CN107664596A - Organic-inorganic hybrid material and preparation method thereof and mechanical test substrate preparation method - Google Patents
Organic-inorganic hybrid material and preparation method thereof and mechanical test substrate preparation method Download PDFInfo
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Abstract
The present invention proposes the preparation method of organic-inorganic hybrid material, its preparation method and mechanical test substrate.The preparation method of the organic-inorganic hybrid material includes：(1) the first solution is mixed with the second solution；(2) mixture resulting in step (1) is centrifuged and collects sediment；And (3) are washed the sediment and drying process, to obtain the Inorganic-organic Hybrid Material.Wherein, first solution contains compound shown in Formulas I；Second solution contains silver ion.Preparation method proposed by the invention, can be by holding the self assembly of sulfydryl alkanoic acid and silver ion to directly obtain organic-inorganic hybrid material, the preparation process is easy, it is green, industrialization large-scale production is advantageously implemented, can also regulate and control the structure of organic-inorganic hybrid material and performance by changing the strand length of compound shown in Formulas I.
Description
Technical field
The present invention relates to Material Field, specifically, the present invention relates to organic-inorganic hybrid material, its preparation method and mechanics
The preparation method of test substrate.
Background technology
High polymer material, it is divided into natural macromolecular material and synthesis high polymer material according to source.
In natural macromolecular material, kind of starch azelon, silk, spider silk etc. are all natural fiber materials, have compared with
High tensile strength and ductility, or even performance is no less than steel in some aspects.At present, fiber is prepared in the industrial production
What method more relied on be " from top to bottom " mode, i.e., first hydrolyzed, purified then by biomaterials such as natural silk-fibroins
Prepare and obtain again.Also, mode " from bottom to top " is than relatively difficult to achieve, specifically, it is more difficult to passes through unit amino acid molecular
Self assembly goes out the fibrous material of high-mechanical property, it is difficult to large-scale production.And on the other hand, synthesis high polymer material is typically
Realized using polycondensation and sudden reaction, its synthesis technique and subsequent processes are complicated, also there is certain harm to environment.
Therefore, it is necessary to develop a kind of similar with natural fiber material mechanical property while industrialization can be met " from lower
On " large-scale production demand, the simple or green material of technique, for substitute natural fiber family macromolecule material and
Partial synthesis high polymer material.
The content of the invention
It is contemplated that at least solves one of technical problem in correlation technique to a certain extent.
The present invention is the following discovery based on inventor and completed：
The present inventor has found that natural fiber material has antiparallel beta sheet chain conformation, is to pass through in research process
The hydrogen bond action of the intermolecular carboxyl and amino of amino acid is assembled into close nano lamellar crystal, so that this kind of material has
Higher mechanical performance.Hydrogen bond, as a kind of one of most weak chemical bond, but shown in beta sheet chain nanocrystal stronger
Mechanical property.Meanwhile under weak hydrogen bond action amino acid molecular self assembly so that natural fiber can be in gentle condition
Lower preparation, and the power of regeneration of hydrogen bond is allowed to the performance that has possessed selfreparing.High mechanicalness based on such high polymer material
Energy and biocompatibility so that it has extensively in fields such as biological medicine, operation suture thread, silk-fibroin non-woven fabrics and cosmetics
Using.
Inventor, which furthers investigate, to be found, end sulfydryl alkanoic acid in the solution, can be self-assembly of organic with silver ion
Inorganic hybrid material, this method is simple, efficient also green, and the excellent in mechanical performance of the organic-inorganic hybrid material, with
Natural fiber material is similar.Also, it can also pass through the mol ratio of control terminal sulfydryl alkanoic acid and silver ion, you can obtain different
Organic-inorganic hybrid material, can have different microstructure and macro-mechanical property.
In view of this, it is an object of the present invention to propose that a kind of mechanical property is similar with natural fiber material, closes
The preparation method of the organic-inorganic hybrid material simple and green into step.
In the first aspect of the present invention, the present invention proposes a kind of method for preparing organic-inorganic hybrid material.
According to an embodiment of the invention, the preparation method of the material includes：(1) the first solution and the second solution are mixed
Close；(2) mixture resulting in step (1) is centrifuged and collects sediment；And (3) are washed the sediment
Wash and drying process, to obtain the Inorganic-organic Hybrid Material.Wherein, first solution contains compound shown in Formulas I：
SH-(CH2)n-COOH
Formulas I
N is 2~15 integer；Second solution contains silver ion.
Inventor is it was unexpectedly observed that compound shown in Formulas I is end sulfydryl alkanoic acid, and two are held sulfydryl alkanoic acid
Stable cyclic structure can be formed between carboxyl by two deuterium bonds；And hold the sulfydryl and silver ion of the sulfydryl alkanoic acid other end
Between there is stronger suction-operated.Therefore, in the presence of specific metal ion, and the first solution, the second solution are spy
During fixed proportioning, hydrogen bond is connected with suction-operated by way of head-head and tail-tail, promotes to hold sulfydryl alkanoic acid can
It is spontaneously assemble into the structure of high-sequential.The ordered structure that this self assembly mode is formed, its Thermodynamically stable, energy are most
Low, accumulation is closely or defect is few.Also, self-assembling technique is simple and easy to do, without special device, generally using water as solvent, tool
There is the advantages of deposition process and membrane structure molecular level control.
Generally, it is considered that in the structure of end sulfydryl alkanoic acid, only the sulfydryl at both ends and carboxyl have reactivity, middle
Carbon skeleton length be not influence directly on self-assembling reaction, in other words, in the tool of compound methylene shown in Formulas I
Body number n, the orderly progress of the self-assembling method can't be significantly affected.But inventor is it was unexpectedly observed that carbon chain lengths meeting
The activity of end sulfydryl alkanoic acid is significantly affected, inventor is found through experiments that carbon chain lengths can significantly affect self assembly and finally obtain
The structure of the organic-inorganic hybrid material obtained.For example, when n is 1, inventor has found the organic-inorganic hybrid material that self assembly obtains
Non-laminar structure, but the structure of hexagonal phase, it may be possible to due to the organic-inorganic hybrid material hydrophobe small volume, formation group
Assembling structure curvature is larger.Likewise, when n is the integer more than 10, the self-assembled structures that inventor has found to obtain easily lack
Fall into, it may be possible to cause interlayer hydrogen bond action not support because carbon chain lengths are long, carbochain is not easy all to keep stretching chain
State.Therefore, when the number n of compound methylene shown in Formulas I is 2~10 integer, organic-inorganic hybrid material is more easy to keep
The layer structure of high-sequential, so as to which the material has more preferable mechanical performance.
Inventor it was unexpectedly observed that using the embodiment of the present invention preparation method, can by hold sulfydryl alkanoic acid with silver
The self assembly of ion directly obtains organic-inorganic hybrid material, and the preparation process is easy, green, is advantageously implemented industrialization
Large-scale production, can also regulate and control the structure of organic-inorganic hybrid material by changing the strand length of compound shown in Formulas I
And performance.
In addition, the method according to the above embodiment of the present invention for preparing organic-inorganic hybrid material, can also have as follows
Additional technical characteristic：
According to an embodiment of the invention, n is 1~10 integer.Inventor is it was unexpectedly observed that with compound shown in Formulas I
There is first increasing becoming of being gradually reduced afterwards in the number n of methylene increase, the mechanical performance of the organic-inorganic hybrid material
Gesture.Wherein, the modulus of elasticity highest of the organic-inorganic hybrid material formed with 3- mercaptopropionic acids during n=2.Thus, using this
The preparation method of inventive embodiments, can be by holding the self assembly of sulfydryl alkanoic acid and silver ion to directly obtain more high-mechanical property
Organic-inorganic hybrid material, can also effectively regulate and control organic-inorganic by changing the strand length of compound shown in Formulas I
The performance of hybrid material.
According to an embodiment of the invention, second solution contains silver nitrate.Thus, using the nitric acid of the embodiment of the present invention
Silver be used as silver ion solution, can self assembly acquisition organic-inorganic hybrid material, and the wide material sources of silver nitrate and cost it is cheap, it is green
Colour circle is protected.
According to an embodiment of the invention, in step (1), the concentration of compound shown in Formulas I is in first solution
0.001~14mol/L, the concentration of silver nitrate is 0.0005~1mol/L in second solution, first solution and second
The ratio between volume of solution is 1:100~1:10.Inventor is it was unexpectedly observed that the self assembly of end sulfydryl alkanoic acid and silver ion
Journey under diluter concentration, it is necessary to carry out.Thus, using the preparation method of the embodiment of the present invention, can accurately regulate and control mixed
The proportioning of liquid middle-end sulfydryl alkanoic acid and silver ion is closed, so as to more effectively obtain organic-inorganic hybrid material.
According to an embodiment of the invention, the organic-inorganic hybrid material is lamellar phase package assembly, and shown in the Formulas I
Compound and the mol ratio of the silver ion are 1:1~20:1；Or the organic-inorganic hybrid material is unordered package assembly,
And compound shown in the Formulas I and the mol ratio of the silver ion are 1:1~1:20.Inventor passes through in depth research and found,
Sulfydryl alkanoic acid and silver ion is held to obtain the organic-inorganic hybrid material with different structure under different ratio, i.e., in order
Lamellar phase either unordered phase.And in two kinds of structures, the mechanical performance of lamellar phase ordered structure is apparently higher than disordered structure
Mechanical performance.
Thus, can be by accurately regulating and controlling mixed liquor middle-end sulfydryl straight chain using the preparation method of the embodiment of the present invention
The different ratio of alkanoic acid and silver ion, so as to obtain lamellar phase structure and the excellent organic-inorganic hybrid material of mechanical performance.
In the second aspect of the present invention, the present invention proposes a kind of organic-inorganic hybrid material.
According to an embodiment of the invention, the organic-inorganic hybrid material is obtained by foregoing method.
Inventor it was unexpectedly observed that using the embodiment of the present invention organic-inorganic hybrid material, its mechanical property with it is natural
Fibrous material is similar, and its preparation method is efficient, easy, green.It will be appreciated to those of skill in the art that above pin
To preparing the feature and advantage described by the method for organic-inorganic hybrid material, the organic-inorganic hybrid material is still applied to,
This is repeated no more.
In addition, organic-inorganic hybrid material according to the above embodiment of the present invention, can also have technology additional as follows
Feature：
According to an embodiment of the invention, the organic-inorganic hybrid material has 0.6~20.9GPa modulus of elasticity.Hair
A person of good sense is surprised to find that in natural fiber, and the modulus of elasticity of wool is 1.2~2.9GPa, the modulus of elasticity of silk for 6.4~
11.7GPa, the modulus of elasticity of spider silk is 12~34GPa, the modulus of elasticity of these natural fibers and the organic inorganic hybridization
The modulus of elasticity of material is close.Meanwhile the modulus of elasticity of the nylon66 fiber in synthetic fibers is 1.8~8.3GPa, PET springform
Measure as 2.0~4.0GPa.Thus, the organic-inorganic hybrid material of the embodiment of the present invention, have similar with natural fiber material
Mechanical property, be expected to substitute natural fiber family macromolecule material and partial synthesis high polymer material, apply medical science, sensing and
In terms of electricity.
It should be noted that the package assembly of the organic-inorganic hybrid material may be orderly lamellar phase or unordered
Phase.When the organic-inorganic hybrid material is lamellar phase package assembly, is tested by XRD and find that its lattice accumulation mode is stratiform
Phase, the membranaceous microscopic appearance of nanoscale is seen under electronic scanner microscope, and can be obtained by nano impress mechanics test system
Its modulus of elasticity scope is obtained in 1.5~20.9GPa.Or under identical method of testing, the organic-inorganic hybrid material is
Unordered package assembly, no lattice accumulation mode have a microscopic appearance of chaotic phase, and its modulus of elasticity scope only 0.6~
2.4GPa。
According to an embodiment of the invention, the Inorganic-organic Hybrid Material has lamellar phase package assembly：Interlamellar spacing is
1.32nm, modulus of elasticity are 11.9~20.9GPa；Interlamellar spacing is 1.83nm, and modulus of elasticity is 5.1~8.3GPa；Interlamellar spacing is
2.35nm or 2.46nm, modulus of elasticity are 1.5~3.3GPa；Or interlamellar spacing is 3.19nm, modulus of elasticity is 1.9~
4.1GPa.Thus, the organic-inorganic hybrid material of the embodiment of the present invention, by changing the strand length of compound shown in Formulas I,
The microcosmic physical dimension of organic-inorganic hybrid material and the mechanical property of macroscopic view can effectively be regulated and controled.
It should be noted that in the present invention, present inventors discovered unexpectedly that methylene in compound shown in Formulas I
Negative correlation be present in the number n of base and the interlamellar spacing d of layer structure, the elastic modulus E of organic-inorganic hybrid material.That is n values are got over
Greatly, the carbochain of the end sulfydryl alkanoic acid is longer, and the spacing d for being similar to twice of sulfydryl alkanoic acid between lamella is got over
Greatly；And in applying power in the vertical direction of lamellar structure, cyclic structure and the absorption of sulfydryl-silver ion that dual hydrogen bond is formed
Act on the self assembly region collectively constituted to be not easy to be compressed, but the region of carbochain extended chain parallel arrangement is easily to produce
The region of defect, n values are bigger, and carbochain is more long to be more easily folded, therefore the elastic modulus E of organic-inorganic hybrid material is smaller.
In the third aspect of the present invention, the present invention proposes a kind of method for preparing mechanical test substrate.
According to an embodiment of the invention, methods described includes：(a) Inorganic-organic Hybrid Material is mixed with solvent,
To form suspension, wherein, the Inorganic-organic Hybrid Material is as described above described in any one；(b) by the suspension
Apply to monocrystalline silicon piece, and carry out vacuum drying treatment, to obtain the mechanical test substrate.
Inventor is it was unexpectedly observed that the preparation method of the mechanical test substrate using the embodiment of the present invention, organic-inorganic are miscellaneous
Change material powder can film forming, for nano impress mechanics test system detection material modulus of elasticity.People in the art
Member is still applicable, it is understood that above for the feature and advantage described by organic-inorganic hybrid material and preparation method thereof
In the preparation method of the mechanical test substrate, will not be repeated here.
It will be appreciated to those of skill in the art that the solvent can be at least one of water and ethanol；The suspension
Concentration is 1~20mg/mL, specific 5~10mg/mL；The size of the monocrystalline silicon piece is 0.5cm × 0.5cm~1cm × 1cm,
Specific 0.5cm × 0.5cm.Wherein, good dispersion of the organic-inorganic hybrid material in water or ethanol, and volatility
It is good, it is green；The concentration of suspension should not exceed 20mg/mL, otherwise poor dispersion, and the surface of mechanical test substrate is easy
It is uneven, is unfavorable for the test of the mechanical property of organic-inorganic hybrid material；The detection displacement of impression mechanics test system point
Resolution is in Nano grade, and the size of monocrystalline silicon piece is 0.5cm × 0.5cm or 1cm × 1cm, and specific 0.5cm × 0.5cm is most
It is good.
In the fourth aspect of the present invention, the present invention proposes a kind of foregoing organic-inorganic hybrid material in medicine, sterilization, biography
Sense and the purposes of electronics.
Inventor it was unexpectedly observed that using the embodiment of the present invention organic-inorganic hybrid material, its good biocompatibility, contain
Some silver elements have antibacterial action and electric conductivity, can have application in medicine, sterilization, sensing and electronics.Art technology
Personnel still fit, it is understood that above for the feature and advantage described by organic-inorganic hybrid material and preparation method thereof
For the application of the organic-inorganic hybrid material, will not be repeated here.
The additional aspect and advantage of the present invention will be set forth in part in the description, and will partly become from the following description
Obtain substantially, or recognized by the practice of the present invention.
Brief description of the drawings
The above-mentioned and/or additional aspect and advantage of the present invention will become in the description from combination accompanying drawings below to embodiment
Substantially and it is readily appreciated that, wherein：
Fig. 1 is the SEM figures and XRD of hexagonal phase structure according to an embodiment of the invention；
Fig. 2 is the SEM figures and XRD of disordered structure in accordance with another embodiment of the present invention；
Fig. 3 is the SEM figures and XRD of lamellar phase structure in accordance with another embodiment of the present invention；
Fig. 4 is the SEM figures and XRD of disordered structure in accordance with another embodiment of the present invention；
Fig. 5 is the SEM figures and XRD of lamellar phase structure in accordance with another embodiment of the present invention；
Fig. 6 is the SEM figures and XRD of disordered structure in accordance with another embodiment of the present invention；
Fig. 7 is the SEM figures and XRD of lamellar phase structure in accordance with another embodiment of the present invention；
Fig. 8 is the SEM figures and XRD of disordered structure in accordance with another embodiment of the present invention；
Fig. 9 is the SEM figures and XRD of lamellar phase structure in accordance with another embodiment of the present invention；
Figure 10 is the SEM figures and XRD of disordered structure in accordance with another embodiment of the present invention；And
Figure 11 is the performance comparison figure of organic-inorganic hybrid material and other materials in accordance with another embodiment of the present invention.
Embodiment
Embodiments of the invention are described below in detail, those skilled in the art is it will be appreciated that example below is intended to be used to solve
The present invention is released, and is not construed as limitation of the present invention.Unless stated otherwise, it is not expressly recited in embodiment below specific
Technology or condition, those skilled in the art can be according to conventional technology in the art or condition or according to product description
Carry out.Agents useful for same or the unreceipted production firm person of instrument, being can be by the conventional products of acquisition purchased in market.
Conventional method
Unless expressly stated, in the examples below that using following preparation methods and detection method：
The preparation of organic-inorganic hybrid material：First, first 100mg silver nitrate is dissolved in 100mL deionized waters, will
The sulfydryl alkanoic acid of specified quantitative is added in 1mL deionized waters, then sulfydryl alkanoic acid solution is injected into rapidly into silver nitrate solution, is obtained
Mixed solution reacted 5 minutes under 500rpm mixing speeds and 5 degree celsius temperatures, to obtain flocculent deposit；Will be cotton-shaped heavy
Form sediment to be centrifuged 5 minutes under 4000rpm rotating speeds, add deionized water continuation centrifuge washing after removing supernatant, so wash repeatedly
After three times, it is freeze-dried, the powder of organic-inorganic hybrid material can be obtained；
The preparation of mechanical test substrate：Organic-inorganic hybrid material powder is mixed with aqueous solvent or ethanol, formed
Concentration is 1~20mg/mL suspension, and the square that suspension is added drop-wise to 0.5cm × 0.5cm~1cm × 1cm of cleaning is single
On crystal silicon chip, vacuumize, finally give the substrate of mechanical test, for nano impress mechanical test；
SEM test conditions：Model JEOL S-4800, accelerating potential 15kV；
XRD test conditions：Model Rigaku Dmax-2500, are tested using powder, and radiation source is that Cu Ka is penetrated
LineVoltage is 50kV, and electric current 200mA, sweep speed is 5 °/min；
Nano impress mechanical test condition：Model TriboScope nano-indenter test system, uses Oliver＆
Pharr methods are corrected and analyzed to test structure.
Embodiment 1
In this embodiment, according to the preparation method essentially identical with conventional method, organic nothing of preparation hexagonal phase structure
Machine hybrid material.Difference is that sulfydryl alkanoic acid is TGA in this embodiment, and 80 microlitres of TGA is added to
In 1mL deionized waters, the mol ratio of TGA and silver ion is 2 in the mixed solution of acquisition：1, obtain organic inorganic hybridization
The yellow powder of material.
In this embodiment, according still further to the test condition essentially identical with conventional method, to organic-inorganic hybrid material powder
End is tested, and AFM tests are carried out to mechanical test substrate prepared by organic-inorganic hybrid material.
The SEM figures and XRD of the embodiment, as shown in Figure 1.As seen from Figure 1, the assembly is under an electron microscope
Section is hexagonal fibrous morphology, and a diameter of 100 ± 20nm, length is up to 10 ± 3 microns；XRD diffraction patterns show the group
The crystal for filling body is orderly hexagonal phase structure, and its lattice parameter is 2.06nm.
Embodiment 2
In this embodiment, according to the preparation method and test condition with embodiment 1, the organic-inorganic of disordered structure is prepared
Hybrid material, and organic-inorganic hybrid material powder is tested, the mechanical test base prepared to organic-inorganic hybrid material
Bottom carries out AFM tests.Difference is, in this embodiment, 10 microlitres of TGA is added in 1mL deionized waters, obtained
The mol ratio of TGA and silver ion is 1 in the mixed solution obtained：10, finally give the white powder of organic-inorganic hybrid material
End.
The SEM figures and XRD of the embodiment, as shown in Figure 2.As seen from Figure 2, the assembly is under an electron microscope
The membranaceous pattern that nano-scale particle is crosslinked and formed；XRD diffraction patterns show that the powder of the assembly is chaotic unordered phase, no
With orderly package assembly.
Embodiment 3
In this embodiment, according to the preparation method and test condition with embodiment 1, organic nothing of lamellar phase structure is prepared
Machine hybrid material, and organic-inorganic hybrid material powder is tested, the mechanical test prepared to organic-inorganic hybrid material
Substrate carries out AFM tests.Difference is that sulfydryl alkanoic acid is 3- mercaptopropionic acids in this embodiment, by 100 microlitres of 3- sulfydryls third
Acid is added in 1mL deionized waters, and the mol ratio of 3- mercaptopropionic acids and silver ion is 2 in the mixed solution of acquisition：1 finally gives
The white powder of organic-inorganic hybrid material.
The SEM figures and XRD of the embodiment, as shown in Figure 3.As seen from Figure 3, the assembly is under an electron microscope
The membranaceous pattern of fold；XRD diffraction patterns show that the crystal of the assembly is lamellar phase structure, and its lattice parameter is 1.32nm, i.e.,
Each interlamellar spacing d is 1.32nm in crystal.
Embodiment 4
In this embodiment, according to the preparation method and test condition with embodiment 3, organic nothing of unordered phase structure is prepared
Machine hybrid material, and organic-inorganic hybrid material powder is tested, the mechanical test prepared to organic-inorganic hybrid material
Substrate carries out AFM tests.Difference is, 15 microlitres of 3- mercaptopropionic acids is added in 1mL deionized waters, the mixing of acquisition is molten
The mol ratio of 3- mercaptopropionic acids and silver ion is 1 in liquid：10, finally give the white powder of organic-inorganic hybrid material.
The SEM figures and XRD of the embodiment, as shown in Figure 4.As seen from Figure 4, the assembly is under an electron microscope
A large amount of random particle aggregates, particle diameter distribution is from 10~200nm；XRD diffraction patterns show that the powder of the assembly is mixed
Random unordered phase, without orderly package assembly.
Embodiment 5
In this embodiment, according to the preparation method and test condition with embodiment 1, organic nothing of lamellar phase structure is prepared
Machine hybrid material, and organic-inorganic hybrid material powder is tested, the mechanical test prepared to organic-inorganic hybrid material
Substrate carries out AFM tests.Difference is that sulfydryl alkanoic acid is 6- mercaptohexanoic acids in this embodiment, by 160 microlitres of 6- sulfydryls oneself
Acid is added in 1mL deionized waters, and the mol ratio of 6- mercaptohexanoic acids and silver ion is 2 in the mixed solution of acquisition：1, final
To the white powder of organic-inorganic hybrid material.
The SEM figures and XRD of the embodiment, as shown in Figure 5.As seen from Figure 5, the assembly is under an electron microscope
The membranaceous pattern of fold；XRD diffraction patterns show that the crystal of the assembly is lamellar phase structure, and its lattice parameter is 1.83nm, i.e.,
Each interlamellar spacing d is 1.83nm in crystal.
Embodiment 6
In this embodiment, according to the preparation method and test condition with embodiment 5, organic nothing of unordered phase structure is prepared
Machine hybrid material, and organic-inorganic hybrid material powder is tested, the mechanical test prepared to organic-inorganic hybrid material
Substrate carries out AFM tests.Difference is, 10 microlitres of 6- mercaptohexanoic acids is added in 1mL deionized waters, the mixing of acquisition is molten
The mol ratio of 6- mercaptohexanoic acids and silver ion is 1 in liquid：10, finally give the white powder of organic-inorganic hybrid material.
The SEM figures and XRD of the embodiment, as shown in Figure 6.As seen from Figure 6, the assembly is under an electron microscope
A large amount of flakey block aggregations, size is up to a few micrometers；XRD diffraction patterns show that the powder of the assembly is the unordered of confusion
Phase, without orderly package assembly.
Embodiment 7
In this embodiment, according to the preparation method and test condition with embodiment 1, organic nothing of lamellar phase structure is prepared
Machine hybrid material, and organic-inorganic hybrid material powder is tested, the mechanical test prepared to organic-inorganic hybrid material
Substrate carries out AFM tests.Difference is that sulfydryl alkanoic acid is 8- sulfydryls octanoic acid in this embodiment, and 200 microlitres of 8- sulfydryls is pungent
Acid is added in 1mL deionized waters, and the mol ratio of 8- sulfydryls octanoic acid and silver ion is 2 in the mixed solution of acquisition：1, final
To the white powder of organic-inorganic hybrid material.
The SEM figures and XRD of the embodiment, as shown in Figure 7.As seen from Figure 7, the assembly is under an electron microscope
The membranaceous pattern of fold；XRD diffraction patterns show that the crystal of the assembly is lamellar phase structure, have two kinds of lattice parameters
2.35nm and 2.46nm, the assembly are the Hybrid assembling body of two kinds of lamellar phase structures.
Embodiment 8
In this embodiment, according to the preparation method and test condition with embodiment 7, organic nothing of unordered phase structure is prepared
Machine hybrid material, and organic-inorganic hybrid material powder is tested, the mechanical test prepared to organic-inorganic hybrid material
Substrate carries out AFM tests.Difference is, 10 microlitres of 8- sulfydryl octanoic acids is added in 1mL deionized waters, the mixing of acquisition is molten
The mol ratio of 8- sulfydryls octanoic acid and silver ion is 1 in liquid：10, finally give the white powder of organic-inorganic hybrid material.
The SEM figures and XRD of the embodiment, as shown in Figure 8.As seen from Figure 8, the assembly and random of accordion
Grain aggregation, particle diameter distribution is from 10~200nm；XRD diffraction patterns show that the powder of the assembly is chaotic unordered phase,
Without orderly package assembly.
Embodiment 9
In this embodiment, according to the preparation method and test condition with embodiment 1, organic nothing of lamellar phase structure is prepared
Machine hybrid material, and organic-inorganic hybrid material powder is tested, the mechanical test prepared to organic-inorganic hybrid material
Substrate carries out AFM tests.Difference is that sulfydryl alkanoic acid is 11- mercaptoundecylic acids in this embodiment, by 250mg 11- sulfydryls
Undecanoic acid is added in 1mL deionized waters, and the mol ratio of 11- mercaptoundecylic acids and silver ion is 2 in the mixed solution of acquisition：1,
Finally give the pale yellow powder of organic-inorganic hybrid material.
The SEM figures and XRD of the embodiment, as shown in Figure 9.As seen from Figure 9, the assembly is under an electron microscope
The membranaceous pattern of fold；XRD diffraction patterns show that the crystal of the assembly is lamellar phase structure, and its lattice parameter is 3.19nm, i.e.,
Each interlamellar spacing d is 3.19nm in crystal.
Embodiment 10
In this embodiment, according to the preparation method and test condition with embodiment 9, organic nothing of unordered phase structure is prepared
Machine hybrid material, and organic-inorganic hybrid material powder is tested, the mechanical test prepared to organic-inorganic hybrid material
Substrate carries out AFM tests.Difference is, 10mg 11- mercaptoundecylic acids is added in 1mL deionized waters, the mixing of acquisition
The mol ratio of 11- mercaptoundecylic acids and silver ion is 1 in solution：10, obtain the pale yellow powder of organic-inorganic hybrid material.
The SEM figures and XRD of the embodiment, as shown in Figure 10.As seen from Figure 10, the assembly under an electron microscope
For a large amount of random particle aggregates, particle diameter distribution is from 10~150nm；XRD diffraction patterns show that the powder of the assembly is
Chaotic unordered phase, without orderly package assembly.
Embodiment 11
In this embodiment, according to the mechanical test substrate preparation method and test condition essentially identical with conventional method,
The mechanical test substrate prepared to the organic-inorganic hybrid material of embodiment 1~10, carries out nano impress mechanical test.In the reality
Apply in example, the organic-inorganic hybrid material of 1mg ordered phases or unordered phase is dispersed in 0.5mL deionized waters, after ultrasonic disperse
200 microlitres of suspensions are taken to be added drop-wise on 0.5cm × 0.5cm of cleaning silicon chip；Applied using nano impress mechanics test system
1000 micro- ox power are tested, each sample test 30 times, to obtain the average elastic modulus of the sample.
The embodiment is tested by nano impress mechanics test system, can obtain the springform of organic-inorganic hybrid material
Amount, specific test value are as shown in the table：
It can be found out by upper table, with the increase of n values, the carbon chain lengths of linear paraffin increase, organic-inorganic hybrid material
Modulus of elasticity, which is presented, first increases the trend reduced afterwards.Wherein, with the organic-inorganic hybrid material of the ordered structure of 3- mercaptopropionic acids
Mechanical performance it is best, its modulus of elasticity reaches 16.4 ± 4.5GPa, can be close with the modulus of elasticity of spider silk in natural fiber.
Also, the modulus of elasticity of orderly phase structure is apparently higher than disordered structure.
Summarize
Integrated embodiment 1~11 can show that proposed by the invention prepares organic-inorganic hybrid material method, can pass through end
The self assembly of sulfydryl alkanoic acid and silver ion directly obtains organic-inorganic hybrid material, and the preparation method is easy, green.
Also having with different structure and performance can be obtained by regulating and controlling the mol ratio of mixed liquor middle-end sulfydryl alkanoic acid and silver ion
Machine inorganic hybrid material, i.e. ordered phase either unordered phase.And in two kinds of structures, the mechanical property of orderly phase structure is substantially high
In the mechanical property of disordered structure.
Organic-inorganic hybrid material proposed by the invention, there is the mechanical property similar with natural fiber material, be expected to
Natural fiber family macromolecule material and partial synthesis high polymer material are substituted, is applied in terms of medical science, sensing and electricity.Its
In, sulfydryl alkanoic acid uses 3- mercaptopropionic acids, the mechanical property of the lamellar phase ordered structure of its organic-inorganic hybrid material prepared
Highest, modulus of elasticity reach 16.4 ± 4.5GPa, can be similar with the modulus of elasticity of spider silk in natural fiber.
In the description of this specification, reference term " one embodiment ", " some embodiments ", " example ", " specifically show
The description of example " or " some examples " etc. means specific features, structure, material or the spy for combining the embodiment or example description
Point is contained at least one embodiment or example of the present invention.In this manual, to the schematic representation of above-mentioned term not
Identical embodiment or example must be directed to.Moreover, specific features, structure, material or the feature of description can be with office
Combined in an appropriate manner in one or more embodiments or example.In addition, in the case of not conflicting, the skill of this area
Art personnel can be tied the different embodiments or example and the feature of different embodiments or example described in this specification
Close and combine.
Although embodiments of the invention have been shown and described above, it is to be understood that above-described embodiment is example
Property, it is impossible to limitation of the present invention is interpreted as, one of ordinary skill in the art within the scope of the invention can be to above-mentioned
Embodiment is changed, changed, replacing and modification.
Claims (10)
- A kind of 1. method for preparing organic-inorganic hybrid material, it is characterised in that the preparation method of the material includes：(1) the first solution is mixed with the second solution；(2) mixture resulting in step (1) is centrifuged and collects sediment；And(3) sediment is washed and drying process, to obtain the Inorganic-organic Hybrid Material,Wherein, first solution contains the compound shown in Formulas I：SH-(CH2)n-COOHFormulas IN is 1~15 integer,Second solution contains silver ion.
- 2. according to the method for claim 1, it is characterised in that n is 2~10 integer.
- 3. according to the method for claim 2, it is characterised in that second solution contains silver nitrate.
- 4. according to the method for claim 3, it is characterised in that in step (1),The concentration of compound in first solution shown in Formulas I is 0.001~14mol/L,The concentration of silver nitrate is 0.0005~1mol/L in second solution,The ratio between volume of first solution and the second solution is 1:100~1:10.
- 5. according to the method for claim 4, it is characterised in thatThe organic-inorganic hybrid material is lamellar phase package assembly, and compound shown in the Formulas I and the silver ion rub You are than being 1:1~20:1；OrThe organic-inorganic hybrid material is unordered package assembly, and compound shown in the Formulas I and mole of the silver ion Than for 1:1~1:20.
- 6. a kind of organic-inorganic hybrid material, the organic-inorganic hybrid material is by described in any one of Claims 1 to 5 What method obtained.
- 7. organic-inorganic hybrid material according to claim 6, it is characterised in that there is 0.6~20.9GPa springform Amount.
- 8. organic-inorganic hybrid material according to claim 7, it is characterised in that the Inorganic-organic Hybrid Material has Lamellar phase package assembly：Interlamellar spacing is 1.32nm, and modulus of elasticity is 11.9~20.9GPa；Interlamellar spacing is 1.83nm, and modulus of elasticity is 5.1~8.3GPa；Interlamellar spacing is 2.35nm and 2.46nm, and modulus of elasticity is 1.5~3.3GPa；OrInterlamellar spacing is 3.19nm, and modulus of elasticity is 1.9~4.1GPa.
- A kind of 9. method for preparing mechanical test substrate, it is characterised in that including：(a) Inorganic-organic Hybrid Material is mixed with solvent, to form suspension, wherein, the inorganic-organic hybrid Material is as described in any one of claim 1~8；(b) suspension is applied to monocrystalline silicon piece, and carries out vacuum drying treatment, to obtain the mechanical test base Bottom.
- 10. organic-inorganic hybrid material described in any one of claim 1~8 is in the use of medicine, sterilization, sensing and electronics On the way.
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