CN108193549A - A kind of preparation method of X, gamma-rays protection aramid paper - Google Patents
A kind of preparation method of X, gamma-rays protection aramid paper Download PDFInfo
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- CN108193549A CN108193549A CN201810189668.3A CN201810189668A CN108193549A CN 108193549 A CN108193549 A CN 108193549A CN 201810189668 A CN201810189668 A CN 201810189668A CN 108193549 A CN108193549 A CN 108193549A
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/54—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen
- D21H17/55—Polyamides; Polyaminoamides; Polyester-amides
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
- D01F1/106—Radiation shielding agents, e.g. absorbing, reflecting agents
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/90—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyamides
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
Abstract
This application provides a kind of X, gamma-rays protects the preparation method of aramid paper, by by X, gamma ray shielding agent-nano-powder is added to by the way that silane coupling agent and dissaving polymer are modified in aramid fiber solution, since aramid fiber and Hyperbranched Polymer with Terminal Amido interfacial effect are good, the additive amount of functional powders is improved in prepared aramid paper, prepared aramid paper not only has good intensity and high temperature resistance, also there is X, gamma ray shielding rate is high, persistence is good, unleaded light-weighted advantage, in X, there is good application prospect in terms of gamma Rays protection.
Description
Technical field
This application involves radiation protection field more particularly to a kind of X, the preparation methods of gamma-rays protection aramid paper.
Background technology
In recent years, with the rapid development of national defence scientific research, Radiation Medicine and atomic energy industry, the use of various rays is increasingly
Extensively.X, gamma-rays is its important one kind.Due to Long Term Contact X, gamma-rays, sexual gland, mammary gland, Hematopoietic marrow etc. can all be produced
Raw injury, even can be carcinogenic more than dosage, and serious threat is brought to human body.Therefore according to X, gamma-ray property and its and substance
The mechanism of action, should select and prepare corresponding material and be protected.
Earliest the metal materials such as stereotype, iron plate for X, gamma ray shielding, have developed again later leaded glass,
The products such as organic glass and rubber, and it is processed into various protective garments, the helmet, protective gloves etc..But these protective articles gas permeabilities
Difference, it is heavy, wear uncomfortable, while all there are serious harm to human body and environment for lead.
The existing related patents about radiation protection paper have very much, such as a kind of Chinese invention patent " system of Radiation-roof wallpaper
Make method " in (CN 105089231A), a kind of preparation method of Radiation-roof wallpaper is disclosed, which includes the back of the body and protects
Layer and superficial layer, back of the body sheath include opposite first side and second side, set metal coating, the closely sealed back of the body on the first side
Sheath and superficial layer form integrated Radiation-roof wallpaper；A kind of Chinese invention patent " radiation-resistant environment-friendly wallpaper " (CN
In 101979799A), disclose a kind of preparation method of radiation-resistant environment-friendly wallpaper, which includes superficial layer, superficial layer its
In be attached with successively for the electro-magnetic screen layer of radiation protection on a side and the back of the body sheath for protecting electro-magnetic screen layer；China
In patent of invention " multifunctional radiation proof wallpaper or wall paper and preparation method thereof " (CN 107326749A), a kind of anti-spoke is disclosed
The preparation method of Multifunctional wallpaper or wall paper is penetrated, the multifunctional radiation proof wallpaper or wall paper include hypothallus and decorative layer, described
Adhesive layer is provided between hypothallus and decorative layer, the adhesive layer includes adhesive and modification infusorial earth, is added in adhesive layer
Modification infusorial earth with shielding property is to achieve the purpose that radiation protection.It is by setting shielded layer to reach the mesh of radiation protection
, the patent for directly preparing radiation proof function paper is but rarely reported, and the present invention is by by X, gamma ray shielding agent-nano-powder
It is modified to be added to the aramid paper prepared in aramid fiber solution with X, gamma-rays safeguard function.
Invention content
In view of this, the embodiment of the present application provides the preparation method of a kind of X, gamma-rays protection aramid paper, with simple high
Effect safe and reliable prepares X, gamma-rays protection aramid paper.
The embodiment of the present application uses following technical proposals：
The embodiment of the present application provides the preparation method of a kind of X, gamma-rays protection aramid paper, including：
Graphene oxide is obtained, and the aqueous graphene oxide of interlayer is prepared according to the graphene oxide；
Prepare the first graphene oxide powder of intercalation bismuth tungstate；
Prepare the second graphene oxide powder of intercalation europium oxide, samarium oxide, gadolinium oxide and barium monoxide；
X-ray radiation safeguard function is prepared according to first graphene oxide powder and the second graphene oxide powder
Unleaded powder；
Modified x-ray radiation safeguard function is prepared without lead powder according to the unleaded powder of the x-ray radiation safeguard function
Body；
Fibrid is prepared according to the unleaded powder of x-ray radiation safeguard function of the modification；
X, gamma-rays protection aramid paper are prepared according to the fibrid.
Preferably, it is protected in the preparation method of aramid paper in above-mentioned X, gamma-rays, obtains the process packet of graphene oxide
It includes：
After expanded graphite and the concentrated sulfuric acid are mixed and are sufficiently stirred according to the first preset ratio, potassium permanganate is added in, until
The potassium permanganate total overall reaction, adds deionized water and is stirred, add in hydrogen peroxide after mixing, and it is mixed to obtain first
Close solution；
With first mixed solution is cleaned under the conditions of hydrochloric acid and deionized water Centrifugal dispersion to neutrality, the oxidation is obtained
Graphene；
Wherein, there is the second preset ratio between the potassium permanganate of addition and the expanded graphite；The peroxide of addition
Changing has third preset ratio between hydrogen and the expanded graphite；Volume ratio between the hydrochloric acid and deionized water is pre- for the 4th
If ratio.
Preferably, it is protected in the preparation method of aramid paper in above-mentioned X, gamma-rays, first preset ratio is 1:30
~1:40；Second preset ratio is 1:30~6:1；The third preset ratio is 3:1~10:1；Described 4th default ratio
Example is 1:5~1:10.
Preferably, it protects in the preparation method of aramid paper in above-mentioned X, gamma-rays, is prepared according to the graphene oxide
The aqueous graphene oxide of interlayer, including：
The graphene oxide is placed in hydrothermal reaction kettle, under the first preset temperature prepared by ultrasonic first preset time
The aqueous graphene oxide of the interlayer；
First preset temperature is 100 DEG C~250 DEG C, and first preset time is 1~10 hour.
Preferably, it is protected in the preparation method of aramid paper in above-mentioned X, gamma-rays, prepares the first oxygen of intercalation bismuth tungstate
Graphite alkene powder, including：
Bismuth nitrate is dissolved in the dust technology for having the 5th preset ratio with it, with vigorous stirring, by the nitre of acquisition
Sour bismuth solution is added in into wolframic acid sodium water solution, adds graphene oxide solution；
It adds in alkaline solution and pH value is adjusted to 5~5.5, then add in cetyltrimethylammonium bromide；Add poly- second
Glycol stirs the second preset time, obtains gel；
After handling the first treatment conditions of gel progress, the first graphene oxide powder of intercalation bismuth tungstate is obtained
Body；
The mass ratio of the bismuth nitrate and sodium tungstate is the 6th preset ratio；The quality of the bismuth nitrate and graphene oxide
Than for the 7th preset ratio.
Wherein, the 5th preset ratio is 1:2~1:5；6th preset ratio is 3:1-5:1；Described 7th is pre-
If ratio is 1:2~1:5；A concentration of 0.01M~0.1M of the cetyltrimethylammonium bromide；The bismuth nitrate and poly- second
The mass ratio of glycol is 1:3~1:5；Second preset time is 6~10 hours；
First treatment conditions include：Washed with ethyl alcohol, 40~60 DEG C drying and 300~500 DEG C calcining.
Preferably, above-mentioned X, gamma-rays protection aramid paper preparation method in, prepare intercalation europium oxide, samarium oxide,
Second graphene oxide powder of gadolinium oxide and barium monoxide, including：
Europium nitrate, gadolinium nitrate, samaric nitrate, barium sulfate mixed solution are added in graphene oxide solution, add in ammonium hydroxide,
After the ultrasonic third preset time of strength, the 4th preset time of hydro-thermal reaction under the second preset temperature is transferred in hydrothermal reaction kettle,
Obtain solution；
The solution obtains intercalation europium oxide, samarium oxide, gadolinium oxide and barium monoxide after the processing of second processing condition
Second graphene oxide powder.
Wherein, in the europium nitrate, gadolinium nitrate, samaric nitrate, barium sulfate mixed solution the mass ratio of europium nitrate for 30%~
40%, the mass ratio of gadolinium nitrate is 30%~40%, and the mass ratio of samaric nitrate is 10%~20%, and the mass ratio of barium sulfate is
10%~20%；The europium nitrate, gadolinium nitrate, samaric nitrate, barium sulfate mixed solution and graphene oxide mass ratio be 1:3~
1:5；The europium nitrate, gadolinium nitrate, samaric nitrate, barium sulfate mixed solution and ammonium hydroxide mass ratio be 1:3~1:6；
Third preset time is 2~4 hours；Second preset temperature is 100~300 DEG C；4th preset time
For 1~48h；
The second processing condition includes：It is washed with ethyl alcohol, 40~60 DEG C of drying, using 900~1200 DEG C of calcinings.
Preferably, it is protected in the preparation method of aramid paper in above-mentioned X, gamma-rays, according to first graphite oxide
Alkene powder and the second graphene oxide powder are prepared in the unleaded powder process of x-ray radiation safeguard function, the first oxidation stone
Molar ratio between black alkene powder and the second graphene oxide powder is 3：1~5：1.
Preferably, it protects in the preparation method of aramid paper in above-mentioned X, gamma-rays, is protected according to the x-ray radiation
The unleaded powder of function prepares the modified unleaded powder of x-ray radiation safeguard function, including：By x-ray radiation safeguard function without
Lead powder body and silane coupling agent uniformly mix, and a small amount of water is added dropwise, and mechanical agitation 1~1.5 hour adds in dissaving polymer and continues
Stirring obtains the modified unleaded powder of x-ray radiation safeguard function in 1~2 hour.
Preferably, it is protected in the preparation method of aramid paper in above-mentioned X, gamma-rays, according to the X-ray spoke of the modification
It penetrates the unleaded powder of safeguard function and prepares fibrid, including：
With the short fibre of meta-aramid for solute, using H2O as coagulator, DMAc is solvent, and anhydrous LiCl is cosolvent, at 80 DEG C
Stirring is placed on magnetic stirring apparatus to light yellow transparent solution, adding in the function powder of a certain amount of modification, to continue stirring 1~3 small
When, preparation obtains meta-aramid solution, then solution is injected in high speed shear coagulating bath, fibrid is prepared；
Wherein, a concentration of 1wt.% of the anhydrous LiCl of the cosolvent, coagulating bath H2O:DMAc quality proportionings are 9:1~1:1,
Meta-aramid solution concentration is 3wt.%-9wt.%, and the mass ratio of function powder and short fibre of aramid fiber is 1:1~1:5, fibrid
Shear rate be 41s-1~101s-1。
Preferably, above-mentioned X, gamma-rays protection aramid paper preparation method in, according to the fibrid prepare X,
Gamma-rays protects aramid paper, including：
Short fine and fibrid is mixed and is stirred evenly in water, using wet method paper machine copy paper, after molding at 80 DEG C
Drying, last 260~280 DEG C are made aramid paper with 14~20MPa pressure hot pressing, 2~8min；
Quality shared by the short fine and fibrid is mixed than being respectively 30%~70%, 70%~30%.
Above-mentioned at least one technical solution that the embodiment of the present application uses can reach following advantageous effect：By by X, γ
Alpha ray shield agent-nano-powder is added to by the way that silane coupling agent and dissaving polymer are modified in aramid fiber solution, due to virtue
Synthetic fibre and Hyperbranched Polymer with Terminal Amido interfacial effect are good, and the additive amount of functional powders is improved in prepared aramid paper,
Prepared aramid paper not only has good intensity and high temperature resistance, and also high with X, gamma ray shielding rate, persistence is good,
Unleaded light-weighted advantage has good application prospect in terms of X, gamma Rays protection.
Description of the drawings
Attached drawing described herein is used for providing further understanding of the present application, forms the part of the application, this Shen
Illustrative embodiments and their description please do not form the improper restriction to the application for explaining the application.In the accompanying drawings：
Fig. 1 is a kind of X provided by the embodiments of the present application, the flow diagram of the preparation method of gamma-rays protection aramid paper.
Specific embodiment
Purpose, technical scheme and advantage to make the application are clearer, below in conjunction with the application specific embodiment and
Technical scheme is clearly and completely described in corresponding attached drawing.Obviously, described embodiment is only the application one
Section Example, instead of all the embodiments.Based on the embodiment in the application, those of ordinary skill in the art are not doing
Go out all other embodiments obtained under the premise of creative work, shall fall in the protection scope of this application.
Below in conjunction with attached drawing, the technical solution that each embodiment of the application provides is described in detail.
Fig. 1 is a kind of X provided by the embodiments of the present application, the flow diagram of the preparation method of gamma-rays protection aramid paper.
The preparation method includes：Graphene oxide is obtained, and the aqueous graphene oxide of interlayer is prepared according to the graphene oxide,
As shown in the step S101 in Fig. 1；The first graphene oxide powder of intercalation bismuth tungstate is prepared, such as the step S103 institutes in Fig. 1
Show；The second graphene oxide powder of intercalation europium oxide, samarium oxide, gadolinium oxide and barium monoxide is prepared, such as the step S105 in Fig. 1
It is shown；It is unleaded that x-ray radiation safeguard function is prepared according to first graphene oxide powder and the second graphene oxide powder
Powder, as shown in the step S107 in Fig. 1；Modified X-ray is prepared according to the unleaded powder of the x-ray radiation safeguard function
The unleaded powder of radiation protection function, as shown in the step S109 in Fig. 1；According to the x-ray radiation safeguard function of the modification without
Lead powder body prepares fibrid, as shown in the step S111 in Fig. 1；X, gamma-rays protection aramid fiber are prepared according to the fibrid
Paper, as shown in the step S113 in Fig. 1.
Specifically, step S101, obtains graphene oxide, and prepare the aqueous oxidation of interlayer according to the graphene oxide
Graphene.
The process for obtaining graphene oxide includes：Expanded graphite and the concentrated sulfuric acid are mixed and abundant according to the first preset ratio
After stirring, potassium permanganate is added in, until the potassium permanganate total overall reaction, adds deionized water and be stirred, is uniformly mixed
After add in hydrogen peroxide, obtain the first mixed solution；It is mixed with cleaning described first under the conditions of hydrochloric acid and deionized water Centrifugal dispersion
Solution is closed to neutrality, obtains the graphene oxide.
Wherein, there is the second preset ratio between the potassium permanganate of addition and the expanded graphite；The peroxide of addition
Changing has third preset ratio between hydrogen and the expanded graphite；Volume ratio between the hydrochloric acid and deionized water is pre- for the 4th
If ratio.
Specifically, first preset ratio is 1:30~1:40；Second preset ratio is 1:30~6:1；It is described
Third preset ratio is 3:1~10:1；4th preset ratio is 1:5~1:10.
Further, the aqueous graphene oxide of interlayer is prepared according to the graphene oxide, including：By the oxidation stone
Black alkene is placed in hydrothermal reaction kettle, and ultrasonic first preset time prepares the aqueous oxidation stone of the interlayer under the first preset temperature
Black alkene；Wherein described first preset temperature is 100 DEG C~250 DEG C, and first preset time is 1~10 hour.
Step S103 prepares the first graphene oxide powder of intercalation bismuth tungstate.
Specifically, the first graphene oxide powder of intercalation bismuth tungstate is prepared, including：Bismuth nitrate is dissolved in be had with it
In the dust technology of 5th preset ratio, with vigorous stirring, the bismuth nitrate solution of acquisition is added in into wolframic acid sodium water solution, then
Add in graphene oxide solution；It adds in alkaline solution and pH value is adjusted to 5~5.5, then add in cetyltrimethylammonium bromide；
It adds polyethylene glycol and stirs the second preset time, obtain gel；After handling the first treatment conditions of gel progress,
Obtain the first graphene oxide powder of intercalation bismuth tungstate；The mass ratio of the bismuth nitrate and sodium tungstate is the 6th preset ratio；
The mass ratio of the bismuth nitrate and graphene oxide is the 7th preset ratio.
Wherein, the 5th preset ratio is 1:2~1:5；6th preset ratio is 3:1-5:1；Described 7th is pre-
If ratio is 1:2~1:5；A concentration of 0.01M~0.1M of the cetyltrimethylammonium bromide；The bismuth nitrate and poly- second
The mass ratio of glycol is 1:3~1:5；Second preset time is 6~10 hours；
First treatment conditions include：Washed with ethyl alcohol, 40~60 DEG C drying and 300~500 DEG C calcining.
Step S105 prepares the second graphene oxide powder of intercalation europium oxide, samarium oxide, gadolinium oxide and barium monoxide.
Specifically, the second graphene oxide powder of intercalation europium oxide, samarium oxide, gadolinium oxide and barium monoxide is prepared, including：
Europium nitrate, gadolinium nitrate, samaric nitrate, barium sulfate mixed solution are added in graphene oxide solution, add in ammonium hydroxide, strength ultrasound
After third preset time, the 4th preset time of hydro-thermal reaction under the second preset temperature is transferred in hydrothermal reaction kettle, obtains solution；
The solution obtains the second oxidation of intercalation europium oxide, samarium oxide, gadolinium oxide and barium monoxide after the processing of second processing condition
Graphene powder.
Wherein, in the europium nitrate, gadolinium nitrate, samaric nitrate, barium sulfate mixed solution the mass ratio of europium nitrate for 30%~
40%, the mass ratio of gadolinium nitrate is 30%~40%, and the mass ratio of samaric nitrate is 10%~20%, and the mass ratio of barium sulfate is
10%~20%；The europium nitrate, gadolinium nitrate, samaric nitrate, barium sulfate mixed solution and graphene oxide mass ratio be 1:3~
1:5；The europium nitrate, gadolinium nitrate, samaric nitrate, barium sulfate mixed solution and ammonium hydroxide mass ratio be 1:3~1:6；Third is preset
Time is 2~4 hours；Second preset temperature is 100~300 DEG C；4th preset time is 1~48h；Described second
Treatment conditions include：It is washed with ethyl alcohol, 40~60 DEG C of drying, using 900~1200 DEG C of calcinings.
It should be noted that in the embodiment of the present application, the execution sequence of step S103 and step S105 can be interchanged,
That is, it is possible to first carry out step S103, then step S105 is carried out, can also first carry out step S105, then carry out step S103.
Step S107 prepares x-ray radiation according to first graphene oxide powder and the second graphene oxide powder
The unleaded powder of safeguard function.
X-ray radiation protection work(is being prepared according to first graphene oxide powder and the second graphene oxide powder
In the unleaded powder process of energy, the molar ratio between first graphene oxide powder and the second graphene oxide powder is 3：1
~5：1.
Specifically, first graphene oxide powder and the second graphene oxide powder are pressed 3：1~5：1 molar ratio
It uniformly mixes up to the unleaded powder of x-ray radiation safeguard function.
Step S109 prepares modified x-ray radiation according to the unleaded powder of the x-ray radiation safeguard function and protects work(
It can unleaded powder.
Specifically, the unleaded powder of x-ray radiation safeguard function and silane coupling agent are uniformly mixed, a small amount of water, machine is added dropwise
Tool stirs 1~1.5 hour, and addition dissaving polymer continues stirring and obtains within 1~2 hour modified x-ray radiation safeguard function
Unleaded powder.
Step S111 prepares fibrid according to the unleaded powder of x-ray radiation safeguard function of the modification.
Specifically, the unleaded powder of x-ray radiation safeguard function according to the modification prepares fibrid, including：With
Aramid fiber short fibre in position is solute, and using H2O as coagulator, DMAc is solvent, and anhydrous LiCl is cosolvent, and magnetic agitation is placed at 80 DEG C
To light yellow transparent solution, the function powder for adding in a certain amount of modification continues stirring 1~3 hour for stirring on device, between preparation obtains
Position aramid fiber solution, then solution is injected in high speed shear coagulating bath, fibrid is prepared.
Wherein, a concentration of 1wt.% of the anhydrous LiCl of the cosolvent, coagulating bath H2O:DMAc quality proportionings are 9:1~1:1,
Meta-aramid solution concentration is 3wt.%-9wt.%, and the mass ratio of function powder and short fibre of aramid fiber is 1:1~1:5, fibrid
Shear rate be 41s-1~101s-1.
Step S113 prepares X according to the fibrid, gamma-rays protects aramid paper.
Specifically, X, gamma-rays protection aramid paper are prepared according to the fibrid, including：Short fine and fibrid is mixed
Conjunction stirs evenly in water, using wet method paper machine copy paper, is dried at 80 DEG C after molding, last 260~280 DEG C with 14~
Aramid paper is made in 2~8min of 20MPa pressure hot pressing.
Wherein, the quality shared by the short fine and fibrid is mixed than being respectively 30%~70%, 70%~30%.
Next, illustrated with specific embodiment.
First, 4g expanded graphites and the 184ml concentrated sulfuric acids is taken to be placed in glass container, is sufficiently stirred under ice-water bath；Slowly add
Enter 3g potassium permanganate up to potassium permanganate total overall reaction, add 200ml deionized waters mechanical agitation at a certain temperature, mix
The hydrogen peroxide of 20ml is added in after uniformly, solution becomes glassy yellow by brownish black；With 300ml hydrochloric acid and deionized water (dilute hydrochloric acid
Ratio with deionized water is 1:9) cleaning solution to neutrality, obtains graphene oxide under the conditions of Centrifugal dispersion；
Then, the graphene oxide of above-mentioned preparation is taken in hydrothermal reaction kettle, and ultrasound is made containing interlayer for 2 hours at 135 DEG C
The graphene oxide of water；
Next, five water bismuth nitrates of 3g are dissolved in 6g dust technologies, with vigorous stirring, nitrate solution is slowly added
Enter into the aqueous solution containing 1g sodium tungstates, add graphene oxide solutions of the 6g containing intermediary water, add in sodium hydroxide solution
PH to 5~5.5 is adjusted, then adds in 2.5g0.01M cetyltrimethylammonium bromide, adds in 9g polyethylene glycol stirring 6~10
Hour, obtained gel is washed with ethyl alcohol, 40~60 DEG C of drying, and 300~500 DEG C of calcinings obtain the oxidation stone of intercalation bismuth tungstate
Black alkene powder A；
Subsequently, the mixed solution of 1g europium nitrates, gadolinium nitrate, samaric nitrate, barium sulfate is added to oxygen of the 2g containing intermediary water
In graphite alkene solution (europium nitrate, gadolinium nitrate, samaric nitrate, the mass component shared by barium sulfate than be respectively 30%, 30%,
20% and 20%), it adds in 3g ammonium hydroxide strength ultrasound 2-4 hours, is transferred to 100~300 DEG C in hydrothermal reaction kettle of temperature condition
1~48h of lower hydro-thermal reaction, obtained solution is washed with ethyl alcohol, 40~60 DEG C of drying, using 900~1200 DEG C of calcinings, is obtained
Intercalation europium oxide, samarium oxide, gadolinium oxide and barium monoxide graphene oxide powder B；
Secondly, powder A and powder B is pressed 4：1 molar ratio is uniformly mixed to get x-ray radiation safeguard function without lead powder
Body.
Next, 1g function powders and 2g silane coupling agents are uniformly mixed, a small amount of water is added dropwise, mechanical agitation 1~1.5 is small
When, 2.5 dissaving polymers of addition continue stirring and obtain modified function powder in 1~2 hour；
Then, with the short fibre of 5g meta-aramids for solute, using 45gH2O as coagulator, 100gDMAc is solvent, and 5g is anhydrous
LiCl is cosolvent, and stirring on magnetic stirring apparatus is placed at 80 DEG C and, to light yellow transparent solution, adds in the work(of a certain amount of modifications of 5g
Energy powder continues stirring 2 hours, and preparation obtains meta-aramid solution, then solution is injected in high speed shear coagulating bath with 41s-1
Shear rate fibrid is prepared；
Finally, it is 3g is short fine and 7g fibrids are mixed and stirred evenly in water, using wet method paper machine copy paper, after molding
It is dried at 80 DEG C, last 270 DEG C are made aramid paper with 14MPa pressure hot pressing 2min.
In the preparation method of a kind of X provided by the embodiments of the present application, gamma-rays protection aramid paper, by by X, gamma-rays screen
It covers agent-nano-powder by the way that silane coupling agent and dissaving polymer are modified to be added in aramid fiber solution, due to aramid fiber and end
Amino dissaving polymer interfacial effect is good, and the additive amount of functional powders is improved in prepared aramid paper, prepared
Aramid paper not only there is good intensity and high temperature resistance, also high with X, gamma ray shielding rate, persistence is good, unleaded light
, there is good application prospect in the advantages of quantization in terms of X, gamma Rays protection.
Each embodiment in this specification is described by the way of progressive, identical similar portion between each embodiment
Point just to refer each other, and the highlights of each of the examples are difference from other examples.
The foregoing is merely embodiments herein, are not limited to the application.For those skilled in the art
For, the application can have various modifications and variations.All any modifications made within spirit herein and principle are equal
Replace, improve etc., it should be included within the scope of claims hereof.
Claims (10)
1. a kind of X, gamma-rays protect the preparation method of aramid paper, which is characterized in that including：
Graphene oxide is obtained, and the aqueous graphene oxide of interlayer is prepared according to the graphene oxide；
Prepare the first graphene oxide powder of intercalation bismuth tungstate；
Prepare the second graphene oxide powder of intercalation europium oxide, samarium oxide, gadolinium oxide and barium monoxide；
It is unleaded that x-ray radiation safeguard function is prepared according to first graphene oxide powder and the second graphene oxide powder
Powder；
The modified unleaded powder of x-ray radiation safeguard function is prepared according to the unleaded powder of the x-ray radiation safeguard function；
Fibrid is prepared according to the unleaded powder of x-ray radiation safeguard function of the modification；
X, gamma-rays protection aramid paper are prepared according to the fibrid.
2. X according to claim 1, gamma-rays protect the preparation method of aramid paper, which is characterized in that obtain graphite oxide
The process of alkene includes：
After expanded graphite and the concentrated sulfuric acid are mixed and are sufficiently stirred according to the first preset ratio, potassium permanganate is added in, until described
Potassium permanganate total overall reaction adds deionized water and is stirred, adds in hydrogen peroxide after mixing, and it is molten to obtain the first mixing
Liquid；
With first mixed solution is cleaned under the conditions of hydrochloric acid and deionized water Centrifugal dispersion to neutrality, the graphite oxide is obtained
Alkene；
Wherein, there is the second preset ratio between the potassium permanganate of addition and the expanded graphite；The hydrogen peroxide of addition
There is third preset ratio between the expanded graphite；Volume ratio between the hydrochloric acid and deionized water is the 4th default ratio
Example.
3. X according to claim 2, gamma-rays protect the preparation method of aramid paper, which is characterized in that described first is default
Ratio is 1:30~1:40；Second preset ratio is 1:30~6:1；The third preset ratio is 3:1~10:1；It is described
4th preset ratio is 1:5~1:10.
4. X according to claim 1, gamma-rays protect the preparation method of aramid paper, which is characterized in that according to the oxidation
Graphene prepares the aqueous graphene oxide of interlayer, including：
The graphene oxide is placed in hydrothermal reaction kettle, under the first preset temperature described in ultrasonic first preset time preparation
The aqueous graphene oxide of interlayer；
First preset temperature is 100 DEG C~250 DEG C, and first preset time is 1~10 hour.
5. X according to claim 1, gamma-rays protect the preparation method of aramid paper, which is characterized in that prepare intercalation wolframic acid
First graphene oxide powder of bismuth, including：
Bismuth nitrate is dissolved in the dust technology for having the 5th preset ratio with it, with vigorous stirring, by the bismuth nitrate of acquisition
Solution is added in into wolframic acid sodium water solution, adds graphene oxide solution；
It adds in alkaline solution and pH value is adjusted to 5~5.5, then add in cetyltrimethylammonium bromide；Add polyethylene glycol
The second preset time is stirred, obtains gel；
After handling the first treatment conditions of gel progress, the first graphene oxide powder of intercalation bismuth tungstate is obtained；
The mass ratio of the bismuth nitrate and sodium tungstate is the 6th preset ratio；The mass ratio of the bismuth nitrate and graphene oxide is
7th preset ratio.
Wherein, the 5th preset ratio is 1:2~1:5；6th preset ratio is 3:1-5:1；Described 7th default ratio
Example is 1:2~1:5；A concentration of 0.01M~0.1M of the cetyltrimethylammonium bromide；The bismuth nitrate and polyethylene glycol
Mass ratio be 1:3~1:5；Second preset time is 6~10 hours；
First treatment conditions include：Washed with ethyl alcohol, 40~60 DEG C drying and 300~500 DEG C calcining.
6. X according to claim 1, gamma-rays protect the preparation method of aramid paper, which is characterized in that prepare intercalation oxidation
Europium, samarium oxide, gadolinium oxide and barium monoxide the second graphene oxide powder, including：
Europium nitrate, gadolinium nitrate, samaric nitrate, barium sulfate mixed solution are added in graphene oxide solution, add in ammonium hydroxide, strength
After ultrasonic third preset time, the 4th preset time of hydro-thermal reaction under the second preset temperature is transferred in hydrothermal reaction kettle, is obtained
Solution；
The solution obtains the second of intercalation europium oxide, samarium oxide, gadolinium oxide and barium monoxide after the processing of second processing condition
Graphene oxide powder.
Wherein, the mass ratio of europium nitrate is 30%~40% in the europium nitrate, gadolinium nitrate, samaric nitrate, barium sulfate mixed solution,
The mass ratio of gadolinium nitrate is 30%~40%, and the mass ratio of samaric nitrate is 10%~20%, the mass ratio of barium sulfate for 10%~
20%；The europium nitrate, gadolinium nitrate, samaric nitrate, barium sulfate mixed solution and graphene oxide mass ratio be 1:3~1:5；Institute
The mass ratio for stating europium nitrate, gadolinium nitrate, samaric nitrate, barium sulfate mixed solution and ammonium hydroxide is 1:3~1:6；
Third preset time is 2~4 hours；Second preset temperature is 100~300 DEG C；4th preset time for 1~
48h；
The second processing condition includes：It is washed with ethyl alcohol, 40~60 DEG C of drying, using 900~1200 DEG C of calcinings.
7. X according to claim 1, gamma-rays protect the preparation method of aramid paper, which is characterized in that according to described the
One graphene oxide powder and the second graphene oxide powder are prepared in the unleaded powder process of x-ray radiation safeguard function, described
Molar ratio between first graphene oxide powder and the second graphene oxide powder is 3：1~5：1.
8. X according to claim 1, gamma-rays protect the preparation method of aramid paper, which is characterized in that are penetrated according to the X-
The unleaded powder of beta radiation safeguard function prepares the modified unleaded powder of x-ray radiation safeguard function, including：By x-ray radiation
The unleaded powder of safeguard function and silane coupling agent uniformly mix, and a small amount of water is added dropwise, and mechanical agitation 1~1.5 hour adds in hyperbranched
Polymer continues stirring and obtains within 1~2 hour the modified unleaded powder of x-ray radiation safeguard function.
9. X according to claim 1, gamma-rays protect the preparation method of aramid paper, which is characterized in that according to the modification
The unleaded powder of x-ray radiation safeguard function prepare fibrid, including：
With the short fibre of meta-aramid for solute, using H2O as coagulator, DMAc is solvent, and anhydrous LiCl is cosolvent, is placed at 80 DEG C
To light yellow transparent solution, the function powder for adding in a certain amount of modification continues stirring 1~3 hour, matches for stirring on magnetic stirring apparatus
Meta-aramid solution is made, then solution is injected in high speed shear coagulating bath, fibrid is prepared；
Wherein, a concentration of 1wt.% of the anhydrous LiCl of the cosolvent, coagulating bath H2O:DMAc quality proportionings are 9:1~1:1, meta position
Aramid fiber solution concentration is 3wt.%-9wt.%, and the mass ratio of function powder and short fibre of aramid fiber is 1:1~1:5, fibrid is cut
Cutting speed rate is 41s-1~101s-1。
10. X according to claim 1, gamma-rays protect the preparation method of aramid paper, which is characterized in that according to described heavy
It analyses fiber and prepares X, gamma-rays protection aramid paper, including：
Short fine and fibrid is mixed and is stirred evenly in water, using wet method paper machine copy paper, is dried at 80 DEG C after molding,
Last 260~280 DEG C are made aramid paper with 14~20MPa pressure hot pressing, 2~8min；
Quality shared by the short fine and fibrid is mixed than being respectively 30%~70%, 70%~30%.
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| CN116987303A (en) * | 2023-07-31 | 2023-11-03 | 陕西科技大学 | CsPbBr of high-efficient X ray shielding 3 ANF flexible composite film and preparation method thereof |
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