CN106883469B - Graphene fitting hexagonal nano lamella boron nitride composite emulsion prepares the high-strength method without quick high isolation medical glove - Google Patents
Graphene fitting hexagonal nano lamella boron nitride composite emulsion prepares the high-strength method without quick high isolation medical glove Download PDFInfo
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- CN106883469B CN106883469B CN201710139685.1A CN201710139685A CN106883469B CN 106883469 B CN106883469 B CN 106883469B CN 201710139685 A CN201710139685 A CN 201710139685A CN 106883469 B CN106883469 B CN 106883469B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L7/00—Compositions of natural rubber
- C08L7/02—Latex
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- A—HUMAN NECESSITIES
- A41—WEARING APPAREL
- A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
- A41D19/00—Gloves
- A41D19/0055—Plastic or rubber gloves
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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Abstract
The present invention relates to composite material and medical instruments field, specially a kind of graphene fitting hexagonal nano lamella boron nitride composite emulsion prepares the high-strength method without quick, high isolation medical glove.The graphene of electric field treatment is bonded with modified hexagonal nano lamella boron nitride compound, forms stable dispersion liquid, pH is in 4.5~7 ranges.It is subsequently dispersed in latex, solid masses ratio 0.1wt ‰~10wt ‰ are compound, finally prepare medical glove.Different from conventional graphite alkene gloves, gloves prepared by the present invention are less prone to the defect that weathering stability is poor, graphene is rotten and burnt hair shades.Graphene with " white graphite alkene " titles nanometer lack layer boron nitride it is compound after, the tensile strength, toughness, heat conduction of latex medical glove can be enhanced, effectively obstruct virus liquid infiltration.The present invention has the characteristics that scientific in principle, inert non-toxic, good weatherability, can produce the gloves of thermostabilization, high heat conduction, high isolation.
Description
Technical field
The present invention relates to composite material and medical instruments field, specially a kind of graphene fitting hexagonal nano lamella nitridation
Boron composite emulsion prepares the high-strength method without quick, high isolation medical glove.
Background technology
Medical latex glove is not only the medical supplies and the standing article of family life of doctor's indispensability.It has good
Hygienic isolation performance and excellent glued membrane intensity.Research report shows：The glued membrane of medical gloves can effectively shield venereal disease, Chinese mugwort
Grow the pathogeny body of the diseases such as disease.The higher elasticity of emgloves assigns its preferable grasping performance and the docile performance of shape.It is this
Characteristic is that any other material is all irreplaceable, and still uses medical latex glove as surgical medical both at home and abroad at present
The main reason for articles for use.
Proper use of medical gloves can significantly reduce bacterium infection probability.Material master currently used for medical gloves
Have：Natural latex rubber, butyronitrile latex rubber represent etc. synthetic latexes.Conventional gloves material also will appear some intensity
Not enough, lead to the crackle or breakage that naked eyes can not be observed, cause to infect.Especially breakneck infectiousness operation doctor
When treatment, the cost of this risk seems very huge.
Therefore, preparing has high barrier, and it is industry development that the advanced composite material (ACM) of high-elastic high intensity, which makes medical gloves,
An important directions.Graphene and hexagonal nano lamella boron nitride are two-dimension nano materials, have high piece diameter/thickness
Than having good toughness and impermeability[1].On the one hand, all modified graphenes, graphene oxide and reduced graphene be all
Become grey black after being long placed in, also will present grey after the eigenstate graphene reunion of even CVD.So merely by graphite
It is unstable that color and luster unavoidably occurs for alkene compounded latex gloves, influences that perception and performance weatherability, the graphene of addition is used to get over
More, the more grey latex the darker[2]。
Compare international patent application：PCT/IN2014/000711, publication No.:WO/2015/068174, title：
GRAPHENE BASED POLYMER COMPOSITES FOR PRODUCING CONDOMS WITH HIGH HEAT
TRANSFER, IMPROVED a kind of SENSITIVITY AND CAPACITY FOR DRUG DELIVERY (graphene-based polymerizations
Object composite material produce high heat conduction, low allergy, can drug conveying gloves), text in be also use simple graphene or derivative
Object carrys out the polymer such as compounded latex manufacture gloves, equally also can maximum probability encounter the above problem, graphene and boron nitride
Nanoscale twins fitting body compounded natural rubber latex can obtain very stable transmitance and colour properties, and the product of preparation has high-strength nothing
Quick, high isolation feature.
Bibliography：
[1]Kerr L.,Chaput M.,Boyd S.,Galevi E.,Millward P.,Characterization
and creation of defects in condoms,Journal of testing and evaluation,2001,29,
214；
[2]Maria Iliuta,Claudio Silvaa,b,Scott Herrickc,Mark McGlothlinc,
Aravind Vijayaraghavana,Graphene and water-based elastomers thin-film
composites by dip-moulding.Carbon,106,2016,228-232。
Invention content
The purpose of the present invention is to provide a kind of graphene fitting hexagonal nano lamella boron nitride composite emulsion prepare it is high-strength
The method of no quick, high isolation medical glove.Gained gloves have more stable color and luster and light transmission than pure graphene composite glove ratio
Degree, inertia not allergy, while also can effectively enhance barrier property, mechanical property, thermal conductivity.
To achieve the goals above, the present invention uses following technical scheme：
A kind of graphene fitting hexagonal nano lamella boron nitride composite emulsion prepares high-strength without quick high isolation medical glove
The graphene aqueous solution of electric field treatment and modified hexagonal nano lamella boron nitride aqueous solution are formed pH 4.5 by method first
Spontaneous fitting in~7 dispersion liquids, solid part mass ratio both in dispersion liquid are 1~20:1~20, the concentration of the two all exists
Between ‰~10wt of 0.1wt ‰；Applying method is：The solid of hexagonal nano lamella boron nitride is obtained and stone after electric treatment by modified
The opposite charge of black alkene surface charge, both high-specific area nano materials pass through the spontaneous suction of a large amount of xenogenesis charges in surface
Draw and be bonded and gather together, form fitting body, by the reunion scale for controlling the total pH value control fitting dispersion liquid of dispersion liquid
And dispersion stabilization；
Then the dispersion liquid of the fitting body is uniformly mixed with latex solution, and compound latex solution is made；It is solid to be bonded dispersion liquid
Content is ‰~10wt of 0.05wt ‰ with solid part mass ratio in latex；Compound latex solution passes through gloves normal process stream
Gloves finished product is made in journey.
The graphene fitting hexagonal nano lamella boron nitride composite emulsion prepares high-strength without quick high isolation medical glove
Method, prepare be bonded dispersion liquid when, solid part mass ratio of fitting body graphene and hexagonal nano lamella boron nitride
It is 1~20:1~20；The dispersion of fitting body is aqueous dispersions of the pH 4.5~7, according to the type and ratio of graphene
It adjusts.
The graphene fitting hexagonal nano lamella boron nitride composite emulsion prepares high-strength without quick high isolation medical glove
Method, prepare be bonded dispersion liquid when, solid part mass ratio of fitting body filler and latex be 0.05wt ‰~
10wt‰。
The graphene fitting hexagonal nano lamella boron nitride composite emulsion prepares high-strength without quick high isolation medical glove
Method, hexagonal nano lamella boron nitride used is hexagonal boron nitride single layer structure prepared by various methods or few layer structure, nitrogen
The number of plies for changing boron is 1~30 layer, i.e. thickness is 10nm hereinafter, each interlamellar spacing of hexagonal boron nitride is 0.335nm；Hexagonal nano used
Surfactant-modified, the acquisition charge opposite with the graphene film surface to be bonded of lamella boron nitride；Surfactant is
Nonionic surface active agent, anion surfactant, a type of cationic surfactant or compounding type.
The graphene fitting hexagonal nano lamella boron nitride composite emulsion prepares high-strength without quick high isolation medical glove
Method, the graphene for being bonded boron nitride is the graphene of electric field treatment, and processing method is simple positive-negative electrode plate to graphene
Solution applies electric field, to load graphene surface charge；Alternatively, completing the charged mesh of graphene colloid with electrodialysis plant
's.
The graphene fitting hexagonal nano lamella boron nitride composite emulsion prepares high-strength without quick high isolation medical glove
Method, the graphene of electric field treatment is the graphene of highly-hydrophilic, high transparency, and the oxygen content of graphene is more than 20wt%,
The number of plies is less than three layers.
The present invention design philosophy be：
Hexagonal boron nitride BN and graphite are all isoelectronic species layer structures, have the title of white graphite, single-layer silicon nitride boron to be known as
" white graphite alkene " clear, colorless has good lubricity, thermal conductivity and materialization inertia, does not have allergy row with biological cell
Different effect.Due to boron nitride nanosheet water white transparency itself, even if nanometer stacking there will not be any color change.In conjunction with two
Aspect, through the invention technical standpoint and means, the soft group that hexagonal nano lamella boron nitride and graphene are passed through into electrostatic attraction
It is poly-, form fitting body, then again with latex composite manufacturing gloves.Both content of the graphene in latex had been reduced, high transparency is kept
Degree, and enhance the heat conductivility of gloves, do not reduce the mechanical property of gloves also.
Compared with prior art, advantages of the present invention and advantageous effect are：
1, the graphene of electric field treatment is bonded compound by the present invention with modified hexagonal nano lamella boron nitride, is formed and is stablized
Dispersion liquid, pH is in 4.5~7 ranges.It being subsequently dispersed in latex, solid masses ratio 0.05wt ‰~10wt ‰ are compound,
Finally prepare medical glove.Different from conventional graphite alkene gloves, gloves prepared by the present invention be less prone to weathering stability it is poor,
Graphene goes bad and the defect of burnt hair obfuscation.It is compound that the nanometer of graphene and the title with " white graphite alkene " lacks layer boron nitride
Afterwards, the tensile strength, toughness, heat conduction of latex medical glove can be enhanced, effectively the infiltration of the viral liquid of barrier.
2, the present invention has the characteristics that scientific in principle, inert non-toxic, good weatherability, can produce thermostabilization, high heat conduction, height
The gloves of isolation.
Description of the drawings
Fig. 1 graphenes fitting hexagonal nano lamella boron nitride composite emulsion prepares high-strength without quick, high isolation medical glove
Method flow diagram.
Fig. 2 graphenes fitting hexagonal nano lamella boron nitride composite emulsion prepares high-strength without quick, high isolation medical glove
Material microstructure schematic diagram.In figure, 1 medical glove；2 rubber particles；3 graphenes and boron nitride lamella fitting body.
Specific implementation mode
As shown in Figure 1, graphene of the present invention fitting hexagonal nano lamella boron nitride composite emulsion prepare it is high-strength without it is quick, high every
The method flow of exhausted medical glove is as follows：
The graphene colloid and boron nitride colloid of negatively charged/positive charge, are bonded by electrostatic attraction, form graphene/nitrogen
Change boron nanoscale twins fitting body, after latex solution is added, graphene/compound medical glove of boron nitride nanometer sheet layer material is made.
As shown in Fig. 2, graphene of the present invention fitting hexagonal nano lamella boron nitride composite emulsion prepare it is high-strength without it is quick, high every
The material microstructure of exhausted medical glove is as follows：The jacket wall of medical glove 1 is rubber particles 2 and graphene and boron nitride lamella patch
Zoarium 3 forms.
In specific implementation process, the method comprises the steps of firstly, preparing graphene/hexagonal nano lamella boron nitride to be bonded liquid solution：
(preferred scope is ‰~10wt of 0.1wt ‰：‰~2wt of 0.5wt ‰) concentration graphene aqueous solution after electric-field charge band
Upper negative electrical charge, under stirring conditions, by ‰~10wt of 0.1wt ‰, (preferred scope is：‰~4wt of 1wt ‰) concentration six sides
The solution of boron nitride nanometer sheet layer material is with surfactant-modified.Then the two is mixed, is allowed to that Electrostatic Absorption occurs
Fitting adjusts pH value by the ratio of graphene oxide or hydrochloric acid in water in control solution, is allowed in 4.5~7 ranges, such as
Hydrophilic graphene oxide or dilute hydrochloric acid provide the acidity on basis, with the content of water, the modified graphene of other types and modification
Hexagonal nano lamella boron nitride synthesis adjusts final pH value together.Then ultrasonic, so that fitting body is uniformly dispersed.Fitting body disperses
In liquid, all kinds of graphene solid masses and boron nitride mass ratio are that (preferred scope is 5wt%~2000wt%：40wt%~
80wt%).The dispersion liquid of fitting body is uniformly mixed with latex solution, and compound latex solution is made.Fitting body solution solids filler with
Solid part mass ratio in latex is that (preferred scope is ‰~10wt of 0.05wt ‰：‰~0.5wt of 0.2wt ‰).Compound
Latex solution passes through gloves normal process flow, and gloves finished product is made.
Wherein, hexagonal nano lamella boron nitride used can be 1~30 layer or so, i.e., thickness is 10nm or less (six side's nitrogen
Change each interlamellar spacing of boron is 0.335nm).Hexagonal nano lamella boron nitride used can be obtained and to be pasted with surfactant-modified
The opposite charge in the graphene film surface of conjunction.Surfactant can be nonionic surface active agent, anion surface active
Agent, a type of cationic surfactant or a certain proportion of compounding type.The graphene of electric field treatment is highly-hydrophilic,
The graphene of high transparency, the oxygen content of graphene are more than 20wt%, and the number of plies is less than three layers, electrically with want compound hexagonal nano
Lamella boron nitride solution colloid is opposite.
In order to facilitate the dispersion pH value of adjusting adhesive body, water graphene oxide and the hexagonal nano-flake of modification may be selected
Layer boron nitride system or other non-oxidized graphite alkene and dilute hydrochloric acid and modified hexagonal nano lamella boron nitride system, pass through tune
Water-saving middle concentration and its mutually stripping, obtain the pH value of needs.The graphene of fitting boron nitride is the graphene of electric field treatment,
Processing method can be that simple positive-negative electrode plate applies electric field to graphene solution, to load graphene surface charge, or use
Electrodialysis plant completes the charged purpose of graphene colloid.
In the following, by embodiment and test result, the present invention is described in more detail.
Embodiment 1
In the present embodiment, graphene fitting hexagonal nano lamella boron nitride composite emulsion prepares high-strength without quick, high isolation doctor
The method for treating gloves is as follows：
It is prepared by graphene/hexagonal nano lamella boron nitride fitting liquid solution：The graphene oxide water of a concentration of 2wt of 1 ㎏ ‰
Solution takes negative electrical charge after electric-field charge.1 ㎏ of aqueous solution of the ‰ hexagonal boron nitride nanosheet layer material containing 0.1wt is used
The polyvinyl pyrrolidone modified of 0.1wt ‰.Then ultrasound is mixed in the two, is allowed to be uniformly dispersed.Then clean
Mixing tank in the Heveatex of 10Kg a concentration of 60wt% is added, it is dense to be gradually added the 2Kg that front prepares under agitation
Graphene/hexagonal nano lamella boron nitride that degree is 2.1wt ‰ is bonded liquid solution, and after addition, 0.1wt ‰ can be added in right amount
Dispersion stabilizer paregal O (alkyl polyoxyethylene ether), persistently stir 1 hour make its be uniformly mixed.Adjusting viscosity at this time is
15mPas or so.Glue after will be compound stands 24 hours or so, it is made fully to cure, and is then added in impregnator and is soaked
Stain post-processing twice produces, and is finally tested for the property and is got product after.
Then the performance advantage of new material and medical gloves product prepared by the verification present invention, inventor is according to national standard
GB10213-2006《Disposable rubber examination glove》, to the compound doctor of graphene/latex of the batch prepared by embodiment 1
Sampling observation test is carried out with gloves, test average result comparison national standard is as shown in table 1：
Table 1：The tensile property index of this example batch sampling observation composite medical gloves and comparison
By table in fact inspection data it could be assumed that：1 class product testing result of classification：The minimum value of breaking tenacity is apparent before aging
Higher than national standard 62.8%, the minimum value of elongation at break improves 11.4% than national standard before aging.The minimum of breaking tenacity after aging
Value is higher than national standard 58.3%, and the minimum value of elongation at break improves 14% than national standard after aging.2 class product testing knot of classification
Fruit：The minimum value of breaking tenacity is obviously higher than national standard 64.2% before aging, and the minimum value of elongation at break is carried than national standard before aging
It is high by 14.0%.The minimum value of breaking tenacity is higher than national standard 50% after aging, and the minimum value of elongation at break is carried than national standard after aging
It is high by 20%.
Embodiment 2
In the present embodiment, graphene fitting hexagonal nano lamella boron nitride composite emulsion prepares high-strength without quick, high isolation doctor
The method for treating gloves is as follows：
It is prepared by graphene/hexagonal nano lamella boron nitride fitting liquid solution：The graphene oxide of a concentration of 1wt of 1 ㎏ ‰ and
‰ amination graphene aqueous solutions of a concentration of 1wt take negative electrical charge after electrodialysis is charged.‰ hexagonal boron nitrides of 0.1wt will be contained
1 ㎏ of aqueous solution of nanoscale twins material is modified with the dodecyl sodium sulfate of 0.1wt ‰.Then ultrasound is mixed in the two,
It is allowed to be uniformly dispersed.Then the Heveatex of a concentration of 60wt% of 10Kg is added in clean mixing tank, in stirring condition
Under be gradually added graphene/hexagonal nano lamella boron nitride fitting liquid solution of a concentration of 2.1wt of 2Kg that front prepares ‰, add
After entering, ‰ dispersion stabilizer polyvinylpyrrolidones of 0.1wt can be added in right amount, persistently stirring 1 hour keeps its mixing equal
It is even.It is 20mPas or so to adjust viscosity at this time.Glue after will be compound stands 24 hours or so, so that it is fully cured, then
It is added in impregnator and is impregnated the production of post-processing twice, be finally tested for the property and got product after.
Embodiment the result shows that, by graphene of the present invention fitting hexagonal nano lamella boron nitride composite emulsion prepare high-strength nothing
Quick, high isolation medical glove is dipped into the reducing liquids such as hydrazine hydrate, is not changed colour, film resistivity inside and outside medical glove
Also do not change, illustrate that the medical glove of rubber particles, graphene and boron nitride lamella fitting body composition is very stable very safe
, prepared medical glove product has splendid barrier property and excellent mechanical property.
The above-described embodiments are merely illustrative of preferred embodiments of the present invention, not to the model of the present invention
It encloses and is defined, under the premise of not departing from the spirit of the invention design, this field ordinary engineering and technical personnel is to the present invention
The various modifications and improvement that technical solution is made should all be fallen into the protection domain of claims of the present invention determination.
Claims (5)
1. a kind of graphene fitting hexagonal nano lamella boron nitride composite emulsion prepares the high-strength side without quick high isolation medical glove
Method, which is characterized in that first by the graphene aqueous solution of electric field treatment and modified hexagonal nano lamella boron nitride aqueous solution shape
The spontaneous fitting in 4.5~7 dispersion liquids at pH, solid part mass ratio both in dispersion liquid are 1~20:1~20, the two
Concentration is all between 0.1 ‰~10wt of wt ‰；Applying method is：The solid of hexagonal nano lamella boron nitride by it is modified obtain with
The charge of graphene surface opposite charge after electric treatment, both high-specific area nano materials pass through a large amount of xenogenesis electricity in surface
The spontaneous attraction of lotus and being bonded gathers together, forms fitting body, passes through and controls the total pH value control fitting dispersion liquid of dispersion liquid
Reunion scale and dispersion stabilization；
Then the dispersion liquid of the fitting body is uniformly mixed with latex solution, and compound latex solution is made；It is bonded dispersion liquid solid content
It is 0.05 wt, ‰~10 wt ‰ with solid part mass ratio in latex；Compound latex solution passes through gloves normal process stream
Gloves finished product is made in journey.
2. graphene described in accordance with the claim 1 fitting hexagonal nano lamella boron nitride composite emulsion prepares it is high-strength without quick height every
The method of exhausted medical glove, which is characterized in that when preparing fitting dispersion liquid, fitting body graphene and hexagonal nano lamella nitrogen
The solid part mass ratio for changing boron is 1~20:1~20；The dispersion of fitting body is pH in 4.5~7 aqueous dispersion, root
According to the type and proportion adjustment of graphene.
3. graphene described in accordance with the claim 1 fitting hexagonal nano lamella boron nitride composite emulsion prepares it is high-strength without quick height every
The method of exhausted medical glove, which is characterized in that hexagonal nano lamella boron nitride used is hexagonal boron nitride prepared by various methods
The number of plies of single layer structure or few layer structure, boron nitride is 1~30 layer, i.e., thickness is 10nm hereinafter, each interlamellar spacing of hexagonal boron nitride
For 0.335nm；Hexagonal nano lamella boron nitride used surfactant-modified, acquisition and the graphene film surface phase to be bonded
Anti- charge；Surfactant is anion surfactant, a type of cationic surfactant or compounding type.
4. graphene described in accordance with the claim 1 fitting hexagonal nano lamella boron nitride composite emulsion prepares it is high-strength without quick height every
The method of exhausted medical glove, which is characterized in that the graphene for being bonded boron nitride is the graphene of electric field treatment, and processing method is letter
Single positive-negative electrode plate applies electric field to graphene solution, to load graphene surface charge；Alternatively, being completed with electrodialysis plant
The charged purpose of graphene colloid.
5. graphene described in accordance with the claim 1 fitting hexagonal nano lamella boron nitride composite emulsion prepares it is high-strength without quick height every
The method of exhausted medical glove, which is characterized in that the graphene of electric field treatment is the graphene of highly-hydrophilic, high transparency, graphite
The oxygen content of alkene is more than 20wt%, and the number of plies is less than three layers.
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| CN103480329A (en) * | 2013-09-05 | 2014-01-01 | 深圳先进技术研究院 | Hexagonal boron nitride/graphene oxide composite adsorption material and preparation method thereof |
| WO2015068174A2 (en) * | 2013-11-11 | 2015-05-14 | Hll Lifecare Limited | Graphene based polymer composites for producing condoms with high heat transfer, improved sensitivity and capacity for drug delivery |
| CN105295090A (en) * | 2015-11-23 | 2016-02-03 | 辽宁兰晶科技有限公司 | Method for preparing high-strength and high-isolation medical gloves by using modified graphene/latex composite material |
| CN105949512A (en) * | 2016-05-12 | 2016-09-21 | 上海大学 | Intercalation assembly based boron nitride-graphene composite material as well as application and preparation method thereof |
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| CN103480329A (en) * | 2013-09-05 | 2014-01-01 | 深圳先进技术研究院 | Hexagonal boron nitride/graphene oxide composite adsorption material and preparation method thereof |
| WO2015068174A2 (en) * | 2013-11-11 | 2015-05-14 | Hll Lifecare Limited | Graphene based polymer composites for producing condoms with high heat transfer, improved sensitivity and capacity for drug delivery |
| CN105295090A (en) * | 2015-11-23 | 2016-02-03 | 辽宁兰晶科技有限公司 | Method for preparing high-strength and high-isolation medical gloves by using modified graphene/latex composite material |
| CN105949512A (en) * | 2016-05-12 | 2016-09-21 | 上海大学 | Intercalation assembly based boron nitride-graphene composite material as well as application and preparation method thereof |
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