CN1403234A - 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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Abstract
The present invention discloses one kind of hollow metal particle with microbe cell template and its preparation process. Hollow metal particle is prepared by using microbe cell with different geometric appearance as template and through chemical plating process to deposit metal layer or alloy layer on the surface. The conducting or magnetic particle thus prepared has small size, varying shape, electromagnetic performance similar to metal and low specific weight. The particle may be used as functional material or in constructing micro device, miniature part, shielding material in micro processing, aviation, aerospace, electronics and other fields.
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 microorganism cells.
Background technology
Metal powder material has good electromagnetism, mechanical property 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 metal composite and be always the focus of research both at home and abroad.
Electroless 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 electroless 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, electroless plating has in preparation and demonstrates remarkable advantages aspect the metal matrix 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 metal refining coating abroad by chemical plating method, thereby report (the The United States Patent 5 for preparing dielectric materials, 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 microorganism cells 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 microorganism cells 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 microorganism cells, be to be coated with metal layer or alloy layer on the microorganism cells surface.
Described hollow metal particle, its particulate be shaped as the different geometries that microorganism cells exists naturally, the shape of particulate can be sphere, rod, volution.
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 microorganism cells 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 microorganism cells 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 microorganism cells, and preparation process is:
First step: choose the desired microorganisms cell;
Second step: microorganism cells is carried out fixed in shape and intensive treatment;
Is that 4 ℃, concentration are that 2.5% glutaraldehyde is molten with the microorganism cells chosen in temperature
Fixing 6h in the liquid after the phosphoric acid buffer washing, is that 4 ℃, concentration are 1% in temperature again
Osmic acid solution in fixing 3h, use washed with de-ionized water again;
Third step: electrochemical activity is handled;
Thalline after second step process is carried out pallamine activation, reduction processing successively,
Make the microorganism cells surface obtain the active trigger layer that one deck is evenly distributed;
The 4th step: metalized;
To microorganism cells being dispersed under whipped state after the processing of the 3rd step
Learn in the plating bath, having on the microorganism cells surface of catalytic activity, in the effect of reductive agent
Down, metal ion cathodic reduction and reductive agent oxidation and to separate out the conjugation of hydrogen anti-take place
Should, the metallic membrane that reduce deposition goes out has catalytic property, and reduction and deposition can be continued into
Row and generate successive, certain thickness metal plating is arranged makes the microorganism cells metallization;
The 5th step: purifying, screening;
Microorganism cells after the processing of the 4th step is carried out fractionation 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 tin protochloride SnCl
22H
2O 2.53g/l
Palladous chloride PdCl
21g/l
Concentrated hydrochloric acid HCl 100ml
Deionized water 200ml
B solution sodium stannate Na
2SnO
33H
2O 7g/l
Crystallization tin protochloride SnCl
22H
2O 75g/l
Concentrated hydrochloric acid HCl 200ml
Described preparation method, the reduction treatment solution that adopts in third step is the ortho phosphorous acid sodium water solution, concentration is 10～30 grams per liters.
Described preparation method needs to adopt mechanical stirring or magnetic agitation in third and fourth step.
Described preparation method needs to add tensio-active agent in third and fourth step.Wherein the tensio-active agent of third step use is the Sodium hexametaphosphate 99 dispersion liquid of concentration 5%.Wherein the tensio-active agent of the 4th step use is the inferior sodium phosphate dispersion liquid of concentration 2%.
The invention has the advantages that:
1, hollow metal particle is template with the microorganism cells, draws materials conveniently, and the prepared particulate form that goes out is various, as spherical, shaft-like, spirrillum, thread etc.
2, adopt chemical plating method skim metal on the microorganism cells 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, magneticsubstance as obtaining electrically conductive particles or magnetic particle to the electromagnetic property of metal.
3, the pallamine activation 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 structure sectional view of a kind of spherical embodiment.
Fig. 3 is single metal-layer structure sectional view.
Fig. 4 is single alloy layer structure sectional view.
Among the figure: 1. microorganism cells 2. metal levels 3. alloy layers
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 microorganism cells surface has coated composite structure.As plating the layer of metal layer earlier on the microorganism cells surface, silver plates one deck alloy layer on the surface of metal level silver again, as cobalt nickel-phosphorus alloy, Rhometal, cobalt Rhometal etc.The hollow micromagnetism particle of making can be used as microwave absorption.
In the present invention, Fig. 3 is illustrated in the microorganism cells surface and has coated single metal level, also can be different metal levels.As microorganism cells 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 microorganism cells surface and has coated single alloy layer, as cobalt nickel-phosphorus alloy, Rhometal etc.
Embodiment 1: preparation is the hollow nickel metal particle of template with spherical microorganism cells.
(1) filters out the microorganism of desired shape as required.
The present invention adopts the Citeromycesbaodingensis bacterium (Citeromyces matritensis) of Institute of Microorganism, Academia Sinica's preservation, and Citeromycesbaodingensis mycetocyte form is elliposoidal, 1.5 microns of major axis, and about 1 micron of minor axis can have one or two bud.Ordinary method is all adopted in its cultivation, centrifugal collection thalline after the logarithmic phase.
(2) fixing, intensive treatment:
To the microorganism cells collected is that 4 ℃, concentration are fixing 6h in 2.5% the glutaraldehyde solution in temperature earlier, after the phosphoric acid buffer washing, is that 4 ℃, concentration are fixing 3h in 1% the osmic acid solution in temperature again, uses washed with de-ionized water again.
(3) electrochemical activity is handled:
Thalline after fixing is carried out sensitization, activation, reduction processing successively, make the microorganism cells surface obtain the active trigger layer that one deck is evenly distributed, metallic reducing is had the surface of katalysis and good combination power.Sensitization, activation can proceed step by step, also can be combined into a step to carry out.
The present invention adopts sensitization, activation to be combined into a step, to disperse 30 minutes in concentration is 5% Sodium hexametaphosphate 99 dispersion liquid by induction stirring through fixing solid capsule bacterium of handling, the volume ratio of pressing then 1: 1 adds the pallamine activation 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 tin protochloride SnCl
22H
2O 2.53g/l
Palladous chloride PdCl
21g/l
Concentrated hydrochloric acid HCl 100ml
Deionized water 200ml
B solution sodium stannate Na
2SnO
33H
2O 7g/l
Crystallization tin protochloride SnCl
22H
2O 75g/l
Concentrated hydrochloric acid HCl 200ml
The preparation of B liquid: B solution is at room temperature, and the crystallization tin protochlorides 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 Palladous chloride with 1 gram fully is dissolved in the mixing solutions 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.), at 30+0.5 ℃ with constantly add 2.53 gram crystallization tin protochlorides of accurate weighing under the agitation condition, picking up counting to add tin protochloride, reaction is 12 minutes under constantly stirring.
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 activation solution then, activate about 10 minutes down at 30 ℃.Fully clean with deionized water then.
With pallamine activatory thalline, surface adsorption be one deck pallamine particulate, this pallamine particulate catalytically inactive, can not become the nucleus of crystal of electroless plating metal, the circumgranular divalent tin ion hydrolysis of palladium glue-line must be sloughed, expose the palladium metal particulate with catalytic activity, this operation is called " dispergation " or " acceleration ".Dispergation is handled the used glue of separating in available traditional non-metallic material 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 stirring, be dispersed in the chemical plating fluid through the microorganism cells after the electrochemical treatment.Having on the microorganism cells surface of catalytic activity, under the effect of reductive agent, metal ion cathodic reduction and reductive agent oxidation take place and separate out the conjugation reaction of hydrogen.The metallic membrane that reduce deposition goes out has catalytic property, thus this conjugation reaction is a kind of autocatalysis send out should, make reduction and deposition can continue to carry out and generate successive, certain thickness metal plating is arranged, make the microorganism cells metallization.It is one or more mixed solution in silver, copper, nickel, the cobalt that the present invention carries out metal that electroless plating coats.In coating, electroless 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 electrochemical activity is by the dissemination of induction stirring, and homodisperse in distilled water adds in the chemical nickel-plating solution then earlier.
The prescription of chemical nickel-plating solution is (unit is mol/l):
| Main salt | Reductive agent | Complexing agent | Stablizer |
| Single nickel salt 0.09 | Inferior sodium phosphate 0.24 | Trisodium Citrate 0.15 trisodium phosphate 0.13 trolamine 0.67 | Ammonium chloride 0.56 fluorochemical 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 reductive agent, under stirring tempestuously, join lentamente in the solution by 2. preparation; 4. will dissolve good pH regulator agent (dilute NaOH solution, ammoniacal liquor etc.) pours under agitation 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 electroless plating and coat under mechanical stirring, 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 electroless plating, the thickness of metal carbonyl coat is difference (can change to the hundreds of nanometer in tens nanometers) also, so may command prepares the hollow metal microballoon that varies in size.
Embodiment 2: preparation is with the hollow metal particle of the template of needle-like microorganism cells.
(1) filters out the microorganism of desired shape as required, cultivate: for ease of observing the behavior of metallization back gained magnetic particle in magnetic field, the template of the bacillus cereus (Bacillus cereus) of Institute of Microorganism, Academia Sinica's preservation as magneticmetalization adopted in this research.The bacillus cereus cellular form is shaft-like, is about 3.0～5.0 microns, about 0.5 micron of diameter, gram-positive microorganism.It is cultivated centrifugal collection thalline after the logarithmic phase through conventional method.
(2), (3) preparation technology is same as embodiment 1.
(4) magneticmetal processing: the bacillus cereus that will handle through electrochemical activity is by the dissemination of induction stirring, elder generation's homodisperse in deionized water, 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 | Reductive agent | Complexing agent | Stablizer |
| Single nickel salt 0.04 rose vitriol 0.06 | Inferior sodium phosphate 0.20 | Sodium malate 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 electroless plating 10 minutes under corresponding processing condition, obtaining with the bacillus cereus is the lightweight magneticmetal particulate of kernel templates;
(5) through operations such as cleaning, layering and precipitatings, the uniform magneticmetal thalline of gained size is fully disperseed in dispersion liquid, drip the magnetic particle suspension liquid on slide glass, push down with cover glass then, form liquid lamella, use bar permanent magnet near sample then, with the behavior of opticmicroscope Real Time Observation magnetic particle under magnetic field.Find that the magneticmetal thalline rotates under the action of a 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 magnetic hysteresis loop of the bacillus cereus behind the deposition CoNiP coating, find that the shape of its magnetic hysteresis loop belongs to thin-and-long.The raw data of surveying is: saturation magnetization Ms=67.83emu/g, residual magnetization Mr=19.95emu/g, Mr/Ms=0.2941, coercivity H=425.012Oe.As seen the thalline behind the electroless plating CoNiP is a kind of magneticsubstance 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 (reductive agent kind and metal-salt composition) and the processing condition of change solution, obtain the component and the different serial polynary compound hollow metal particle of content thereof of metal level: a) change the reductive 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 add mantoquita, molysite, cobalt salt etc., can obtain binary (Ni-Cu, Ni-Fe, Ni-Co etc.), multi-element metal (Ni-Cu-Fe, Ni-Fe-Co, Ni-Cu-C, Ni-Cu-Fe-Co etc.) compound outer shell, each component content can be regulated easily by the adding proportion of each metal ion; C) be under the reductive 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 layer of metal (nickel) compound hollow particle, make with double-level-metal compound hollow ball; 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, spirrillum, makes proportion reduce proportion greatly again in the electromagnetic performance that keeps metal itself.Can be used as micro parts or structure hertzian wave, micro-wave screening material, be widely used in fields such as microfabrication, Aeronautics and Astronautics, electronics.
Claims (13)
1, a kind of is the hollow metal particle of template with the microorganism cells, it is characterized in that: the microorganism cells 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 microorganism cells exists naturally, the shape of particulate can be sphere, rod, volution.
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 microorganism cells 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 microorganism cells 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 microorganism cells, it is characterized in that: preparation process is:
First step: choose the desired microorganisms cell;
Second step: microorganism cells is carried out fixed in shape and intensive treatment;
Is that 4 ℃, concentration are that 2.5% glutaraldehyde is molten with the microorganism cells chosen in temperature
Fixing 6h in the liquid after the phosphoric acid buffer washing, is that 4 ℃, concentration are 1% in temperature again
Osmic acid solution in fixing 3h, use washed with de-ionized water again;
Third step: electrochemical activity is handled;
Thalline after second step process is carried out pallamine activation, reduction processing successively,
Make the microorganism cells surface obtain the active trigger layer that one deck is evenly distributed;
The 4th step: metalized;
To microorganism cells being dispersed under whipped state after the processing of the 3rd step
Learn in the plating bath, having on the microorganism cells surface of catalytic activity, in the effect of reductive agent
Down, metal ion cathodic reduction and reductive agent oxidation and to separate out the conjugation of hydrogen anti-take place
Should, the metallic membrane that reduce deposition goes out has catalytic property, and reduction and deposition can be continued into
Row and generate successive, certain thickness metal plating is arranged makes the microorganism cells metallization;
The 5th step: purifying, screening;
Microorganism cells after the processing of the 4th step is carried out fractionation 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 tin protochloride SnCl
22H
2O 2.53g/l
Palladous chloride PdCl
21g/l
Concentrated hydrochloric acid HCl 100ml
Deionized water 200ml
B solution sodium stannate Na
2SnO
33H
2O 7g/l
Crystallization tin protochloride SnCl
22H
2O 75g/l
Concentrated hydrochloric acid HCl 200ml
9, preparation method according to claim 6 is characterized in that: the reduction treatment solution that adopts in the third step is the ortho phosphorous acid sodium water solution, and concentration is 10～30 grams per liters.
10, preparation method according to claim 6 is characterized in that: need to adopt mechanical stirring or magnetic agitation in third and fourth step.
11, preparation method according to claim 6 is characterized in that: need to add tensio-active agent in third and fourth step.
12, preparation method according to claim 11 is characterized in that: the tensio-active agent that third step uses is the Sodium hexametaphosphate 99 dispersion liquid of concentration 5%.
13, preparation method according to claim 11 is characterized in that: the tensio-active agent that the 4th step is used is the inferior sodium phosphate dispersion liquid of concentration 2%.
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| CN103752845A (en) * | 2014-01-15 | 2014-04-30 | 上海交通大学 | Nickel or nickel alloy perforated nanosphere and method for manufacturing same |
| CN107227509A (en) * | 2017-06-27 | 2017-10-03 | 江苏大学 | A kind of nano material microfibre using fungal hyphae as template 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 |
| CN110732332A (en) * | 2019-09-29 | 2020-01-31 | 济南大学 | method for preparing hollow balls of phosphorus-nickel sulfide by using single-cell biological template |
| 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 |
| CN115673318A (en) * | 2022-10-11 | 2023-02-03 | 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 |
| 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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