead-free and light weight, and has good application prospect in the aspect of X and gamma ray radiation protection.
The embodiments in the present specification are described in a progressive manner, and the same and similar parts among the embodiments are referred to each other, and each embodiment focuses on the differences from the other embodiments.
The above description is only an example of the present application and is not intended to limit the present application. Various modifications and changes may occur to those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the scope of the claims of the present application.