CN110143601A - The preparation method of antifungin nano wire and its application in the epoxy - Google Patents
The preparation method of antifungin nano wire and its application in the epoxy Download PDFInfo
- Publication number
- CN110143601A CN110143601A CN201810142196.6A CN201810142196A CN110143601A CN 110143601 A CN110143601 A CN 110143601A CN 201810142196 A CN201810142196 A CN 201810142196A CN 110143601 A CN110143601 A CN 110143601A
- Authority
- CN
- China
- Prior art keywords
- antifungin
- nano wire
- epoxy resin
- preparation
- white powder
- 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.)
- Granted
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B35/00—Boron; Compounds thereof
- C01B35/08—Compounds containing boron and nitrogen, phosphorus, oxygen, sulfur, selenium or tellurium
- C01B35/10—Compounds containing boron and oxygen
- C01B35/12—Borates
- C01B35/126—Borates of alkaline-earth metals, beryllium, aluminium or magnesium
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
-
- 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
- C08K7/00—Use of ingredients characterised by shape
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/88—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by thermal analysis data, e.g. TGA, DTA, DSC
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
- C01P2004/16—Nanowires or nanorods, i.e. solid nanofibres with two nearly equal dimensions between 1-100 nanometer
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
- C08K2003/387—Borates
-
- 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
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
-
- 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
- C08K2201/002—Physical properties
- C08K2201/004—Additives being defined by their length
-
- 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
Abstract
Application the invention discloses a kind of preparation method of antifungin nano wire and its in the epoxy, magnesium chloride and boric acid is evenly dispersed in deionized water, obtain colourless transparent solution；Excessive ammonia is added in the form of being added dropwise in colourless transparent solution, obtains white precipitate；Gained white precipitate is reacted at least 6 hours in closed autoclave in 120~180 DEG C, room temperature is down to after reaction naturally, obtains white depositions；It is cleaned the white depositions at least 3 times with deionized water, filters and at least 6 hours dry in 100~150 DEG C, obtain white powder；By step 4 gained white powder heat preservation 3 hours or more under conditions of being not less than 700 DEG C, it is down to room temperature naturally, obtains antifungin nano wire.The antifungin nano wire that the present invention obtains is applied in the epoxy as inorganic reinforcement, antifungin nano wire and epoxy resin synthetic epoxy resin composite material, so that the bending property of epoxy resin is obviously improved.
Description
Technical field
The invention belongs to technical field of preparation for inorganic material, relate in particular to a kind of preparation method of antifungin nano wire
And its application in the epoxy.
Background technique
The intensity of composite material depends primarily on intensity, content, draw ratio and the interfacial adhesion strength of reinforcement.It is one-dimensional
External force can be transmitted to after matrix is by external force by composite material of the nano material as reinforcement in elastic deformation early period
Reinforcement, so that reinforcement bears a part of power, to improve the performance of material.Since the intensity of reinforcement is much larger than collective
Material is so slight crack cannot pass through nano whisker and be to bypass nano whisker fracture in fracture；In addition the increasing of reinforcement content
Add and also have certain influence on matrix, excessive reinforcement can be because of itself orientation in the base and overstocked or there is part
Reunite, so that the transmitting of power hinders between matrix；Interface bond strength declines between matrix simultaneously, so that matrix is to reinforcement
Transmit the ability decline of load.High length-diameter ratio one-dimensional material not only can be with extension fracture path, and can reduce dosage and avoid
Part is reunited, therefore high aspect ratio materials can preferably improve the performance of basis material.So how to obtain high aspect ratio materials
It is the key that the research hotspot for improving basis material performance and researchers at home and abroad.
Summary of the invention
In view of the deficiencies of the prior art, the purpose of the present invention is to provide a kind of antifungin nano wire with high length-diameter ratio
Preparation method.
It is a further object of the present invention to provide a kind of antifungin nano wire with high length-diameter ratio.
It is a further object of the present invention to provide the application of antifungin nano wire in the epoxy.
The purpose of the present invention is what is be achieved by following technical proposals.
A kind of preparation method of antifungin nano wire, comprising the following steps:
Step 1, magnesium chloride and boric acid is evenly dispersed in deionized water, obtain colourless transparent solution, wherein the chlorine
The ratio for changing the amount of the substance of magnesium and boric acid is 1:1.5, in the colourless transparent solution concentration of magnesium chloride be 0.02~
0.05mol/L；
In the step 1, by the evenly dispersed operating method in deionized water of magnesium chloride and boric acid are as follows: by magnesium chloride
It is added in deionized water and is stirred to being completely dissolved with boric acid.
In the step 1, the concentration of magnesium chloride is 0.02~0.03mol/L in the colourless transparent solution.
Step 2, excessive ammonia is added in the form of being added dropwise in step 1 gained colourless transparent solution, obtains white precipitate；
Step 3, by step 2 gained white precipitate in closed autoclave in 120~180 DEG C react at least 6 hours, instead
Then 20~25 DEG C of room temperature should be down to naturally, obtain white depositions；
In the step 3, step 2 gained white precipitate reacts 12 hours in closed autoclave in 180 DEG C.
Step 4, it is cleaned the white depositions at least 3 times, is filtered and in 100~150 DEG C dry at least 6 with deionized water
Hour, obtain white powder；
In the step 4, the white powder is MgBO2(OH)。
Step 5, step 4 gained white powder is down to naturally heat preservation 3 hours or more under conditions of being not less than 700 DEG C
Room temperature obtains antifungin nano wire.
In the step 5, the heating rate of white powder heating is 1~5 DEG C/min, preferably 1~2 DEG C/
min。
The antifungin nano wire that above-mentioned preparation method obtains, the length of the antifungin nano wire are 1~5 micron, diameter
It is 20~30 nanometers.
Above-mentioned antifungin nano wire is improving the application in epoxy resin bending property, and curing agent and above-mentioned antifungin are received
Rice noodles, which mix, simultaneously be ultrasonically treated 2~5 minutes in supersonic cleaning machine, then to add epoxy resin evenly dispersed, is consolidated after evenly dispersed
Change, obtain epoxy resin composite material, wherein according to the mass fraction, the antifungin nano wire is the epoxy resin
The ratio of the mass fraction of 0.25~1wt%, the curing agent and the epoxy resin is 1:3.
In the above-mentioned technical solutions, it was realized with magnetic stirrer at least 20 minutes described evenly dispersed.
In the above-mentioned technical solutions, the curing agent is fatty amines curing agent.
Compared with the prior art, the preparation method of antifungin nano wire of the invention is by adjusting reaction density, reaction temperature
Degree and reaction time optimize antifungin nano wire draw ratio, obtain the nano wire of high length-diameter ratio.
In addition, the antifungin nano wire that the present invention obtains is applied in the epoxy as inorganic reinforcement, antifungin
Nano wire works as addition so that the bending property of epoxy resin is obviously improved with epoxy resin synthetic epoxy resin composite material
When appropriate antifungin nano wire, epoxy resin bending elastic modulus improves 66.8%, and maximum deflection power improves 41.8%.
Detailed description of the invention
Fig. 1 is the XRD of white powder in embodiment 1~12；
Fig. 2 is the SEM of white powder in embodiment 4~12；
Fig. 3 is the XRD of white powder in embodiment 13~15；
Fig. 4 is that the SEM of white powder schemes；
Fig. 5 (a) is the XRD diagram of white powder, and 5 (b) be the TG-DTG curve of white powder, and Fig. 5 (c) is white powder
SEM figure；
Fig. 6 (a) is different Mg2B2O5The compression sag curve of the epoxy resin composite material of nano wire additive amount, Fig. 6
It (b) is different Mg2B2O5Bending elastic modulus (the E of the epoxy resin composite material of nano wire additive amountb), Fig. 6 (c) is difference
Mg2B2O5Maximum deflection power (the σ of the epoxy resin composite material of nano wire additive amountbb)。
Specific embodiment
In a specific embodiment of the invention, anhydrous magnesium chloride (99.9%), boric acid (GR >=99.8%), ammonium hydroxide (GR,
25-28%) and epoxy AB glue is purchased from Aladdin.
Crystal structure is characterized using the X-ray diffractometer of BRUKER D8 FOCUSXRD；Using HITACHI S-4800's
Scanning electron microscope characterizes microscopic appearance；Using the omnipotent mechanical test of Changchun Academy of Machinery Science & Technology Co., Ltd. DDL10
Machine characterizes bending property.
Technical solution of the present invention is further illustrated combined with specific embodiments below.
A kind of preparation method of antifungin nano wire, comprising the following steps:
Step 1, magnesium chloride and boric acid are added in deionized water and magnetic agitation 30min is to being completely dissolved, so that chlorination
Magnesium and boric acid are evenly dispersed in deionized water, obtain colourless transparent solution, wherein the ratio of the amount of the substance of magnesium chloride and boric acid
For 1:1.5, the concentration of magnesium chloride is C mol/L in colourless transparent solution；
Step 2, excessive ammonia is added in the form of being added dropwise in step 1 gained colourless transparent solution, obtains white precipitate；
Step 3, step 2 gained white precipitate is fitted into the autoclave vessel that liner is polytetrafluoroethylene (PTFE) in (50ml),
It is reacted 6 hours in closed autoclave in T DEG C, is down to 20~25 DEG C of room temperature after reaction naturally, obtains white depositions；
Step 4, it is cleaned white depositions 3 times with deionized water, filters and dry, obtain white powder, wherein when dry
Between be 6 hours, drying temperature be 100 DEG C；
Step 5, step 4 gained white powder is kept the temperature 3 hours in 700 DEG C, is down to room temperature naturally, obtains product, wherein
The heating rate that white powder is warming up to 700 DEG C is 2 DEG C/min.
It carries out forming embodiment 1~12 according to above-mentioned steps, the numerical value of C and T sees below table 1 in embodiment 1~12.
The numerical value of C and T in 1 embodiment 1~12 of table
Fig. 1 is the XRD of white powder in embodiment 1~12, wherein C is 0.01mol/L in Fig. 1 (a), and C is in Fig. 1 (b)
C is 0.03mol/L in 0.02mol/L, Fig. 1 (c), and C is 0.05mol/L in Fig. 1 (d).
As seen from the figure, as shown in Fig. 1 (a), when the concentration of magnesium chloride in colourless transparent solution is 0.01mol/L, 120
DEG C, 150 DEG C, drying reacts in 6 hours white powders and MgBO is not observed at 180 DEG C2(OH)(PDF NO.33-0860)
Diffraction maximum, and show Mg7B4O13·7H2The diffraction maximum of O (PDF No.19-0754).It may occur in this process following
Chemical reaction:
As shown in Fig. 1 (b), when the concentration of magnesium chloride in colourless transparent solution is increased to 0.02mol/L, diffraction maximum has bright
Aobvious variation, the results showed that reaction temperature begins with MgBO at 120 DEG C2(OH) (PDF NO.33-0860) is formed, and with
The raising MgBO of reaction temperature2(OH) content steps up, but does not synthesize still when drying reaction temperature and being 180 DEG C
Pure MgBO2(OH)。
As shown in Fig. 1 (c), when the concentration of magnesium chloride in colourless transparent solution continues to improve to 0.03mol/L, 120
DEG C drying reaction temperature under observe the alkali formula magnesium borate Mg BO of monocline2(OH) diffraction maximum, it is only a small amount of
Mg7B4O13·7H2O diffraction maximum.When drying reaction temperature is 150 DEG C and 180 DEG C, Mg7B4O13·7H2O diffraction maximum disappears completely
It loses, illustrates that the MgBO of absolutely not impurity can be prepared by improving reaction temperature2(OH)。
As shown in Fig. 1 (d), when the concentration of magnesium chloride in colourless transparent solution is increased to 0.05mol/L, at 120 DEG C
It can be obtained by pure MgBO under drying reaction temperature2(OH), illustrate that higher solution concentration advantageously forms the alkali of monocline
Formula antifungin, under the conditions of a certain concentration, as the raising of reaction temperature is also beneficial to MgBO2(OH) synthesis, but concentration
Raising be more conducive to MgBO2(OH) synthesis.Following chemically react may occur for high temperature high pressure process:
Mg7B4O13·7H2O(s)+3B(OH)4 -(aq.)→7MgB2(OH)(s)+3OH-(aq.)+8H2O (2)
In addition, with the raising of T and C tree numerical value, MgBO2(OH) crystallinity increases.
Fig. 2 is the SEM of white powder in embodiment 4~12, wherein C is 0.02mol/L, Fig. 2 (a1) in Fig. 2 (a1-a3)
Middle T is that T is that T is that C is 0.03mol/L, T in Fig. 2 (b1) in 180, Fig. 2 (b1-b3) in 150, Fig. 2 (a3) in 120, Fig. 2 (a2)
It is that T is that C is 0.05mol/L in 180, Fig. 2 (c1-c3) in 150, Fig. 2 (b3) for T in 120, Fig. 2 (b2), T is in Fig. 2 (c1)
T is that T is 180 in 150, Fig. 2 (c3) in 120, Fig. 2 (c2).
When C is 0.02mol/L: when drying reaction temperature T is 120 DEG C, white powder is the flower of nano flake composition；With
The raising of reaction temperature begin with a small amount of nanobelt when drying reaction temperature T is 150 DEG C and occur, such as Fig. 2 (a2) institute
Show；Reaction temperature will be dried by continuing when being increased to 180 DEG C, and flower-shaped three-dimensional structure disappears, and observe the nano flake and length of dispersion
The long nanobelt of diameter, such as Fig. 2 (a3).According in Fig. 1 XRD's as a result, nanometer sheet may it is corresponding be Mg7B4O13·7H2O,
And it is MgBO that nanobelt is corresponding2(OH)。
Fig. 2 (b1-b3) is when C is 0.03mol/L, and the SEM that drying reaction temperature is 120 DEG C, 150 DEG C and 180 DEG C schemes,
As we can see from the figure with the raising of reaction temperature, shorter flat of major diameter is transformed by the nanometer thin band mutually wound
Nanometer rods.
As shown in Fig. 2 (c1-c3), when continuing raising reaction density makes C 0.05, obtained under the conditions of 120 DEG C mutually
There are the nanometer rods of bonding.When reaction temperature is 180 DEG C, nanometer rods further shorten, and increase reaction temperature nanometer rods and tend to point
It dissipates, attenuating shortens.
Experimental result illustrates the increase with reaction solution concentration, is conducive to the formation of one-dimensional nano structure, but concentration mistake
Nucleating point increase is unfavorable for the further growth of one-dimensional square so forming many short nanometer rods when big.The raising of reaction temperature
It is equally beneficial for the synthesis of material, but high reaction temperature accelerates the nucleating point that increase of reaction and is unfavorable for preparing high length
The one-dimensional material of diameter ratio.So to control suitable solution concentration and reaction temperature, it is ensured that MgBO2(OH) there is high major diameter
Than.
A kind of preparation method of antifungin nano wire, comprising the following steps:
Step 1, magnesium chloride and boric acid are added into deionized water and magnetic agitation 30min is to being completely dissolved, so that chlorine
Change magnesium and boric acid is evenly dispersed in deionized water, obtains colourless transparent solution, wherein the amount of the substance of magnesium chloride and boric acid
Than for 1:1.5, the concentration of magnesium chloride is C mol/L in colourless transparent solution；
Step 2, excessive ammonia is added in the form of being added dropwise in step 1 gained colourless transparent solution, obtains white precipitate；
Step 3, step 2 gained white precipitate is fitted into the autoclave vessel of inner liner polytetrafluoroethylene in (50ml),
It is reacted 12 hours in closed autoclave in T DEG C, is down to 20~25 DEG C of room temperature after reaction naturally, obtains white depositions；
Step 4, it is cleaned white depositions 3 times with deionized water, filters and dry, obtain white powder, wherein when dry
Between be 6 hours, drying temperature be 100 DEG C；
Step 5, step 4 gained white powder is kept the temperature 3 hours in 700 DEG C, is down to room temperature naturally, obtains antifungin nanometer
Line, wherein the heating rate that white powder is warming up to 700 DEG C is 2 DEG C/min.
It carries out forming embodiment 13~17 according to above-mentioned steps, the numerical value of C and T sees below table 2 in embodiment 13~17.
The numerical value of C and T in 2 embodiment 13~17 of table
Fig. 3 is the XRD diagram of white powder in embodiment 13~15, and as seen from the figure, embodiment 13 (i.e. T=120) is prepared into
The white powder arrived is MgBO2(OH) and Mg7B4O13·7H2The mixture of O, embodiment 14 (i.e. T=150) are prepared white
Color powder is substantially MgBO2(OH).The white powder that embodiment 15 (i.e. T=180) is prepared is single-phase MgBO2(OH)。
Fig. 4 (a-c) is that the SEM of white powder in embodiment 13~15 schemes (i.e. MgCl2It is different when concentration is 0.02mol/L
Kept for 12 hours under reaction temperature), as seen from the figure, the white powder in embodiment 13 is substantially nano flake, after increasing temperature
Embodiment 14 obtain the nanometer thin band that white powder becomes, the white powder of embodiment 15 for continuing to increase temperature becomes to have
Compared with the nano wire of high length-diameter ratio, diameter is about 30nm, and length is about 1-2 μm.
Fig. 4 (d) is the SEM (C=0.03mol/L) of white powder in embodiment 16, and Fig. 4 (e) is white in embodiment 17
The SEM (C=0.05mol/L) of powder, as seen from the figure, when C=0.03mol/L, the diameter of white powder is about 20nm, and length is
3~5 microns, the nano wire of high length-diameter ratio is synthesized.But according to Fig. 4 (e) it is found that when concentration further increases, white powder
The draw ratio at end shortens rapidly, and length is not essentially exceeding 1 μm.Therefore, in MgBO2(OH) it to be controlled in the synthesis process of nano wire
The concentration of reactant processed and reaction temperature appropriate, there are also the longer reaction time.
Antifungin (Mg2B2O5) synthesis can be heat-treated to obtain by alkali formula antifungin, Fig. 5 (a) be shown implement
The white powder MgBO that example 16 obtains2(OH) it is not heat-treated the XRD diagram with 700 DEG C of heat treatment 3 hours, diffraction maximum illustrates 700
DEG C heat treatment after crystal structure be entirely Mg2B2O5Phase.5 (b) be the white powder MgBO that embodiment 16 obtains2(OH) nano wire
TG-DTG curve.At 25-350 DEG C of temperature, the weightlessness of sample is relatively slow, and weightlessness is that the moisture of sample surfaces absorption causes
, weight-loss ratio 6.2%.350 DEG C to 450 DEG C sample quick weight loss, as long as the weightlessness sample of this part is from MgBO2(OH) turn
Become Mg2B2O5It is generated, by calculating from 350 DEG C to 540 DEG C sample weight-loss ratio 11.1%, this and MgBO2(OH)
It is completely transformed into Mg2B2O5When theoretical weight-loss ratio 10.7% it is very close.When the weight that temperature is more than 450 DEG C of samples is protected always
It holds constant, illustrates MgBO2(OH) it has been completely transformed into Mg2B2O5.Following formula is MgBO2(OH) it is changed into Mg2B2O5Chemical equation
Formula:
2MgBO2(OH)(s)-Mg2B2O5(s)+H2O(g) (3)
DTA, which is shown, an endothermic peak at 518 DEG C, this corresponding endothermic peak is MgBO2(OH) to Mg2B2O5Turn
Become, illustrates to need to absorb a large amount of heat in this transition process.And having an exothermic peak at 673 DEG C, this may be Mg2B2O5
Caused by latent heat, because of MgBO2(OH) to Mg2B2O5Both transformations crystal structure it is different, Mg2B2O5It needs to tie again
It is brilliant.During heat treatment, to prevent the fracture heating rate of nano wire should be slow as far as possible, Fig. 5 (c) be that embodiment 16 obtains
White powder by 700 DEG C heat treatment after obtain antifungin nano wire SEM figure, heating rate be 2 DEG C/min, the results showed that
It is heat-treated the pattern without changing original nano wire.Its diameter is still about 20nm, and length is still 3~5 microns.It can be seen that logical
Overheating Treatment alkali formula antifungin can keep original high length-diameter ratio to obtain antifungin.
Following Mg for being all made of embodiment 16 and being prepared2B2O5Nano wire, curing agent are fatty amines curing agent divinyl
Triamine (DETA), content >=99.9%, the synthetic method of epoxy resin composite material, comprising the following steps:
The antifungin nano wire that 2.5g curing agent and embodiment 16 are prepared mixes and the ultrasound in supersonic cleaning machine
Processing 5 minutes, then adds 7.5g epoxy resin, with magnetic stirrer 20 minutes it is evenly dispersed after be poured into dumbbell shaped mold
Middle solidification, obtains epoxy resin composite material, wherein according to the mass fraction, antifungin nano wire be epoxy resin 0wt%,
The ratio of the mass fraction of 0.25wt%, 0.5wt%, 0.75wt%, 1wt% and 1.5wt%, curing agent and epoxy resin is 1:3.
Fig. 6 (a) is different Mg2B2O5The compression sag curve of the epoxy resin composite material of nano wire additive amount.According to
Bending elastic modulus (E is calculated in bending elastic modulus formulab) and maximum deflection power (σbb), such as Fig. 6 (b) and (c).It is bent bullet
Property tangent elastic modulus is as follows:
F is the bending force applied, and Ls is span, and f is amount of deflection, and b is specimen width, and h is height of specimen, and L is that test specimen is long
Degree, I are the moment of inertia of the test specimen section to neutral axis.
Maximum deflection power formula is as follows
FbbFor maximum deflection power, W is the bending resistant section coefficient of test specimen.
The result shows that Mg2B2O5The addition of nano wire is so that the bending property of epoxy resin is obviously improved, elasticity of flexure mould
Amount and maximum deflection power significantly improve.Pure epoxy resin bending elastic modulus and maximum deflection power be respectively 877.9MPa and
90.9MPa, with Mg2B2O5The increase bending elastic modulus and maximum deflection power of nano wire additive amount gradually increase, and are adding
The bending elastic modulus of epoxy resin is 1134.2Mpa when amount is 0.25%, improves 29.2% relative to pure epoxy resin, most
Macrobending power is that 115.4MPa improves 27%.When additive amount is 0.5%, epoxy resin (epoxy resin composite material) is curved
Modulus in elasticity in bending is that 1463.9MPa improves 66.8%, and maximum deflection power is 128.9MPa, improves 41.8%.When matrix by
External force can be transmitted to Mg after to external force2B2O5Nano wire makes it bear most power so as to improve sliding and bending deformation.
When continuing growing Mg2B2O5The content of nano wire, bending elastic modulus and maximum deflection power are decreased obviously, it may be possible to because with
Mg2B2O5The increase Mg of nano wire content2B2O5Interface bond strength weakens accordingly between nano wire and matrix, and matrix is to nano wire
The ability decline of load is transmitted, the shear drag that nano wire is subject to is substantially reduced.Mg2B2O5After nano wire content increase due to
The orientation of oneself and the overstocked transmitting for making power between matrix hinder in matrix.
Illustrative description has been done to the present invention above, it should explanation, the case where not departing from core of the invention
Under, any simple deformation, modification or other skilled in the art can not spend the equivalent replacement of creative work equal
Fall into protection scope of the present invention.
Claims (9)
1. a kind of preparation method of antifungin nano wire, which comprises the following steps:
Step 1, magnesium chloride and boric acid is evenly dispersed in deionized water, obtain colourless transparent solution, wherein the magnesium chloride
Ratio with the amount of the substance of boric acid is 1:1.5, and the concentration of magnesium chloride is 0.02~0.05mol/L in the colourless transparent solution；
Step 2, excessive ammonia is added in the form of being added dropwise in step 1 gained colourless transparent solution, obtains white precipitate；
Step 3, step 2 gained white precipitate is reacted at least 6 hours in closed autoclave in 120~180 DEG C, after reaction
Naturally 20~25 DEG C of room temperature are down to, white depositions are obtained；
Step 4, it is cleaned the white depositions at least 3 times, is filtered and small in 100~150 DEG C of dryings at least 6 with deionized water
When, obtain white powder；
Step 5, step 4 gained white powder is down to room temperature heat preservation 3 hours or more under conditions of being not less than 700 DEG C naturally,
Obtain antifungin nano wire.
2. preparation method according to claim 1, which is characterized in that in the step 1, magnesium chloride and boric acid is uniform
Dispersion operating method in deionized water are as follows: magnesium chloride and boric acid are added in deionized water and stir to being completely dissolved.
3. preparation method according to claim 1, which is characterized in that in the step 1, in the colourless transparent solution
The concentration of magnesium chloride is 0.02~0.03mol/L.
4. preparation method according to claim 1, which is characterized in that in the step 3, step 2 gained white precipitate
It is reacted 12 hours in closed autoclave in 180 DEG C.
5. preparation method according to claim 1, which is characterized in that in the step 4, the white powder is MgBO2
(OH)。
6. preparation method according to claim 1, which is characterized in that in the step 5, the white powder heating
Heating rate is 1~5 DEG C/min, preferably 1~2 DEG C/min.
7. the antifungin nano wire that the preparation method as described in claim 1~6 any one obtains, which is characterized in that the boron
The length of sour magnesium nano wire is 1~5 micron, and diameter is 20~30 nanometers.
8. a kind of antifungin nano wire is improving the application in epoxy resin bending property, which is characterized in that by curing agent and power
Benefit requires the 7 antifungin nano wires to mix and be ultrasonically treated 2~5 minutes in supersonic cleaning machine, then adds epoxy resin simultaneously
It is evenly dispersed, solidify after evenly dispersed, obtains epoxy resin composite material, wherein according to the mass fraction, the antifungin nanometer
Line is 0.25~1wt% of the epoxy resin, and the ratio of the mass fraction of the curing agent and the epoxy resin is 1:3.
9. application according to claim 8, which is characterized in that realized with magnetic stirrer at least 20 minutes described equal
Even dispersion；The curing agent is fatty amines curing agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810142196.6A CN110143601B (en) | 2018-02-11 | 2018-02-11 | Preparation method of magnesium borate nanowire and application of magnesium borate nanowire in epoxy resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810142196.6A CN110143601B (en) | 2018-02-11 | 2018-02-11 | Preparation method of magnesium borate nanowire and application of magnesium borate nanowire in epoxy resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110143601A true CN110143601A (en) | 2019-08-20 |
| CN110143601B CN110143601B (en) | 2022-12-23 |
Family
ID=67589038
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810142196.6A Active CN110143601B (en) | 2018-02-11 | 2018-02-11 | Preparation method of magnesium borate nanowire and application of magnesium borate nanowire in epoxy resin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110143601B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110776718A (en) * | 2019-10-17 | 2020-02-11 | 中国科学院青海盐湖研究所 | Epoxy resin composite material and preparation method thereof |
| CN116959815A (en) * | 2023-07-05 | 2023-10-27 | 苏州道旺电子科技有限公司 | Preparation process of polyethylene insulated cable |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004315237A (en) * | 2003-01-14 | 2004-11-11 | National Institute For Materials Science | Single-crystal magnesium borate nanotube and its preparation method |
| CN1936104A (en) * | 2006-09-08 | 2007-03-28 | 清华大学 | Magnesium borate whisker hydrothermal synthesis preparation method |
| CN101311372A (en) * | 2008-03-24 | 2008-11-26 | 清华大学 | Low-temperature molten salt thermal inversion preparation method of aporate-crystal antifungin whiskers |
| CN101585544A (en) * | 2009-06-08 | 2009-11-25 | 浙江工业大学 | Method for preparing aluminum borate nanowire |
| CN105821476A (en) * | 2016-05-09 | 2016-08-03 | 曲阜师范大学 | Mild hydrothermal-thermal transition synthetic method for high-draw-ratio hydrated and anhydrous calcium borate nanowhisker |
-
2018
- 2018-02-11 CN CN201810142196.6A patent/CN110143601B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004315237A (en) * | 2003-01-14 | 2004-11-11 | National Institute For Materials Science | Single-crystal magnesium borate nanotube and its preparation method |
| CN1936104A (en) * | 2006-09-08 | 2007-03-28 | 清华大学 | Magnesium borate whisker hydrothermal synthesis preparation method |
| CN101311372A (en) * | 2008-03-24 | 2008-11-26 | 清华大学 | Low-temperature molten salt thermal inversion preparation method of aporate-crystal antifungin whiskers |
| CN101585544A (en) * | 2009-06-08 | 2009-11-25 | 浙江工业大学 | Method for preparing aluminum borate nanowire |
| CN105821476A (en) * | 2016-05-09 | 2016-08-03 | 曲阜师范大学 | Mild hydrothermal-thermal transition synthetic method for high-draw-ratio hydrated and anhydrous calcium borate nanowhisker |
Non-Patent Citations (7)
| Title |
|---|
| WANCHENG ZHU等: "Hydrothermal Formation of the Head-to-Head Coalesced Szaibelyite MgBO2(OH) Nanowires", 《NANOSCALE RES LETT》 * |
| 丁田田等: "硼酸镁晶须的可控合成及表征", 《无机盐工业》 * |
| 侯嘉: "硼酸镁纳米线的合成", 《辽东学院学报(自然科学版)》 * |
| 张亮等: "晶须对环氧树脂改性的研究进展", 《塑料助剂》 * |
| 戴静等: "硼酸盐晶须改性环氧树脂性能研究", 《功能材料》 * |
| 谭文娟: "硼酸镁一维纳米材料的合成研究", 《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》 * |
| 郝志红等: "硼酸镁纳米线的制备和对环氧树脂的增强作用", 《材料科学与工程学报》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110776718A (en) * | 2019-10-17 | 2020-02-11 | 中国科学院青海盐湖研究所 | Epoxy resin composite material and preparation method thereof |
| CN116959815A (en) * | 2023-07-05 | 2023-10-27 | 苏州道旺电子科技有限公司 | Preparation process of polyethylene insulated cable |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110143601B (en) | 2022-12-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110143601A (en) | The preparation method of antifungin nano wire and its application in the epoxy | |
| CN114573875B (en) | Preparation method of nano silicon dioxide-calcium silicate whisker and modified phenolic resin | |
| CN107460545B (en) | A kind of preparation method of rodlike zirconium oxide whisker | |
| CN114134574B (en) | High-length-diameter-ratio basic magnesium sulfate whisker and preparation method thereof | |
| CN109292790B (en) | Preparation method of basic magnesium borate nanorod | |
| CN107539965B (en) | A kind of preparation method of nano-calcium carbonate calcium pyroborate/hexagonal nanometer boron nitride composite material | |
| JP6516594B2 (en) | Hexagonal boron nitride particles and method for producing the same | |
| CN107383725B (en) | Preparation method of gadolinium metal organic framework/polyvinyl alcohol nano composite film | |
| CA1297658C (en) | Process for producing alumina-based fiber | |
| JP3700964B2 (en) | Aluminosilicate filler | |
| JPH0640715A (en) | Production of spherical secondary particles of calcium silicate | |
| JP3643915B2 (en) | Novel calcium silicate whisker and method for producing the same | |
| Wang et al. | Morphology control and characteristic parameter R of molten-salt-synthesized K 2 Ti 6 O 13 whiskers | |
| CN115612456A (en) | Crystal seed induced synthetic phase-change high-strength gypsum powder and preparation method thereof | |
| CN109843808B (en) | Method for preparing potassium titanate | |
| JPS62132719A (en) | Synthetic xonotlite crystal aggregate and manufacture | |
| Wang et al. | A cost-effective process for synthesizing magnesium borate nanorods and its mechanical property for reinforced nylon-6 composites | |
| JPS62260796A (en) | Production of potassium titanate fiber | |
| Mo et al. | Controllable synthesis of high aspect ratio Mg2B2O5 nanowires and their applications in reinforced polyhydroxyalkanoate composites | |
| JP3219859B2 (en) | Potassium titanate whisker and composite material containing the same | |
| JPH04144997A (en) | Alkali titanate spherical coagulated whisker and production of the same | |
| CN108706611A (en) | A kind of magnesium hydroxide one-dimensional material preparation method that size is controllable | |
| JP3219858B2 (en) | Potassium titanate whisker and composite material containing the same | |
| JPH0244774B2 (en) | ||
| JPH07206440A (en) | Production of sodium hexatitanate fiber |
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 |