CN1238145C - Hollow metal particle with microbe cell template and its prepn process - Google Patents
Hollow metal particle with microbe cell template and its prepn process Download PDFInfo
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- CN1238145C CN1238145C CN 02130836 CN02130836A CN1238145C CN 1238145 C CN1238145 C CN 1238145C CN 02130836 CN02130836 CN 02130836 CN 02130836 A CN02130836 A CN 02130836A CN 1238145 C CN1238145 C CN 1238145C
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Abstract
The present invention discloses a hollow metal particle using microbe cells as a template, and a preparing method thereof. Microbe cells with different geometric shapes are used as a template, and a metal layer or an alloy plating layer is deposited on the surface of the template by using a chemical plating method to prepare a light hollow metal particle. The conductive or magnetic particle which is prepared by the preparing method of the present invention has the advantages of small dimension and various shapes. Besides, except that the proper electromagnetic properties of metals are maintained, the gravity is reduced greatly. The particle of the present invention can be used as a functional material or a micro structural device, such as a micro part, a structural electromagnetic wave, and a microwave shielding material. The present invention can be widely applied to the fields of micro machining, aviation, aerospace, electron, etc.
Description
Technical field
The present invention relates to a kind of functional material, be meant that more particularly a kind of is the hollow metal particle and preparation method thereof of template with the microbial cell.
Background technology
Metal powder material has good electromagnetism, mechanical performance and is employed extensively, but because the proportion of metal powder is bigger, makes it be subjected to a lot of restrictions on using, and therefore prepares the novel light metallic composite and be always the focus of research both at home and abroad.
Chemical plating (electroless plating, be called auto-catalytic chemicalplating again) be meant do not have extrinsic current to pass through, utilize appropriate reductant that the solution metal ion is reduced into metal simple-substance and is deposited on the catalytic activity body surface, form a kind of technology of metal level, it is simple to have technology, and coating is even, fine and close, and is wear-resistant, substrate need not conduction, can deposit on metal and nonmetal any substrate material surface.Therefore chemical plating is to realize the metallized important means of nonmetallic surface, and is common as at coating surface metallic nickel, copper etc. such as plastics, carbon fiber, pottery, cement based, is widely used in every profession and trades such as electronics, information, instrument manufacturing, chemical engineering industries.Therefore, chemical plating has in preparation and demonstrates remarkable advantages aspect the Metal Substrate composite powder material of nucleocapsid structure, and becomes new research focus in recent years.Along with the development of Micrometer-Nanometer Processing Technology, the manufacturing of micro element (as microballoon, microtubule, little spiral etc.) and functional particles processing has also caused increasing interest.Construct metallization microballoon, microtubule as having at lipid microtubule or carbon nano tube surface plated metal coating abroad by chemical plating method, thereby report (the The United States Patent 5 for preparing dielectric material, field-transmitting cathode etc., 096,551, The United StatesPatent 5,138,220), the preparation method (CN 1333387A, CN 1327894A) of the domestic light metallic microspheres that also to have with ceramic microsphere or natural pollen be core skeleton by the chemical plating method structure.Above two kinds of preparation methods of grain slightly, all exist material single, lack the deficiency that changes, and the preparation section of lipid microtubule complexity comparatively just itself.
Summary of the invention
It is the functional material of the hollow metal particle of template with the microbial cell that one of purpose of the present invention provides a kind of.
It is the preparation method of the hollow metal particle of template with the microbial cell that two of purpose of the present invention provides a kind of.
Of the present invention a kind of be the hollow metal particle of template with the microbial cell, be to be coated with metal layer or alloy layer on the microbial cell surface.
Described hollow metal particle, its particulate be shaped as the different geometries that microbial cell exists naturally, the shape of particulate can be sphere, rod, spirality.
Described hollow metal particle, the particle diameter of its spherical particle are 1～5 micron, and the particle diameter of rod particulate is 1 * 5～10 microns of Φ, and thickness of coating is 40 nanometers～1 micron.
Described hollow metal particle, its metal level that is coated on the microbial cell surface can be one or more the metal levels in silver, copper, nickel, cobalt, the ferro element.
Described hollow metal particle, its alloy-layer that is coated on the microbial cell surface can be the alloy that two or more metals in silver, copper, nickel, cobalt, the iron are formed.
Of the present invention is the preparation method of the hollow metal particle of template with the microbial cell, and preparation process is:
First step: choose the desired microorganisms cell;
Second step: microbial cell is carried out fixed in shape and intensive treatment;
Is that 4 ℃, concentration are to fix 6 hours in 2.5% the glutaraldehyde solution with the microbial cell chosen in temperature, after the phosphate buffer washing, is that 4 ℃, concentration are to fix 3 hours in 1% the osmic acid solution in temperature again, uses washed with de-ionized water again;
Third step: electro-chemical activity is handled;
Thalline after second step process is carried out pallamine activation, reduction processing successively, make the microbial cell surface obtain the active trigger layer that one deck is evenly distributed;
The 4th step: metalized;
Microbial cell after the processing of the 3rd step is dispersed in the chemical plating fluid under stirring, having on the microbial cell surface of catalytic activity, under the effect of reducing agent, metal ion cathodic reduction and reducing agent oxidation take place and separate out the conjugation reaction of hydrogen, the metal film that reduce deposition goes out has catalytic property, make reduction and deposition can continue to carry out and generate continuous, the certain thickness coat of metal is arranged, make the microbial cell metallization;
The 5th step: purifying, screening;
Microbial cell after the processing of the 4th step is carried out fractional precipitation, and screening;
The 6th step: promptly obtain hollow metal particle after the drying.
Described preparation method, the mode that the pallamine activation in third step adopts sensitization and activation to unite two into one.Pallamine liquid in third step is B solution+A solution, and color is tan solution, and this pallamine liquid is incubated 3.0～3.5 hours in 60～65 ℃ water is abundant, after the insulation, with pallamine liquid with deionized water be diluted to 1000 milliliters standby; Wherein,
A solution crystallization stannous chloride SnCl
22H
2O 2.53g/l
Palladium bichloride PdCl
21g/l
Concentrated hydrochloric acid HCl 100ml
Deionized water 200ml;
B solution sodium stannate Na
2SnO
33H
2O 7g/l
Crystallization stannous chloride SnCl
22H
2O 75g/l
Concentrated hydrochloric acid HCl 200ml.
Described preparation method, wherein the surfactant of third step use is the calgon dispersion liquid of concentration 5%.
The invention has the advantages that:
1, hollow metal particle is template with the microbial cell, draws materials conveniently, and the prepared particulate form that goes out is various, as spherical, shaft-like, helical form, thread etc.
2, adopt chemical plating method skim metal on the microbial cell surface-coated, resulting hollow metal particle regular shape, composition controlled (metal level composition and thickness are all adjustable).Not only reduce the proportion of material greatly, and can carry out modulation, realize required function,, can be used for multiple functions such as electromagnetic radiation shielding, absorbing material, magnetic material as obtaining electrically conductive particles or magnetic particle to the electromagnetic property of metal.
3, the pallamine activating solution of Cai Yonging carries out sensitization, a synthetic step of activation, has reduced manufacturing procedure, makes the preparation method more simple.
Description of drawings
Fig. 1 is a process flow diagram of the present invention.
Fig. 2 is the particulate composite construction cutaway view of a kind of spherical embodiment.
Fig. 3 is single metal-layer structure cutaway view.
Fig. 4 is single alloy-layer structure cutaway view.
Among the figure: 1. microbial cell 2. metal levels 3. alloy-layers
The specific embodiment
The present invention is described in further detail below in conjunction with drawings and Examples.
Please referring to shown in Fig. 2,3,4.
In the present invention, Fig. 2 is illustrated in the particulate that the microbial cell surface has coated composite construction.As plating the layer of metal layer earlier on the microbial cell surface, silver plates one deck alloy-layer on the surface of metal level silver again, as cobalt nickel-phosphorus alloy, dilval, cobalt dilval etc.The hollow micromagnetism particle of making can be used as microwave absorption.
In the present invention, Fig. 3 is illustrated in the microbial cell surface and has coated single metal level, also can be different metal levels.As microbial cell surface plating layer of copper, also can silver etc.Perhaps plate layer of copper, nickel, cobalt etc. again on silver-plated surface.
In the present invention, Fig. 4 is illustrated in the microbial cell surface and has coated single alloy-layer, as cobalt nickel-phosphorus alloy, dilval etc.
Embodiment 1: preparation is the hollow nickel metal particle of template with spherical microbial cell.
(1) filters out the microorganism of required form as required.
The present invention adopts the Citeromycesbaodingensis bacterium (Citeromyces matritensis) of Institute of Microorganism, Academia Sinica's preservation, and Citeromycesbaodingensis bacterial cell form is elliposoidal, 1.5 microns of major axis, and about 1 micron of minor axis can have one or two bud.Conventional method is all adopted in its cultivation, centrifugal collection thalline after the logarithmic phase.
(2) fixing, intensive treatment:
To the microbial cell collected is that 4 ℃, concentration are to fix 6 hours in 2.5% the glutaraldehyde solution in temperature earlier, after the phosphate buffer washing, is that 4 ℃, concentration are to fix 3 hours in 1% the osmic acid solution in temperature again, uses washed with de-ionized water again.
(3) electro-chemical activity is handled:
Thalline after fixing is carried out sensitization, activation, reduction processing successively, make the microbial cell surface obtain the active trigger layer that one deck is evenly distributed, metallic reducing is had the surface of catalytic action and good combination power.Sensitization, the activation can carry out step by step, also can be combined into one the step carry out.
The present invention adopts sensitization, activation to be combined into a step, to disperse 30 minutes in concentration is 5% calgon dispersion liquid by electromagnetic agitation through fixing solid capsule bacterium of handling, the volume ratio of pressing then 1: 1 adds the pallamine activating solution, under 30 ℃, directly activate 10 minutes, clean with deionized water then.Separate glue process with the sodium stannate aqueous solution of 30g/l dispergation 1 minute at normal temperatures, and then use washed with de-ionized water.
Pallamine liquid of the present invention is B solution+A solution, and color is tan solution, and this pallamine liquid is incubated 3.0～3.5 hours in 60～65 ℃ water is abundant, after the insulation, with pallamine liquid with deionized water be diluted to 1000 milliliters standby.Wherein,
A solution crystallization stannous chloride SnCl
22H
2O 2.53g/l
Palladium bichloride PdCl
21g/l
Concentrated hydrochloric acid HCl 100ml
Deionized water 200ml;
B solution sodium stannate Na
2SnO
33H
2O 7g/l
Crystallization stannous chloride SnCl
22H
2O 75g/l
Concentrated hydrochloric acid HCl 200ml.
The preparation of B liquid: B solution is at room temperature, and the crystallization stannous chlorides of 75 grams are joined in 200 milliliters the concentrated hydrochloric acid, constantly be stirred to dissolving fully after, add the sodium stannates of 7 grams again, obtain a kind of muddy liquid of white.
The preparation of A liquid: be that palladium bichloride with 1 gram fully is dissolved in the mixed solution of 100 milliliters of concentrated hydrochloric acids and 200 ml deionized water and (is dissolved in concentrated hydrochloric acid and part deionized water earlier, fills up deionized water again after treating to dissolve fully.), 30 ± 0.5 ℃ and constantly stirring condition add 2.53 gram crystallization stannous chlorides of accurate weighing down, pick up counting to add stannous chloride, under constantly stirring, reacted 12 minutes.
Mixed diluting: the B solution that will prepare is in advance immediately then slowly poured in the A group solution under continuous condition of stirring, and high degree of agitation is even, obtains tan solution.This solution is incubated 3 hours in 60～65 ℃ water is abundant, after the insulation solution is diluted to 1000 milliliters with deionized water, can use.
For thalline is fully disperseed, about 30 minutes of the thalline magnetic agitation in dispersant solution after will fixing earlier directly will add with the pallamine activating solution then, activate about 10 minutes down at 30 ℃.Fully clean with deionized water then.
Thalline with the pallamine activation, what adsorbed on the surface is one deck pallamine particulate, this pallamine particulate catalytically inactive, can not become the nucleus of crystal of chemical deposition metal, the circumgranular divalent tin ion hydrolysis of palladium glue-line must be sloughed, expose the Metal Palladium particulate with catalytic activity, this operation is called " dispergation " or " acceleration ".Dispergation is handled the used glue of separating in available traditional nonmetallic materials pre-electroplating treatment, is generally the sodium stannate aqueous solution of 10～30 grams per liters, at room temperature carries out dispergation.Still to clean behind the dispergation with deionized water.
(4) metalized:
To under mechanical agitation, be dispersed in the chemical plating fluid through the microbial cell after the electrochemical treatments.Having on the microbial cell surface of catalytic activity, under the effect of reducing agent, metal ion cathodic reduction and reducing agent oxidation take place and separate out the conjugation reaction of hydrogen.The metal film that reduce deposition goes out has catalytic property, thus this conjugation reaction is a kind of self-catalysis send out should, make reduction and deposition can continue to carry out and generate continuous, the certain thickness coat of metal is arranged, make the microbial cell metallization.
It is one or more mixed liquor in silver, copper, nickel, the cobalt that the present invention carries out metal that chemical plating coats.In coating, chemical plating, can prepare the hollow metal particle of the function match of multilayer metal compound by repeatedly containing the processing of different metal plating bath.
The solid capsule bacterium that to handle through electro-chemical activity evenly disperses in distilled water earlier by the peptizaiton of electromagnetic agitation, adds in the chemical nickel-plating solution then.
The prescription of chemical nickel-plating solution is (unit is mol/l):
| Main salt | Reducing agent | Complexing agent | Stabilizing agent |
| Nickelous sulfate 0.09 | Inferior sodium phosphate 0.24 | Natrium citricum 0.15 sodium pyrophosphate 0.13 triethanolamine 0.67 | Ammonium chloride 0.56 fluoride 0.05 thiocarbamide 0.05 |
Prepare 1000 milliliters of chemical nickel-plating solutions, pH=9, surplus is a deionized water.
Preparation: 1. with dissolving respectively in 800 ml deionized water after the accurate weighing of mentioned reagent; 2. with consoluet main salt under constantly stirring, join in the solution that contains complexing agent; 3. with consoluet reducing agent, under stirring tempestuously, join lentamente in the solution by 2. preparation; 4. will dissolve good pH conditioning agent (dilute NaOH solution, ammoniacal liquor etc.) pours under stirring condition bit by bit by in the solution of 3. preparing; 5. test pH value to 9, add stabiliser solution, and be diluted to 1000 milliliters; 6. test the pH value once more, adjust pH value to 9; 7. filtering solution; 8. the chemical nickel-plating solution that takes a morsel tries plating to ABS plastic, after affirmation can be used, and the plating of heating.
To contain the plating bath that thalline gets and heat to 40 ℃, and carry out chemical plating and coat under mechanical agitation, obtaining with the Citeromycesbaodingensis bacterium is the lightweight nickel metallic microspheres of kernel templates;
(5) by regulating the plating time (being 2～30 minutes) of chemical plating, the thickness of metal carbonyl coat also different (can change to the hundreds of nanometer in tens nanometers) therefore can be controlled the hollow metal microballoon that preparation varies in size.
Embodiment 2: preparation is with the hollow metal particle of the template of needle-like microbial cell.
(1) filters out the microorganism of required form as required, cultivate: for ease of observing the behavior of metallization back gained magnetic particle in magnetic field, this research employing Chinese Academy of Sciences microbe research
The Bacillus cercus of institute's preservation (Bacillus cereus) is as the template of magnetic metalization.The Bacillus cercus cellular morphology is shaft-like, is about 3.0～5.0 microns, about 0.5 micron of diameter, gram-positive bacteria.It is cultivated centrifugal collection thalline after the logarithmic phase through conventional method.
(2), (3) preparation technology is same as embodiment 1.
(4) magnetic metal processing: the Bacillus cercus that will handle through electro-chemical activity is by the peptizaiton of electromagnetic agitation, in deionized water, evenly disperse earlier, add then in cobalt nickel phosphorus (CoNiP) plating bath, the prescription of electroless cobalt plating nickel phosphorus (CoNiP) solution is (unit is mol/l):
| Main salt | Reducing agent | Complexing agent | Stabilizing agent |
| Nickelous sulfate 0.04 cobaltous sulfate 0.06 | Inferior sodium phosphate 0.20 | Natrium malicum 0.40 sodium malonate 0.30 sodium succinate 0.50 | Ammonium sulfate 0.10 |
Also transfer pH to 9 with dilute NaOH solution, ammoniacal liquor etc., the solution plating temperature is 80 ℃.The plating bath preparation procedure is with (4) described among the embodiment 1:
Carried out chemical plating 10 minutes under corresponding process conditions, obtaining with the Bacillus cercus is the lightweight magnetic metal particulate of kernel templates;
(5) through operations such as cleaning, layering and precipitatings, the uniform magnetic metal thalline of gained size is fully disperseed in dispersion liquid, drip the magnetic particle suspension on slide, push down with cover glass then, form liquid lamella, use bar permanent magnet near sample then, with the behavior of light microscope Real Time Observation magnetic particle under magnetic field.Find that the magnetic metal thalline is rotating under the effect of magnetic field: when cell concentration is low, obtained the magnetic particle array; When higher the and magnetic field of cell concentration is strong, obtained the magnetic particle string.
(6) we have at room temperature measured the hysteresis curve of the Bacillus cercus behind the deposition CoNiP coating, find that the shape of its hysteresis curve belongs to thin-and-long.The initial data of surveying is: saturation magnetization Ms=67.83emu/g, remanent magnetization Mr=19.95emu/g, Mr/Ms=0.2941, coercivity H=425.0120e.As seen the thalline behind the chemical plating CoNiP is a kind of magnetic material between soft magnetic materials and hard magnetic material.
In addition, we are studying aspect other bacterial classification, the coating, find:
(1) by conversion different microorganisms kind, change shape of template, do above-mentioned processing, then can obtain all adjustable hollow metal particle of inner chamber and metal layer thickness;
(2) composition (reducing agent kind and slaine composition) and the process conditions of change solution, obtain the component and the different serial polynary compound hollow metal particle of content thereof of metal level: a) change the reducing agent kind (as formaldehyde or inferior sodium phosphate or sodium borohydride etc.) in the nickel-plating liquid, can obtain the outer cover metal layer that pure nickel, Ni-P alloy, Ni-B alloy etc. contain different Ni contents; B) composition of main salt metal ion in the change plating bath as adding mantoquita, molysite, cobalt salt etc., can obtain binary (Ni-Cu, Ni-Fe, Ni-Co etc.), multi-element metal (Ni-Cu-Fe, Ni-Fe-C., Ni-Cu-C, Ni-Cu-Fe-Co etc.) and compound outer shell, each component content can be regulated easily by the adding proportion of each metal ion; C) be under the reducing agent with the inferior sodium phosphate, changing concrete plating technology condition, can make the metal level that contains different Ni-P ratio;
(3) will after fully cleaning, put into another metal plating liquid (as copper, chromium, silver, gold etc.) through being coated with the compound hollow particle of layer of metal (nickel), make with the compound hollow ball of double-level-metal; So repeatedly, can make the hollow ball of multilayer metal compound, function match.
Through conduction or magnetic particle that preparation method of the present invention makes, size is little, and shape is various, can be spherical, shaft-like, helical form, makes proportion reduce proportion greatly again in the electromagnetic performance that keeps metal itself.Can be used as micro parts or structure electromagnetic wave, micro-wave screening material, be widely used in fields such as microfabrication, Aeronautics and Astronautics, electronics.
Claims (10)
1, a kind of is the hollow metal particle of template with the microbial cell, it is characterized in that: the microbial cell surface is coated with metal layer or alloy layer.
2, hollow metal particle according to claim 1 is characterized in that: particulate be shaped as the different geometries that microbial cell exists naturally, the shape of particulate can be sphere, rod, spirality.
3, hollow metal particle according to claim 1 is characterized in that: the particle diameter of spherical particle is 1～5 micron, and the particle diameter of rod particulate is 1 * 5～10 microns of Φ, and thickness of coating is 40 nanometers～1 micron.
4, hollow metal particle according to claim 1 is characterized in that: the metal level that is coated on the microbial cell surface can be one or more the metal level in silver, copper, nickel, cobalt, the ferro element.
5, hollow metal particle according to claim 1 is characterized in that: the alloy-layer that is coated on the microbial cell surface can be the alloy that two or more metals in silver, copper, nickel, cobalt, the iron are formed.
6, a kind of is the preparation method of the hollow metal particle of template with the microbial cell, it is characterized in that: preparation process is:
First step: choose the desired microorganisms cell;
Second step: microbial cell is carried out fixed in shape and intensive treatment;
Is that 4 ℃, concentration are to fix 6 hours in 2.5% the glutaraldehyde solution with the microbial cell chosen in temperature, after the phosphate buffer washing, is that 4 ℃, concentration are to fix 3 hours in 1% the osmic acid solution in temperature again, uses washed with de-ionized water again;
Third step: electro-chemical activity is handled;
Thalline after second step process is carried out pallamine activation, reduction processing successively,
Make the microbial cell surface obtain the active trigger layer that one deck is evenly distributed;
The 4th step: metalized;
Microbial cell after the processing of the 3rd step is dispersed in the chemical plating fluid under stirring, having on the microbial cell surface of catalytic activity, under the effect of reducing agent, metal ion cathodic reduction and reducing agent oxidation take place and separate out the conjugation reaction of hydrogen, the metal film that reduce deposition goes out has catalytic property, make reduction and deposition can continue to carry out and generate continuous, the certain thickness coat of metal is arranged, make the microbial cell metallization;
The 5th step: purifying, screening;
Microbial cell after the processing of the 4th step is carried out fractional precipitation, and screening;
The 6th step: promptly obtain hollow metal particle after the drying.
7, preparation method according to claim 6 is characterized in that: the mode that the pallamine activation in third step adopts sensitization and activation to unite two into one.
8, preparation method according to claim 6, it is characterized in that: the pallamine liquid in third step is B solution+A solution, color is tan solution, this pallamine liquid is incubated 3.0～3.5 hours in 60～65 ℃ water is abundant, after the insulation, with pallamine liquid with deionized water be diluted to 1000 milliliters standby; Wherein,
A solution crystallization stannous chloride SnCl
22H
2O 2.53g/l
Palladium bichloride PdCl
21g/l
Concentrated hydrochloric acid HCl 100ml
Deionized water 200ml;
B solution sodium stannate Na
2SnO
33H
2O 7g/l
Crystallization stannous chloride SnCl
22H
2O 75g/l
Concentrated hydrochloric acid HCl 200ml.
9, preparation method according to claim 6 is characterized in that: need to adopt mechanical agitation or magnetic agitation in third and fourth step.
10, preparation method according to claim 11 is characterized in that: the surfactant that third step uses is the calgon dispersion liquid of concentration 5%.
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| CN102070201B (en) * | 2010-11-15 | 2013-10-23 | 北京航空航天大学 | Preparation method of electromagnetic wave absorbing particles by taking microorganism as template |
| CN102021622A (en) * | 2010-12-09 | 2011-04-20 | 北京航空航天大学 | Method and device for plating cladding magnetic material on microorganism surface |
| CN102019427A (en) * | 2010-12-20 | 2011-04-20 | 吴浩 | High-efficiency wave-absorbing particles, wave-absorbing material, and application and preparation method thereof |
| CN102330131A (en) * | 2011-07-25 | 2012-01-25 | 太仓市金鹿电镀有限公司 | Method for preparing plastic plating colloid palladium activating solution |
| CN102492941B (en) * | 2011-12-23 | 2013-05-15 | 北京航空航天大学 | Hollow shell-shell structural micro-nano metal material prepared from microorganism inoculant |
| CN102794458B (en) * | 2012-08-24 | 2014-11-05 | 济南大学 | Hollow silver particle and preparation method thereof |
| WO2015004770A1 (en) * | 2013-07-11 | 2015-01-15 | 株式会社応用ナノ粒子研究所 | Nanoparticle production method, production device and automatic production device |
| CN103418786B (en) * | 2013-09-10 | 2016-05-25 | 北京理工大学 | A kind of low W-W connection degree W-Cu-Ni alloy material |
| CN103752845B (en) * | 2014-01-15 | 2016-03-02 | 上海交通大学 | Nickel or nickel alloy nanometer perforation ball and preparation method thereof |
| CN107227509B (en) * | 2017-06-27 | 2020-06-09 | 江苏大学 | Nano material microfiber using mold hyphae as template and preparation method thereof |
| CN110732332B (en) * | 2019-09-29 | 2022-06-07 | 济南大学 | Method for preparing phosphorus-nickel sulfide hollow spheres by adopting single-cell biological template |
| CN115673318B (en) * | 2022-10-11 | 2023-12-19 | 深圳飞世尔新材料股份有限公司 | Low-cost and low-resistance conductive microsphere, preparation method thereof, conductive adhesive and preparation method thereof |
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