CN115745623A - Aluminum nitride composite material, preparation method and application thereof - Google Patents
Aluminum nitride composite material, preparation method and application thereof Download PDFInfo
- Publication number
- CN115745623A CN115745623A CN202211478310.5A CN202211478310A CN115745623A CN 115745623 A CN115745623 A CN 115745623A CN 202211478310 A CN202211478310 A CN 202211478310A CN 115745623 A CN115745623 A CN 115745623A
- Authority
- CN
- China
- Prior art keywords
- aluminum nitride
- parts
- composite material
- powder
- weight
- 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
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 title claims abstract description 115
- 239000002131 composite material Substances 0.000 title claims abstract description 80
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000000843 powder Substances 0.000 claims abstract description 64
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 25
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000002994 raw material Substances 0.000 claims abstract description 15
- 238000005245 sintering Methods 0.000 claims description 50
- 238000000034 method Methods 0.000 claims description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- 239000002002 slurry Substances 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 15
- 229910017083 AlN Inorganic materials 0.000 claims description 12
- PIGFYZPCRLYGLF-UHFFFAOYSA-N Aluminum nitride Chemical compound [Al]#N PIGFYZPCRLYGLF-UHFFFAOYSA-N 0.000 claims description 12
- 238000000748 compression moulding Methods 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000011230 binding agent Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- 229910004261 CaF 2 Inorganic materials 0.000 claims description 8
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 4
- 239000000853 adhesive Substances 0.000 claims description 3
- 230000001070 adhesive effect Effects 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 229910018068 Li 2 O Inorganic materials 0.000 claims description 2
- 230000001476 alcoholic effect Effects 0.000 claims description 2
- 239000000022 bacteriostatic agent Substances 0.000 claims description 2
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 14
- 229910010293 ceramic material Inorganic materials 0.000 abstract description 3
- 239000000919 ceramic Substances 0.000 description 23
- 239000000463 material Substances 0.000 description 15
- 229910017109 AlON Inorganic materials 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 8
- 241000588724 Escherichia coli Species 0.000 description 7
- 230000003385 bacteriostatic effect Effects 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 241000894006 Bacteria Species 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 238000001272 pressureless sintering Methods 0.000 description 5
- 230000001580 bacterial effect Effects 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910001385 heavy metal Inorganic materials 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000003242 anti bacterial agent Substances 0.000 description 2
- 229940088710 antibiotic agent Drugs 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 210000003470 mitochondria Anatomy 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 230000035755 proliferation Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229920001817 Agar Polymers 0.000 description 1
- 206010059866 Drug resistance Diseases 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 239000008272 agar Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 210000000805 cytoplasm Anatomy 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000012217 deletion Methods 0.000 description 1
- 230000037430 deletion Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000001963 growth medium Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000001513 hot isostatic pressing Methods 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 208000015181 infectious disease Diseases 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000009768 microwave sintering Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000008450 motivation Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000006916 nutrient agar Substances 0.000 description 1
- 239000004482 other powder Substances 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000002490 spark plasma sintering Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
Landscapes
- Ceramic Products (AREA)
Abstract
The invention provides an aluminum nitride composite material, a preparation method and application thereof, and belongs to the technical field of ceramic materials. The aluminum nitride composite material comprises the following raw materials: the aluminum nitride powder comprises, by weight, 35-75 parts of aluminum nitride powder, 10-30 parts of aluminum powder and 10-35 parts of aluminum oxide powder. The aluminum nitride composite material provided by the invention has obvious antibacterial performance.
Description
Technical Field
The invention belongs to the technical field of ceramic materials, and particularly relates to an aluminum nitride composite material, a preparation method and application thereof.
Background
Bacteria are affused in the aspects of human life, and the infection ways to human bodies are various. Although antibiotics are widely used in the market, the excessive use of antibiotics can cause the bacteria to generate drug resistance and bring about oneAnd (4) series side effects. Therefore, it is very important to research and develop antibacterial materials. At present, tiO 2 And ceramics containing Ag/Cu ions are more common bacteriostatic materials. TiO 2 2 Free radicals generated under ultraviolet rays can damage the bacterial structure, so that a bacteriostatic effect is generated, and Ag/Cu ions containing ceramics can release Ag, cu and other ions with a bactericidal effect in an aqueous solution, so that the aim of sterilization is fulfilled. But TiO is not limited to 2 Ultraviolet light is needed to sterilize in the using process and limited by application conditions, and Ag, cu and other ions belong to heavy metals, so that heavy metal residues can be caused in a water body after sterilization. Because the antibacterial materials have the defects of strict use conditions, difficult control and the like, more excellent materials still need to be further searched.
In the prior art, aluminium nitride powder is mainly used for preparing aluminium nitride ceramics, for example, document CN109402441A discloses a refractory AlN and Al 2 O 3 The method comprises pressing superfine aluminum powder to appropriate porosity, packaging into a sheath, sealing, and drilling around to allow air to enter; the sheath is placed in an air furnace for low-temperature heating to realize thickening of the oxide film; raising the temperature to high temperature, and respectively generating AlN and Al by using nitrogen and oxygen in the air 2 O 3 Sintering and hot working the powder after high temperature treatment to obtain (AlN + Al) with good high temperature strength and heat resistance 2 O 3 ) a/Al composite material. For another example, document CN111484333A discloses the preparation of pressureless sintered high thermal conductivity high strength aluminum nitride ceramics. The aluminum nitride ceramics is prepared by oxidizing the aluminum nitride sintered body obtained by pressureless sintering, an oxidation layer with proper thickness and compactness can be formed on the surface of the aluminum nitride sintered body by proper oxidation treatment, the formation of the oxidation layer can increase the residual compressive stress in the aluminum nitride matrix, and the change of the residual stress is helpful to prevent the expansion of cracks in the aluminum nitride ceramics and reduce the contact thermal resistance of aluminum nitride crystal boundaries. The aluminum nitride ceramic provided by the invention can meet the application requirements of industries such as semiconductor devices, integrated circuits and the like.
Therefore, the application potential of aluminum nitride in bacteriostasis is not found in the prior art, and the aluminum nitride composite material with corresponding bacteriostasis performance is explored and developed.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The first technical problem to be solved by the invention is to provide an aluminum nitride composite material with obvious antibacterial performance aiming at the defects of the prior art.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows: the aluminum nitride composite material comprises the following raw materials: the aluminum nitride powder comprises, by weight, 35-75 parts of aluminum nitride powder, 10-30 parts of aluminum powder and 10-35 parts of aluminum trioxide powder.
The aluminium nitride powder is very easy to hydrate in humid air and very easy to release NH under the action of water 3 And NO, but because of strong reaction with water, poor stability and great storage difficulty, the inventors thought that it was necessary to perform complex treatment or complex preparation by adding other powders so that it could exhibit stable bacteriostatic properties. The aluminum oxide has a series of excellent physical and chemical properties such as high hardness, high temperature resistance, oxidation resistance, corrosion resistance and the like, so that the aluminum nitride powder, the aluminum powder and the aluminum oxide powder are combined in a specific proportion to prepare the composite ceramic material, the stability of the aluminum nitride is regulated and controlled, the service performance of the aluminum nitride is improved, the obtained aluminum nitride composite material shows obvious antibacterial performance, and heavy metal ions cannot be generated in the using process.
In a specific embodiment of the present invention, the weight part of the aluminum nitride powder is preferably 40 to 70 parts, more preferably 50 to 70 parts, and can be selected from: 35 parts by weight, 40 parts by weight, 45 parts by weight, 50 parts by weight, 55 parts by weight, 60 parts by weight, 65 parts by weight, 70 parts by weight or 75 parts by weight;
in the embodiment of the present invention, the weight portion of the aluminum powder is preferably 15 to 25 weight portions, and can be selected from: 10 parts by weight, 12 parts by weight, 15 parts by weight, 18 parts by weight, 20 parts by weight, 23 parts by weight, 25 parts by weight, or 30 parts by weight;
in the embodiment of the present invention, the weight portion of the alumina is preferably 15 to 30, and may be selected from: 10 parts by weight, 12 parts by weight, 15 parts by weight, 20 parts by weight, 25 parts by weight, 30 parts by weight or 35 parts by weight.
Preferably, the aluminum nitride powder has a particle size of 200 mesh or less, preferably 200 mesh; the particle size of the aluminum powder is 325 meshes or less, preferably 325 meshes; the alumina powder has a particle size of 325 mesh or less, preferably 325 mesh. The aluminum nitride powder, the aluminum powder and the aluminum oxide powder which meet the particle sizes are selected to be combined, so that the preparation is convenient, and the stability of the obtained composite material is good.
Preferably, the aluminum nitride composite material further comprises: a sintering aid, wherein the sintering aid is Y 2 O 3 、CaO、Li 2 O、B 2 O 3 、CaF 2 And YF 3 One or a combination of two or more of them. Wherein the combination form is as follows: caO-Y 2 O 3 、YF 3 -CaF 2 Or Y 2 O 3 -Li 2 O-CaO, but is not limited thereto.
Preferably, the weight portion of the sintering aid is 2-10 portions.
In a specific embodiment of the present invention, the sintering aid may be selected from: 2 parts by weight, 3 parts by weight, 4 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight or 10 parts by weight.
According to the invention, 2-10 parts by weight of sintering aid is added into the composite material, so that the sintering temperature of the material is reduced, the requirements of a forming process are met, and the microstructure and the performance of the material are improved. The sintering aid in the present invention is preferably YF-containing 3 Or Y 2 O 3 Two or more composite sintering aids, for example: such as: YF 3 -CaF 2 Or Y is 2 O 3 -Li 2 And the composite sintering aid promotes the sintering of alumina in a liquid phase form, the increase of the content of the sintering aid is beneficial to the densification of alumina ceramics, but the mechanical property of the material is reduced due to the excessive addition of the composite sintering aid.
Preferably, the aluminum nitride composite material further comprises: the adhesive is an alcoholic solution or an aqueous solution of one or more of polyvinyl alcohol (PVA), polyvinyl butyral (PVB), polyethylene glycol (PEG) and polyvinylpyrrolidone (PVP), and the mass concentration of the adhesive is 1-10%.
Preferably, the binder is 5-10 parts by weight.
In a specific embodiment of the invention, the binder may be selected from: 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight or 10 parts by weight.
The invention adds 5-10 weight parts of the binder into the composite material, so as to facilitate the compression molding of the material and have the capability of keeping a certain shape.
The invention also provides a preparation method of the aluminum nitride composite material, which comprises the following steps:
(1) Providing aluminum nitride powder, aluminum oxide powder and sintering aid, premixing, adding into deionized water or ethanol solution, and ultrasonically stirring to uniformly mix to obtain slurry;
(2) Drying the slurry, adding a binder, and then carrying out compression molding to obtain a blank;
(3) And drying the blank, and sintering in a nitrogen atmosphere to obtain the aluminum nitride composite material.
The preparation method of the invention is beneficial to the mass production of products and the control of the shape of the products.
Preferably, the sintering adopts a multi-section sintering process, and the temperature of the multi-section sintering is 600-800 ℃, 1000-1200 ℃ and 1300-1700 ℃ in sequence.
In the specific embodiment of the invention, the sintering is carried out from room temperature to 600-800 ℃ at the speed of 5-15 ℃/min, the temperature is kept for 1h, then the temperature is increased to 1000-1200 ℃ at the speed of 5-10 ℃/min, the temperature is kept for 1-1.5 h, then the temperature is increased to 1300-1700 ℃ at the speed of 2-3 ℃/min, and the temperature is kept for 6-8 h.
In the preparation method, the aluminum nitride powder, the aluminum oxide powder, the sintering aid and the binder are sequentially prepared from the following components in parts by weight: 35-75 parts, 10-30 parts, 10-35 parts, 2-10 parts and 5-10 parts.
Preferably, the compression moulding pressure is 80-120MPa, optionally 80MPa, 90MPa, 100MPa, 110MPa or 120MPa.
In particular embodiments of the invention, the ethanol solution has a concentration of 50-95% by volume, optionally 50%, 60%, 75%, 85% or 95%.
The invention also provides application of the aluminum nitride composite material as a bacteriostatic agent for inhibiting escherichia coli.
In the existing aluminum nitride composite materials, alN ceramics and AlON ceramics, both of which use aluminum nitride as a main raw material, have received much attention.
AlN ceramic is used as a chip substrate and a packaging material because of its high thermal conductivity, high strength, linear expansion coefficient close to that of silicon, small dielectric constant, high temperature resistance and excellent corrosion resistance, and its comprehensive properties are superior to those of SiC and Al 2 O 3 And BeO ceramics, which is an ideal material for the packaging of new-generation semiconductor substrates and electronic devices. In addition, the material also has good physical properties such as high strength, high hardness (12 GPa), high bending strength (300-400 MPa) and the like, excellent chemical stability and corrosion resistance, still has good high temperature and chemical stability even at high temperature, and can still keep stable when the temperature in the air is 1000 ℃ and the temperature in vacuum reaches 1400 ℃, thereby being an inorganic material with wide application prospect and developing rapidly.
For AlON ceramics, the high-temperature resistance, the thermal vibration stability, the erosion resistance, the light transmission and the processability are good, the light transmission is good in the range from near ultraviolet light to mid-infrared light (0.2-5.0 um), the transmittance of the AlON ceramics can exceed 80%, and the light transmission is isotropic, so that the AlON ceramics are widely applied to the fields of national defense and civil use. Therefore, the prior art does not relate to the antibacterial performance and the application of the AlN ceramic in the aspect, and related technologies in the field are not available for reference.
In the existing preparation of aluminum nitride composite materials, for AlN ceramics, the synthesis energy consumption of aluminum nitride powder is high (the sintering temperature is generally 1800K), the production period is long, and the production cost is high. Thus, it is possible to provideResearchers typically improve the performance of AlN ceramics by optimizing the sintering technique and adding sintering aids. For AlON ceramics, the preparation method is various and mainly comprises a one-step method and a two-step method. The one-step method is to take powder of aluminum oxide, aluminum nitride and the like as raw materials, and directly react and sinter the raw materials into AlON ceramic; the two-step method is to synthesize AlON powder by using powders of aluminum oxide, aluminum nitride and the like as raw materials, and then sinter the AlON powder into AlON ceramic. At present, the method for preparing AlON ceramic mainly comprises pressureless sintering, hot pressing sintering, hot isostatic pressing sintering, spark plasma sintering, microwave sintering and the like. Therefore, in the preparation process of the aluminum nitride composite material, a sintering technology is adopted, and in the existing sintering technology, aluminum oxide is generally added to adjust the product performance. The prior publications show that the weight proportion of aluminum oxide added in the aluminum nitride composite material is generally above 70%, and the weight proportion of aluminum nitride added is below 30%, for example: the aluminum oxynitride ceramic in CN100506750C is 80-95% of Al 2 O 3 And 5-20% of AlN, and then a sintering aid is added to prepare the material; for example, in CN107344854A, the mass ratio of alumina powder to aluminum nitride powder is (70-73): (27-30), adding a sintering aid to prepare the material; and the aluminum nitride composite material prepared by the method has different performances or characteristics, has application potentials and values in different directions, but does not relate to the antibacterial performance and the application aspect thereof.
Therefore, the skilled person can not easily think about exploring and researching the application of the aluminum nitride material in bacteriostasis based on the related prior art of the aluminum nitride material, and further obtain the aluminum nitride composite material with stable bacteriostasis performance. Moreover, even if motivation is obtained in terms of the properties of the aluminum nitride powder itself, specific technical teaching in this direction cannot be obtained based on the raw material composition and the preparation technique thereof related to the conventional aluminum nitride material.
The inventor bases on that the aluminum nitride powder is very easy to hydrate in humid air and very easy to release NH under the action of water 3 However, it is considered that the reaction with water is strong, the stability is poor and the storage difficulty is large, and the complex treatment of the compound or the complex preparation by adding other powder can be realizedImprove the antibacterial performance and stability thereof. Meanwhile, the aluminum oxide has a series of excellent physicochemical properties such as high hardness, high temperature resistance, oxidation resistance, corrosion resistance and the like, so that the inventor prepares the aluminum nitride composite material by combining aluminum nitride powder, aluminum powder and aluminum oxide powder in a specific ratio through long-term exploration and research.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides an aluminum nitride composite material through the technical scheme, the composite material is prepared by combining aluminum nitride powder, aluminum powder and aluminum oxide powder in a specific ratio, and the composite material realizes the regulation and control of the stability of the aluminum nitride based on the specific combination of the raw materials and the support of the preparation method, so that the aluminum nitride composite material shows obvious antibacterial performance, and does not generate heavy metal ions in the using process, thereby improving the safety.
The antibacterial performance of the aluminum nitride composite material is enhanced in the alkaline environment provided by the aluminum nitride, and the aluminum nitride composite material is decomposed in water to generate NH 3 ，NH 3 Electrolysis in water to form NH 4+ ，NH 4+ Enters cytoplasm to destroy the stability of DNA and RNA in cells and is reduced to generate NO, and the NO inhibits mitochondria to cause the deletion of the mitochondria of bacteria and cause the death of the bacteria, thereby having bacteriostatic effect.
The Escherichia coli culture experiment proves that the aluminum nitride composite material has an obvious inhibition effect on Escherichia coli proliferation, and the aluminum nitride composite material has antibacterial performance.
The aluminum nitride composite material adopts aluminum nitride powder, aluminum powder and aluminum oxide powder as raw materials, and is prepared by the steps of mixing the raw materials by a wet method, stirring the raw materials by ultrasonic waves to uniformly mix the raw materials, adding a binder, carrying out compression molding at room temperature, and finally carrying out sintering molding by a pressureless sintering process. In addition, the pressureless sintering process is carried out by combining three-section sintering processes, the selectable range of the final-section sintering temperature is 1300-1700 ℃, the preparation can be completed at the lowest temperature of 1300 ℃, the sintering temperature is relatively low, and the energy consumption is saved. In general, in the preparation process of the aluminum nitride composite material, all the steps and parameters are matched with each other, namely, a wet process is adopted to enable powder raw materials to be easily and uniformly mixed, then a binder is added to provide a forming basis for compression molding, and then favorable conditions are provided for pressureless sintering.
In addition, after the aluminum nitride composite material is soaked in deionized water for 0 day, 7 days and 14 days, the appearance and the performance are not obviously changed, which shows that the aluminum nitride composite material has good stability.
Drawings
The invention is further illustrated with reference to the following figures and examples.
FIG. 1: e.coli colony map;
FIG. 2 is a schematic diagram: coli growth profile.
Detailed Description
In order to better understand the present invention, the following examples are further provided to clearly illustrate the contents of the present invention, but the contents of the present invention are not limited to the following examples. In the following description, numerous specific details are set forth in order to provide a more thorough understanding of the present invention. It will be apparent, however, to one skilled in the art, that the present invention may be practiced without one or more of these specific details. All other embodiments, which can be obtained by a person skilled in the art without inventive step based on the embodiments of the present invention, are within the scope of protection of the present invention.
In all examples shown and discussed herein, any particular value should be construed as exemplary only and not as limiting. Thus, other examples of the exemplary embodiments may have different values.
All raw materials are derived from commercially available products unless otherwise specified, and contain no other components not specifically specified except for unavoidable impurities.
In the following examples, room temperature is 25. + -. 5 ℃; the granularity of the aluminum nitride powder is 200 meshes; the particle size of the aluminum powder is 325 meshes; the alumina powder had a particle size of 325 mesh.
Examples 1 to 6 and comparative examples 1 to 2 described below are examples of preparation of aluminum nitride composites.
Example 1
Providing 67 parts by weight of aluminum nitride powder, 14 parts by weight of aluminum powder, 16 parts by weight of aluminum oxide powder and YF 3 -CaF 2 3 parts by weight of composite sintering aid is premixed, added into absolute ethyl alcohol with volume concentration of 80%, and stirred by ultrasonic wave to be uniformly mixed, so that slurry is obtained;
drying the slurry, adding 5wt% of PVB alcohol solution by 8 parts by weight, and then carrying out compression molding under 100MPa to obtain a blank body;
and drying the blank, placing the blank in a nitrogen atmosphere, raising the temperature from room temperature to 700 ℃ at a speed of 10 ℃/min, preserving the heat for 1h, then raising the temperature to 1100 ℃ at a speed of 8 ℃/min, preserving the heat for 1.2h, raising the temperature to 1500 ℃ at a speed of 2.5 ℃/min, and preserving the heat for 7h to obtain the aluminum nitride composite material.
Example 2
Providing 56 parts by weight of aluminum nitride powder, 18 parts by weight of aluminum powder, 24 parts by weight of aluminum oxide powder and Y 2 O 3 -Li 2 2 parts by weight of O-CaO composite sintering aid, premixing, adding into absolute ethyl alcohol with volume concentration of 80%, and stirring by ultrasonic waves to uniformly mix to obtain slurry;
drying the slurry, adding 7 parts by weight of the PVB alcohol solution according to the percentage by weight of 3 weight, and then carrying out compression molding under 100MPa to obtain a blank body;
and drying the blank, placing the blank in a nitrogen atmosphere, raising the temperature from room temperature to 650 ℃ at the speed of 8 ℃/min, preserving the heat for 1h, then raising the temperature to 1000 ℃ at the speed of 5 ℃/min, preserving the heat for 1h, raising the temperature to 1400 ℃ at the speed of 2 ℃/min, and preserving the heat for 6.5h to obtain the aluminum nitride composite material.
Example 3
Providing 48 parts by weight of aluminum nitride powder, 24 parts by weight of aluminum powder, 25 parts by weight of aluminum oxide powder and Y 2 O 3 3 parts by weight of sintering aid is premixed, added into anhydrous ethanol with the volume concentration of 75%, and stirred by ultrasonic waves to be uniformly mixed to obtain slurry;
drying the slurry, adding 7wt% of PVP aqueous solution 9 parts by weight, and then carrying out compression molding under 100MPa to obtain a blank body;
and drying the blank, placing the blank in a nitrogen atmosphere, raising the temperature from room temperature to 600 ℃ at the speed of 5 ℃/min, preserving the heat for 1h, then raising the temperature to 1200 ℃ at the speed of 10 ℃/min, preserving the heat for 1.5h, then raising the temperature to 1700 ℃ at the speed of 3 ℃/min, and preserving the heat for 6h to obtain the aluminum nitride composite material.
Example 4
Providing 40 parts by weight of aluminum nitride powder, 25 parts by weight of aluminum powder, 30 parts by weight of aluminum trioxide powder and CaO-Y 2 O 3 5 parts by weight of composite sintering aid is premixed, added into absolute ethyl alcohol with the volume concentration of 85 percent, and stirred by ultrasonic waves to be uniformly mixed to obtain slurry;
drying the slurry, adding 6wt% of PEG aqueous solution 5 parts by weight, and then carrying out compression molding under 100MPa to obtain a blank;
and drying the blank, placing the blank in a nitrogen atmosphere, raising the temperature from room temperature to 750 ℃ at the speed of 12 ℃/min, preserving heat for 1h, then raising the temperature to 1150 ℃ at the speed of 9 ℃/min, preserving heat for 1.2h, raising the temperature to 1600 ℃ at the speed of 2.1 ℃/min, preserving heat for 7.5h, and obtaining the aluminum nitride composite material.
Example 5
Providing 35 parts by weight of aluminum nitride powder, 28 parts by weight of aluminum powder, 33 parts by weight of aluminum oxide powder and YF 3 4 parts by weight of sintering aid is premixed, added into absolute ethyl alcohol with volume concentration of 65%, and stirred by ultrasonic wave to be uniformly mixed, so that slurry is obtained;
oven drying the slurry, adding 8wt% PVA aqueous solution 9 parts by weight, and then compression molding at 100MPa to obtain a green body;
and drying the blank, placing the blank in a nitrogen atmosphere, raising the temperature from room temperature to 800 ℃ at a speed of 15 ℃/min, preserving the heat for 1h, then raising the temperature to 1050 ℃ at a speed of 9 ℃/min, preserving the heat for 1.3h, raising the temperature to 1450 ℃ at a speed of 2.6 ℃/min, and preserving the heat for 7.5h to obtain the aluminum nitride composite material.
Example 6
Providing 72 parts by weight of aluminum nitride powder, 10 parts by weight of aluminum oxide powder and YF 3 -CaF 2 8 parts by weight of composite sintering aid is premixed,adding the mixture into absolute ethyl alcohol with the volume concentration of 75%, and stirring the mixture by ultrasonic waves to uniformly mix the mixture to obtain slurry;
drying the slurry, adding 6wt% of PVB alcohol solution 7 parts by weight, and then carrying out compression molding under 100MPa to obtain a blank body;
and drying the blank, placing the blank in a nitrogen atmosphere, raising the temperature from room temperature to 720 ℃ at the speed of 7 ℃/min, preserving the heat for 1h, then raising the temperature to 1120 ℃ at the speed of 6 ℃/min, preserving the heat for 1.4h, raising the temperature to 1550 ℃ at the speed of 2.8 ℃/min, and preserving the heat for 7h to obtain the aluminum nitride composite material.
Comparative example 1
An aluminum nitride composite was prepared in the same manner as in example 1, except that: 10 parts by weight of aluminum nitride powder, 43 parts by weight of aluminum powder, 44 parts by weight of aluminum oxide powder and YF 3 -CaF 2 3 parts of composite sintering aid.
Comparative example 2
An aluminum nitride composite was prepared in the same manner as in example 1, except that: 30 parts by weight of aluminum nitride powder, 32 parts by weight of aluminum powder, 35 parts by weight of aluminum oxide powder and YF 3 -CaF 2 3 parts of composite sintering aid.
The antibacterial performance of the aluminum nitride composite materials prepared in example 1 and comparative examples 1 to 2 was measured by the dip shaking method.
The experimental method comprises the following steps: the aluminum nitride composite materials prepared in example 1 and comparative examples 1 to 2 were cut into 5mm × 5mm × 1mm pieces, washed with tap water, and washed with sterile distilled water 3 times. Collecting fresh slant culture of Escherichia coli third generation nutrient agar culture medium, washing thallus Porphyrae with 5ml sterilized normal saline, shaking and knocking for 80 times, mixing, diluting to obtain diluted bacteria solution with concentration of 10 4 ～10 5 cfu/ml. The sample pieces were placed in 250ml Erlenmeyer flasks, 95ml of PBS and 5ml of bacterial solution were added, the Erlenmeyer flasks were fixed on a shaking table and shaken at 270r/min for 24 hours. And simultaneously setting a blank control group without the sample wafer, and repeating the operation.
(1) 0.5ml of the shaken bacterial solution is taken from each group, the plates are inoculated by an agar pouring method, the culture is carried out for 24 hours, photographing is carried out when the culture is finished, the growth state of bacterial colonies is observed, and the result is shown in figure 1.
(2) The OD values of the samples were measured at 0h, 4h, 8h, 12h, 16h, 20h and 24h of shaking culture, respectively, and the change curves of OD values with the culture time were plotted, and the results are shown in FIG. 2.
The experimental results are as follows:
(1) As shown in fig. 1, the aluminum nitride composite material prepared in example 1 has significantly fewer colonies, and the growth state of the colonies is significantly different from that of the blank control group, which indicates that the aluminum nitride composite material prepared in example 1 has a significant bacteriostatic effect.
The colony growth state of the aluminum nitride composite materials prepared by adding the aluminum nitride composite materials prepared by the comparative examples 1 and 2 is not different from that of the blank control group, which shows that the aluminum nitride composite materials prepared by the comparative examples 1 and 2 have no bacteriostatic effect.
(2) As shown in fig. 2, the OD value of the culture solution added with the aluminum nitride composite material prepared in example 1 only increased by about 0.6 at 24 hours, and was almost unchanged after 16 hours, which indicates that the antibacterial performance of the aluminum nitride composite material of the present invention is stable.
The culture solution added with the aluminum nitride composite material prepared in the comparative example 1 and the aluminum nitride composite material prepared in the comparative example 2 has the OD value and the change trend which are basically the same as those of the blank control group in the whole culture process, and the OD is increased to more than 1.1 at 24 hours.
The results show that the aluminum nitride composite material has obvious effect of inhibiting the proliferation of escherichia coli and good stability.
Based on the results, the aluminum nitride composite material has obvious bacteriostasis and obvious inhibition effect on escherichia coli, and is expected to be applied as a bacteriostat.
Finally, the above embodiments are only used for illustrating the technical solutions of the present invention and are not limited, and other modifications or equivalent substitutions made by the technical solutions of the present invention by the persons skilled in the art should be covered within the scope of the claims of the present invention as long as they do not depart from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. The aluminum nitride composite material is characterized in that: the raw materials comprise: the aluminum nitride powder comprises, by weight, 35-75 parts of aluminum nitride powder, 10-30 parts of aluminum powder and 10-35 parts of aluminum oxide powder.
2. The aluminum nitride composite material of claim 1, wherein: the aluminum nitride powder has a particle size of 200 meshes or less, the aluminum powder has a particle size of 325 meshes or less, and the aluminum oxide powder has a particle size of 325 meshes or less.
3. The aluminum nitride composite material of claim 1, wherein: further comprising: a sintering aid, wherein the sintering aid is Y 2 O 3 、CaO、Li 2 O、B 2 O 3 、CaF 2 And YF 3 One or a combination of two or more of them.
4. The aluminum nitride composite material of claim 3, wherein: the weight portion of the sintering aid is 2-10 portions.
5. The aluminum nitride composite material of claim 4, wherein: further comprising: the adhesive is an alcoholic solution or an aqueous solution of one or more of polyvinyl alcohol, polyvinyl butyral, polyethylene glycol and polyvinylpyrrolidone.
6. The aluminum nitride composite material according to claim 5, wherein: the weight portion of the binder is 5-10 portions.
7. The preparation method of the aluminum nitride composite material is characterized by comprising the following steps: the method comprises the following steps:
(1) Providing aluminum nitride powder, aluminum oxide powder and a sintering aid, premixing, adding into deionized water or an ethanol solution, and ultrasonically stirring to uniformly mix to obtain slurry;
(2) Drying the slurry, adding a binder, and then carrying out compression molding to obtain a blank;
(3) And drying the blank, and sintering in a nitrogen atmosphere to obtain the aluminum nitride composite material.
8. The method for producing an aluminum nitride composite material according to claim 7, characterized in that: the sintering adopts a multistage sintering process, and the multistage sintering temperature is 600-800 ℃, 1000-1200 ℃ and 1300-1700 ℃ in sequence.
9. The method for producing an aluminum nitride composite material according to claim 7, characterized in that: the aluminum nitride powder, the aluminum oxide powder, the sintering aid and the binder are sequentially prepared from the following components in parts by weight: 35-75 parts, 10-30 parts, 10-35 parts, 2-10 parts and 5-10 parts.
10. Use of an aluminium nitride composite material according to any one of claims 1 to 6 or obtained by a method according to any one of claims 7 to 9 as a bacteriostatic agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211478310.5A CN115745623B (en) | 2022-11-23 | 2022-11-23 | Aluminum nitride composite material, preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211478310.5A CN115745623B (en) | 2022-11-23 | 2022-11-23 | Aluminum nitride composite material, preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115745623A true CN115745623A (en) | 2023-03-07 |
| CN115745623B CN115745623B (en) | 2024-02-06 |
Family
ID=85336485
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211478310.5A Active CN115745623B (en) | 2022-11-23 | 2022-11-23 | Aluminum nitride composite material, preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115745623B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5036026A (en) * | 1987-08-28 | 1991-07-30 | Sumitomo Electric Industries, Ltd. | Sintered body of aluminum nitride and method for producing the same |
| CN1142813A (en) * | 1993-12-22 | 1997-02-12 | 金刚砂公司 | A low temperature sintering route for aluminum nitride ceramics |
| JP2002173373A (en) * | 2000-12-07 | 2002-06-21 | Toshiba Corp | Aluminum nitride sintered compact, method of producing the same and electronic component using the same |
| CN101734923A (en) * | 2009-12-04 | 2010-06-16 | 西安交通大学 | Aluminum nitride porous ceramic and preparation method thereof |
| CN104987081A (en) * | 2015-06-05 | 2015-10-21 | 黄勤 | Method for preparing aluminum nitride ceramic substrate with composite powder grain shape |
| CN110015648A (en) * | 2019-03-28 | 2019-07-16 | 北京中材人工晶体研究院有限公司 | A kind of high-purity aluminium nitride powder and aluminium nitride powder method of purification |
-
2022
- 2022-11-23 CN CN202211478310.5A patent/CN115745623B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5036026A (en) * | 1987-08-28 | 1991-07-30 | Sumitomo Electric Industries, Ltd. | Sintered body of aluminum nitride and method for producing the same |
| CN1142813A (en) * | 1993-12-22 | 1997-02-12 | 金刚砂公司 | A low temperature sintering route for aluminum nitride ceramics |
| JP2002173373A (en) * | 2000-12-07 | 2002-06-21 | Toshiba Corp | Aluminum nitride sintered compact, method of producing the same and electronic component using the same |
| CN101734923A (en) * | 2009-12-04 | 2010-06-16 | 西安交通大学 | Aluminum nitride porous ceramic and preparation method thereof |
| CN104987081A (en) * | 2015-06-05 | 2015-10-21 | 黄勤 | Method for preparing aluminum nitride ceramic substrate with composite powder grain shape |
| CN110015648A (en) * | 2019-03-28 | 2019-07-16 | 北京中材人工晶体研究院有限公司 | A kind of high-purity aluminium nitride powder and aluminium nitride powder method of purification |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115745623B (en) | 2024-02-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110272270B (en) | Bismuth ferrite-barium titanate-based high-temperature lead-free piezoelectric ceramic with low dielectric loss and high-temperature stability and preparation method thereof | |
| WO2011016325A1 (en) | Transparent zirconia sintered body, method for producing same, and use of same | |
| CN110128127B (en) | Bismuth ferrite-barium titanate-based lead-free piezoelectric ceramic with high piezoelectric performance and high-temperature stability and preparation method thereof | |
| CN110128126B (en) | Bismuth ferrite-barium titanate-zinc bismuth titanate-bismuth aluminate high-temperature lead-free piezoelectric ceramic and preparation method thereof | |
| CN105601277A (en) | Preparation method of yttrium oxide-based transparent ceramic | |
| CN111925202B (en) | Yttrium aluminum garnet powder without sintering aid, yttrium aluminum garnet ceramic, and preparation method and application thereof | |
| CN108751991B (en) | Preparation of Tb: Lu by laser sintering2O3Method for producing ceramic | |
| KR102270157B1 (en) | Aluminum oxynitride ceramic heater and method for preparing the same | |
| CN110128128B (en) | Bismuth ferrite-bismuth aluminate-bismuth zinc titanate high-temperature piezoelectric ceramic with zero temperature coefficient and high-temperature stability and preparation method thereof | |
| CN1673173A (en) | Nano crystal adding alumina ceramic material and its low temperature liquid phase sintering process | |
| Shen et al. | Effect of debinding and sintering profile on the optical properties of DLP-3D printed YAG transparent ceramic | |
| CN103265286B (en) | Method for low-temperature preparation of Y2O3 and MgO codoped ZrO2 transparent ceramic through microwave sintering | |
| CN102815941A (en) | Rare-earth-ion-doped lanthanum gadolinium zirconate transparent ceramic material and preparation method thereof | |
| CN111196727A (en) | High-thermal-conductivity silicon nitride ceramic material and preparation method thereof | |
| CN115745623B (en) | Aluminum nitride composite material, preparation method and application thereof | |
| JP2002029742A (en) | Rare earth oxide powder and method for manufacturing the same | |
| CN100509692C (en) | Tungsten corundum ceramic material and low temperature sintering method | |
| CN112645709A (en) | PZT-based piezoelectric ceramic and preparation method thereof | |
| CN115947598B (en) | Antiferroelectric material capable of being co-fired with base metal inner electrode and preparation method thereof | |
| CN115073160B (en) | Hot-pressed sintering preparation method of bismuth ferrite-barium titanate ceramic with micro-nano electric domain structure | |
| CN1431164A (en) | High performance alumina bioceramic sintered under normal pressure and low temp | |
| CN110590353A (en) | Method for improving solid solubility of doped ions of YAG-based transparent ceramic | |
| CN102815945A (en) | Lanthanum gadolinium zirconate transparent ceramic material and preparation method thereof | |
| CN107399972A (en) | A kind of method that transparent aluminium nitride ceramic is prepared based on SPS methods | |
| CN111825451A (en) | Rare earth element Tm doped silver niobate antiferroelectric ceramic material and preparation method thereof |
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 |