CN108193549B - 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
- Publication number
- CN108193549B CN108193549B CN201810189668.3A CN201810189668A CN108193549B CN 108193549 B CN108193549 B CN 108193549B CN 201810189668 A CN201810189668 A CN 201810189668A CN 108193549 B CN108193549 B CN 108193549B
- Authority
- CN
- China
- Prior art keywords
- graphene oxide
- powder
- nitrate
- gamma
- ratio
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
-
- 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, the preparation method of gamma-rays protection aramid paper, by by X, gamma ray shielding agent-nano-powder is by silane coupling agent and dissaving polymer is modified is added 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, gamma Rays protection aspect has good application prospect.
Description
Technical field
This application involves radiation protection field more particularly to the preparation methods of a kind of X, gamma-rays protection aramid paper.
Background technique
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 is more than that dosage even can be carcinogenic, brings and seriously threaten 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 be processed into various protective garments, the helmet, protective gloves etc..But these protective articles gas permeabilities
Difference, it is heavy, wear uncomfortable, while lead all has serious harm to human body and environment.
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 back shield
Layer and superficial layer, back sheath includes opposite first side and second side, and metal coating, closely sealed back are arranged 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 successively attached with for the electro-magnetic screen layer of radiation protection on a side and the back 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 passes through the mesh that setting shielded layer reaches 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.
Summary of the invention
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 adopts the following technical solutions:
The embodiment of the present application provides the preparation method of a kind of X, gamma-rays protection aramid paper, comprising:
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；
According to the modified x-ray radiation safeguard function of the unleaded powder preparation of the x-ray radiation safeguard function without lead powder
Body；
Fibrid is prepared according to the unleaded powder of x-ray radiation safeguard function of the modification；
X is prepared according to the fibrid, gamma-rays protects aramid paper.
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, until
The potassium permanganate total overall reaction, adds deionized water and is stirred, hydrogen peroxide is added 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 and the expanded graphite of addition；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 the 4th pre-
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, comprising:
The graphene oxide is placed in hydrothermal reaction kettle, the ultrasonic first preset time preparation under the first preset temperature
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, comprising:
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 into wolframic acid sodium water solution, adds graphene oxide solution；
Alkaline solution is added, pH value is adjusted to 5~5.5, cetyltrimethylammonium bromide is then added；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；The concentration of the cetyltrimethylammonium bromide is 0.01M~0.1M；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: with ethanol washing, 40~60 DEG C of drying and 300~500 DEG C of calcinings.
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, comprising:
Europium nitrate, gadolinium nitrate, samaric nitrate, barium sulfate mixed solution are added in graphene oxide solution, ammonium hydroxide is added,
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, the europium nitrate, gadolinium nitrate, samaric nitrate, in barium sulfate mixed solution the mass ratio of europium nitrate be 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: to be dried with ethanol washing, 40~60 DEG C, is calcined using 900~1200 DEG C.
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 modified unleaded powder of x-ray radiation safeguard function of function unleaded powder preparation, comprising: 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, mechanical stirring 1~1.5 hour, dissaving polymer is added 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, comprising:
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, the function powder of a certain amount of modification is added, and 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, the anhydrous LiCl concentration of the cosolvent is 1wt.%, coagulating bath H2O:DMAc quality proportioning is 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, comprising:
Short fine and fibrid is mixed and is stirred evenly in water, using wet process paper machine copy paper, after molding at 80 DEG C
Drying, last 260~280 DEG C are made aramid paper with 14~20MPa, 2~8min of pressure hot pressing；
Quality shared by the short fine and fibrid is mixed than being respectively 30%~70%, 70%~30%.
At least one above-mentioned technical solution that the embodiment of the present application uses can reach following the utility model has the advantages that by by X, γ
Alpha ray shield agent-nano-powder is by silane coupling agent and dissaving polymer is modified is added 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, also has X, gamma ray shielding rate high, and persistence is good,
Unleaded light-weighted advantage has good application prospect in terms of X, gamma Rays protection.
Detailed description of the invention
The drawings described herein are used to provide a further understanding of the present application, constitutes part of this application, this Shen
Illustrative embodiments and their description please are not constituted an undue limitation on the present application for explaining the application.In the accompanying drawings:
Fig. 1 is a kind of X provided by the embodiments of the present application, gamma-rays protect aramid paper preparation method flow diagram.
Specific embodiment
To keep the purposes, technical schemes and advantages of the application 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
Every other embodiment obtained under the premise of creative work out, shall fall in the protection scope of this application.
Below in conjunction with attached drawing, the technical scheme provided by various embodiments of the present application will be described in detail.
Fig. 1 is a kind of X provided by the embodiments of the present application, gamma-rays protect aramid paper preparation method flow diagram.
The preparation method includes: acquisition graphene oxide, and prepares the aqueous graphene oxide of interlayer according to the graphene oxide,
Shown in step S101 as shown in figure 1；The first graphene oxide powder of intercalation bismuth tungstate is prepared, step S103 institute as shown in figure 1
Show；Prepare the second graphene oxide powder of intercalation europium oxide, samarium oxide, gadolinium oxide and barium monoxide, step S105 as shown in figure 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, shown in step S107 as shown in figure 1；According to the modified X-ray of the unleaded powder preparation of the x-ray radiation safeguard function
The unleaded powder of radiation protection function, shown in step S109 as shown in figure 1；According to the x-ray radiation safeguard function of the modification without
Lead powder body prepares fibrid, shown in step S111 as shown in figure 1；X is prepared according to the fibrid, gamma-rays protects aramid fiber
Paper, shown in step S113 as shown in figure 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: to mix expanded graphite and the concentrated sulfuric acid and abundant according to the first preset ratio
After stirring, potassium permanganate is added, until the potassium permanganate total overall reaction, adds deionized water and be stirred, is uniformly mixed
After hydrogen peroxide is added, 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 and the expanded graphite of addition；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 the 4th pre-
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, comprising: 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 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, preparing the first graphene oxide powder of intercalation bismuth tungstate, comprising: be dissolved in bismuth nitrate has with it
In the dust technology of 5th preset ratio, with vigorous stirring, the bismuth nitrate solution of acquisition is added into wolframic acid sodium water solution, then
Graphene oxide solution is added；Alkaline solution is added, pH value is adjusted to 5~5.5, cetyltrimethylammonium bromide is then added；
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；The concentration of the cetyltrimethylammonium bromide is 0.01M~0.1M；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: with ethanol washing, 40~60 DEG C of drying and 300~500 DEG C of calcinings.
Step S105 prepares the second graphene oxide powder of intercalation europium oxide, samarium oxide, gadolinium oxide and barium monoxide.
Specifically, preparing the second graphene oxide powder of intercalation europium oxide, samarium oxide, gadolinium oxide and barium monoxide, comprising:
Europium nitrate, gadolinium nitrate, samaric nitrate, barium sulfate mixed solution are added in graphene oxide solution, ammonium hydroxide, strength ultrasound is added
After third preset time, it is transferred in hydrothermal reaction kettle the 4th preset time of hydro-thermal reaction under the second preset temperature, 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, the europium nitrate, gadolinium nitrate, samaric nitrate, in barium sulfate mixed solution the mass ratio of europium nitrate be 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 default
Time is 2~4 hours；Second preset temperature is 100~300 DEG C；4th preset time is 1~48h；Described second
Treatment conditions include: to be dried with ethanol washing, 40~60 DEG C, are calcined using 900~1200 DEG C.
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 function 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 to be pressed to the molar ratio of 3:1~5:1
It uniformly mixes up to the unleaded powder of x-ray radiation safeguard function.
Step S109, according to the unleaded powder preparation of the x-ray radiation safeguard function, modified x-ray radiation protects function
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 dissaving polymer is added and continues to obtain modified x-ray radiation safeguard function in stirring 1~2 hour
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, comprising: with
Aramid fiber short fibre in position is solute, and using H2O as coagulator, DMAc is solvent, and anhydrous LiCl is cosolvent, is placed in magnetic agitation at 80 DEG C
To light yellow transparent solution, the function powder that a certain amount of modification is added 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, the anhydrous LiCl concentration of the cosolvent is 1wt.%, and coagulating bath H2O:DMAc quality proportioning is 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, preparing X according to the fibrid, gamma-rays protects aramid paper, comprising: mix short fine and fibrid
Conjunction stirs evenly in water, using wet process paper machine copy paper, dries at 80 DEG C after molding, last 260~280 DEG C with 14~
Aramid paper is made in 20MPa 2~8min of pressure hot pressing.
Wherein, quality shared by the short fine and fibrid is mixed than being respectively 30%~70%, 70%~30%.
Next, being illustrated with specific embodiment.
Firstly, 4g expanded graphite and the 184ml concentrated sulfuric acid is taken to be placed in glass container, it is sufficiently stirred under ice-water bath；Slowly add
Enter 3g potassium permanganate up to potassium permanganate total overall reaction, add 200ml deionized water mechanical stirring at a certain temperature, mixes
The hydrogen peroxide of 20ml is added after uniformly, solution becomes glassy yellow by brownish black；With 300ml hydrochloric acid and deionized water (dilute hydrochloric acid
Ratio with deionized water is cleaning solution under the conditions of 1:9) Centrifugal dispersion to neutrality, obtains graphene oxide；
Then, it takes the graphene oxide of above-mentioned preparation in hydrothermal reaction kettle, is made within ultrasound 2 hours at 135 DEG C and contains interlayer
The graphene oxide of water；
Next, five water bismuth nitrate of 3g is dissolved in 6g dust technology, with vigorous stirring, nitrate solution is slowly added
Enter into the aqueous solution containing 1g sodium tungstate, add graphene oxide solution of the 6g containing intermediary water, sodium hydroxide solution is added
PH to 5~5.5 is adjusted, 2.5g0.01M cetyltrimethylammonium bromide is then added, 9g polyethylene glycol stirring 6~10 is added
Hour, obtained gel ethanol washing, 40~60 DEG C of drying, 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 nitrate, 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, mass component shared by barium sulfate than be respectively 30%, 30%,
20% and 20%), 3g ammonium hydroxide strength is added 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 ethanol washing, 40~60 DEG C of drying, calcines using 900~1200 DEG C, obtains
Intercalation europium oxide, samarium oxide, gadolinium oxide and barium monoxide graphene oxide powder B；
Secondly, powder A and powder B is uniformly mixed to get x-ray radiation safeguard function without lead powder by the molar ratio of 4:1
Body.
Next, 1g function powder and 2g silane coupling agent are uniformly mixed, a small amount of water is added dropwise, mechanical stirring 1~1.5 is small
When, 2.5 dissaving polymers are added and continue to obtain modified function powder in stirring 1~2 hour；
Then, with the short fibre of 5g meta-aramid for solute, using 45gH2O as coagulator, 100gDMAc is solvent, and 5g is anhydrous
LiCl is cosolvent, stirring on magnetic stirring apparatus is placed at 80 DEG C, the function of a certain amount of modification of 5g is added to light yellow transparent solution
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；
It is stirred evenly in water finally, the short fine and 7g fibrid of 3g is mixed, using wet process 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
Agent-nano-powder is covered by silane coupling agent and dissaving polymer is modified is 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 have X, gamma ray shielding rate high, persistence is good, unleaded light
, there is good application prospect in the advantages of quantization in terms of X, gamma Rays protection.
All the embodiments in this specification are described in a progressive manner, same and similar portion between each embodiment
Dividing may refer to each other, and each embodiment focuses on the differences from other embodiments.
The above description is only an example of the present application, is not intended to limit this application.For those skilled in the art
For, various changes and changes are possible in this application.All any modifications made within the spirit and principles of the present application are equal
Replacement, improvement etc., should be included within the scope of the claims of this application.
Claims (9)
1. the preparation method of a kind of X, gamma-rays protection aramid paper characterized by comprising acquisition graphene oxide, and according to
The graphene oxide prepares the aqueous graphene oxide of interlayer；Prepare the first graphene oxide powder of intercalation bismuth tungstate；System
Second graphene oxide powder of standby 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；
According to the modified unleaded powder of x-ray radiation safeguard function of the unleaded powder preparation 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 is prepared according to the fibrid, gamma-rays protects aramid paper；
Prepare the second graphene oxide powder of intercalation europium oxide, samarium oxide, gadolinium oxide and barium monoxide, comprising:
Europium nitrate, gadolinium nitrate, samaric nitrate, barium sulfate mixed solution are added in graphene oxide solution, ammonium hydroxide, strength is added
After ultrasonic third preset time, it is transferred in hydrothermal reaction kettle the 4th preset time of hydro-thermal reaction under the second preset temperature, 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 europium nitrate, gadolinium nitrate, samaric nitrate, the mass ratio of europium nitrate is 30%~40% in 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 is 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 is 1~48h；
The second processing condition includes: to be dried with ethanol washing, 40~60 DEG C, is calcined using 900~1200 DEG C.
2. the preparation method of X according to claim 1, gamma-rays protection 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 of mass volume ratio, permanganic acid is added
Potassium, until the potassium permanganate total overall reaction, adds deionized water and be stirred, hydrogen peroxide is added after mixing, obtain
To the first mixed solution；
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, the mass ratio between the potassium permanganate and the expanded graphite of addition is the second preset ratio；The mistake of addition
Volume mass ratio between hydrogen oxide and the expanded graphite is third preset ratio；Body between the hydrochloric acid and deionized water
Product is than being the 4th preset ratio.
3. the preparation method of X according to claim 2, gamma-rays protection 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. the preparation method of X according to claim 1, gamma-rays protection aramid paper, which is characterized in that according to the oxidation
Graphene prepares the aqueous graphene oxide of interlayer, comprising:
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. the preparation method of X according to claim 1, gamma-rays protection aramid paper, which is characterized in that prepare intercalation wolframic acid
First graphene oxide powder of bismuth, comprising:
Bismuth nitrate is dissolved in the dust technology for having the 5th preset ratio with it, the 5th preset ratio is mass ratio,
It is vigorously stirred down, the bismuth nitrate solution of acquisition is added into wolframic acid sodium water solution, graphene oxide solution is added；
Alkaline solution is added, pH value is adjusted to 5~5.5, cetyltrimethylammonium bromide is then added；Add polyethylene glycol
The second preset time is stirred, gel is obtained；
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 the 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；The concentration of the cetyltrimethylammonium bromide is 0.01M~0.1M；The bismuth nitrate and polyethylene glycol
Mass ratio be 1:3~1:5；Second preset time is 6~10 hours；First treatment conditions include: to be washed with ethyl alcohol
Wash, 40~60 DEG C drying and 300~500 DEG C calcining.
6. the preparation method of X according to claim 1, gamma-rays protection 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.
7. the preparation method of X according to claim 1, gamma-rays protection aramid paper, which is characterized in that penetrated according to the X-
The modified unleaded powder of x-ray radiation safeguard function of the unleaded powder preparation of beta radiation safeguard function, comprising: 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, mechanical stirring 1~1.5 hour, is added hyperbranched
Polymer continues to obtain within stirring 1~2 hour the modified unleaded powder of x-ray radiation safeguard function.
8. the preparation method of X according to claim 1, gamma-rays protection aramid paper, which is characterized in that according to the modification
The unleaded powder of x-ray radiation safeguard function prepare fibrid, comprising:
With the short fibre of meta-aramid for solute, with H2O is coagulator, and DMAc is solvent, and anhydrous LiCl is cosolvent, is placed at 80 DEG C
To light yellow transparent solution, the function powder that a certain amount of modification is added 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, the anhydrous LiCl concentration of the cosolvent is 1wt.%, coagulating bath H2O:DMAc quality proportioning is 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, and fibrid is cut
Cutting speed rate is 41s-1~101s-1。
9. the preparation method of X according to claim 1, gamma-rays protection aramid paper, which is characterized in that according to the precipitating
Fiber prepares X, gamma-rays protects aramid paper, comprising:
Short fine and fibrid is mixed and is stirred evenly in water, using wet process paper machine copy paper, is dried at 80 DEG C after molding,
Last 260~280 DEG C are made aramid paper with 14~20MPa, 2~8min of pressure hot pressing；
Quality shared by the short fine and fibrid is mixed than being respectively 30%~70%, 70%~30%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810189668.3A CN108193549B (en) | 2018-03-08 | 2018-03-08 | A kind of preparation method of X, gamma-rays protection aramid paper |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810189668.3A CN108193549B (en) | 2018-03-08 | 2018-03-08 | A kind of preparation method of X, gamma-rays protection aramid paper |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108193549A CN108193549A (en) | 2018-06-22 |
| CN108193549B true CN108193549B (en) | 2019-10-22 |
Family
ID=62595274
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810189668.3A Active CN108193549B (en) | 2018-03-08 | 2018-03-08 | A kind of preparation method of X, gamma-rays protection aramid paper |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108193549B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115627556B (en) * | 2022-10-17 | 2024-01-19 | 株洲时代新材料科技股份有限公司 | High-conductivity meta-aramid fibrid resin and preparation method of fibrid thereof |
| CN116987303B (en) * | 2023-07-31 | 2024-04-26 | 陕西科技大学 | CsPbBr of high-efficient X ray shielding3ANF flexible composite film and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103066292A (en) * | 2013-01-30 | 2013-04-24 | 同济大学 | Grapheme/rare earth oxide nanometer composite material and preparation method and application thereof |
| CN103657639A (en) * | 2013-12-31 | 2014-03-26 | 长沙理工大学 | Preparation method and silicon modification method of visible light catalysis material for graphene/bismuth tungstate flake nanostructure |
| CN104846465A (en) * | 2015-05-10 | 2015-08-19 | 北京服装学院 | Preparation method of X-ray shielding surface activity rare earth/polypropylene nanocomposite fiber |
| CN105440280A (en) * | 2015-07-20 | 2016-03-30 | 杭州师范大学 | Preparation method and application of anti-radiation nylon 6 resin |
| CN106245411A (en) * | 2016-08-30 | 2016-12-21 | 烟台民士达特种纸业股份有限公司 | A kind of production method of meta-aramid fibers paper base material |
| CN106544858A (en) * | 2016-09-30 | 2017-03-29 | 旷达纤维科技有限公司 | It is a kind of that there is catalytic degradation function polyster fibre and preparation method thereof |
-
2018
- 2018-03-08 CN CN201810189668.3A patent/CN108193549B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103066292A (en) * | 2013-01-30 | 2013-04-24 | 同济大学 | Grapheme/rare earth oxide nanometer composite material and preparation method and application thereof |
| CN103657639A (en) * | 2013-12-31 | 2014-03-26 | 长沙理工大学 | Preparation method and silicon modification method of visible light catalysis material for graphene/bismuth tungstate flake nanostructure |
| CN104846465A (en) * | 2015-05-10 | 2015-08-19 | 北京服装学院 | Preparation method of X-ray shielding surface activity rare earth/polypropylene nanocomposite fiber |
| CN105440280A (en) * | 2015-07-20 | 2016-03-30 | 杭州师范大学 | Preparation method and application of anti-radiation nylon 6 resin |
| CN106245411A (en) * | 2016-08-30 | 2016-12-21 | 烟台民士达特种纸业股份有限公司 | A kind of production method of meta-aramid fibers paper base material |
| CN106544858A (en) * | 2016-09-30 | 2017-03-29 | 旷达纤维科技有限公司 | It is a kind of that there is catalytic degradation function polyster fibre and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108193549A (en) | 2018-06-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108399959B (en) | A kind of X, gamma-rays safeguard function raw powder's production technology | |
| CN108411492A (en) | A kind of preparation method of X, gamma-rays protection non-woven fabrics | |
| CN108193549B (en) | A kind of preparation method of X, gamma-rays protection aramid paper | |
| CN108411618A (en) | A kind of preparation method of X, gamma-rays protective fabric | |
| CN104313687B (en) | Preparation technology of silver nanowires with small diameter and high length-diameter ratio | |
| CN106700356B (en) | A kind of preparation method of graphene-polymer composite material | |
| CN105032341B (en) | For handling the inorganic material and preparation method thereof containing caesium, strontium, cobalt waste water | |
| CN110359151B (en) | Nuclear radiation protection yarn with temperature control function and preparation method thereof | |
| CN105399152B (en) | A kind of solvothermal preparation method of the sour nickel nano material of cobalt | |
| CN104088132A (en) | Surface modification method for carbon fiber powder | |
| CN107345063A (en) | A kind of flame retardant type nylon 6 of magnesium hydroxide expansible graphite compounding and preparation method thereof | |
| CN102320662A (en) | Cesium tungsten bronze powder and preparation method thereof | |
| CN106410187B (en) | A kind of preparation method of the nickel cobalt lithium aluminate cathode material of doping vario-property | |
| CN1566512A (en) | Antibacterial fabric and its preparation method and application | |
| CN110527252A (en) | A kind of epoxy resin neutron shielding material and the preparation method and application thereof | |
| CN108854987A (en) | The preparation method and application of iodide ion adsorbent material in a kind of waste water | |
| CN109759033A (en) | A method of haydite adsorbent material is prepared using manganese slag | |
| CN103466701A (en) | Method for preparing bismuth trioxide nanowires by using solid-phase chemical reaction | |
| CN106541150A (en) | A kind of Fe3+The preparation method of auxiliary overlength nano-silver thread | |
| CN104558703B (en) | A kind of tungsten-based composite material and preparation method thereof applied to alpha ray shield | |
| CN100360424C (en) | Method for preparing nano antimony-doped tin dioxide powder | |
| CN103603089A (en) | Radiation shielding non-woven fabric and preparation method thereof | |
| CN105624821B (en) | A kind of barium sulfate/polyvinyl alcohol composite fiber and preparation method thereof, non-woven cloth | |
| CN109763190A (en) | A kind of preparation method of conduction radiation-proof fabric | |
| CN112812498A (en) | Preparation method of functionalized carbon nanotube modified resin-based composite radiation protection material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20210926 Address after: 215200 room 217, building 23, 1188, West 2nd Ring Road, Shengze Town, Wujiang District, Suzhou City, Jiangsu Province Patentee after: SUZHOU HUAZONG TEXTILE NEW MATERIAL TECHNOLOGY Co.,Ltd. Address before: 226019 Jiangsu city of Nantong province sik Road No. 9 Patentee before: NANTONG University |
|
| TR01 | Transfer of patent right |