CN1925941A - Highly crystalline silver powder and method for production thereof - Google Patents
Highly crystalline silver powder and method for production thereof Download PDFInfo
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- CN1925941A CN1925941A CNA2005800063565A CN200580006356A CN1925941A CN 1925941 A CN1925941 A CN 1925941A CN A2005800063565 A CNA2005800063565 A CN A2005800063565A CN 200580006356 A CN200580006356 A CN 200580006356A CN 1925941 A CN1925941 A CN 1925941A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/07—Metallic powder characterised by particles having a nanoscale microstructure
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- 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
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- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
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- Y10T428/12014—All metal or with adjacent metals having metal particles
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Abstract
An object of the present invention is to provide highly crystalline silver powder which is characterized in fine particles, showing high dispersibility, it's particle size distribution is not excessively sharp but relatively broad and crystallites are large; and a method for producing the same. In order to achieve the object, a method for producing highly crystalline silver powder is characterized in that mixing a first aqueous solution and a second aqueous solution, wherein the first aqueous solution contains silver nitrate, a dispersing agent and nitric acid, and the second solution contains ascorbic acid. For dispersing agent, polyvinylpyrrolidone or gelatin is preferred. Highly crystalline silver powder produced by the above-described method is preferred to be a crystallite diameter of 300 AA or more, an average particle diameter D 50 in the range from 0.5 [mu]m to 10 [mu]m, and a thermal shrinkage rate for the length direction after heating at 700 DEG C in the range from -3% to 3%. For ratio D 90 /D 10 of the silver powder is preferred to be in the range from 2.1 to 5.0.
Description
Technical field
The present invention relates to a kind of highly crystalline silver powder and manufacture method thereof, relate to a kind of like this highly crystalline silver powder and manufacture method thereof in more detail, for example can preferably make granular largely, formation has high density and high accuracy, and the chip part of high reliability, the conductive paste of electrodes such as plasm display panel and circuit, particularly can form the conductive paste of smoothly filming etc. in fine distribution with high density and high accuracy and high reliability or the thin layer, its particulate, good dispersion, size distribution is within reason narrow and compare broad, because crystallite is big, when being used as the raw material of conductive paste, dispersiveness and silver powder the fillibility in conductive paste of silver powder in cream is good, electrode that forms from silver thick film and circuit etc. are granular more, the heat-resisting shrinkage of the silver thick film that obtains from conductive paste is good, lower than resistance (resistivity) simultaneously.
Background technology
In the past, as the electrode of electronic unit etc. and the formation method of circuit, the silver powder of known handlebar conductive material is dispersed in after conductive paste in the cream is printed on the substrate, the in addition roasting or solidify it is solidified of this cream, by forming the method that silver thick film forms circuit.Yet, in recent years,, therefore,, when making conductive paste, wished its particulate, fillibility and dispersed good for silver powder as the conductive paste material because the multifunction of electronic instrument requires the small-sized densification of electronic installation.Also have, so-called dispersiveness among the present invention, short of prior special instruction is the dispersiveness of silver powder in cream, then means the difficulty that the primary particle of silver powder condenses each other.For example, the state of so-called favorable dispersibility means the state that ratio that primary particle condenses each other is little or do not have fully, and the state of so-called bad dispersibility means greatly or the fully state of cohesion of ratio that primary particle condenses each other.
As the substrate that is printed with above-mentioned conductive paste, be generally used for the big parts etc. of generating heat such as IC assembly in the ceramic substrate.Yet, on this ceramic substrate during printing conductive cream, because the percent thermal shrinkage of ceramic substrate is generally different with the percent thermal shrinkage of the silver thick film that is generated by the conductive paste that prints, so when roasting, have the worry that ceramic substrate and silver thick film are peeled off or substrate itself deforms.Therefore, the percent thermal shrinkage of the silver thick film that the percent thermal shrinkage of ceramic substrate and conductive paste by printing generate, it is preferred adopting the approaching value of trying one's best.
When this roasting,, can think that the silver powder in the conductive paste causes due to the sintering when roasting as one of reason of the thermal contraction of above-mentioned silver thick film.That is, can think that silver powder is by the small polycrystal that crystallite constituted, when the conductive paste that contains silver powder in roasting was used to form silver thick film, change in size took place and causes thermal contraction before and after silver thick film generates in the tiny crystallite generation sintering in the silver powder.Therefore, in order to obtain the few conductive paste that contains silver powder of thermal contraction, wish that the crystallite in the silver powder is big as far as possible, so that the crystallite sintering not to take place as far as possible.
In recent years, require further to improve the high frequency characteristics of circuit and the substrate size precision before and after the roasting, therefore, as the substrate that forms silver thick film, (Low Temperature Co-firedCeramic: LTCC) substrate replaces above-mentioned common ceramic substrate to adopt LTCC.In addition, because of this ltcc substrate is to be got with the conductive paste roasting simultaneously that contains low resistance conductors such as silver powder by the living embolium of ltcc substrate (giving birth to plate), so with the above-mentioned common ceramic substrate of employing, printing conductive cream thereon, the technology that forms the silver thick film circuit is compared, and the roasting number of times is few, control the thickness of ceramic electrical amboceptor easily, the conductor resistance step-down of the circuit that is formed by conductive paste improves the surface smoothing of substrate easily, therefore sees that from these aspects LTCC is preferred.Yet because the dimensional stability of LTCC is very excellent, so the use therein silver powder thermal contraction as the conductive paste material of strong request is littler, therefore, more the crystallite in the strong request silver powder is big.
In addition, when the crystallite in this silver powder is big, the impurity content of general silver powder is low, the easy step-down of ratio resistance of the circuit that the silver thick film that obtains thus forms, therefore, the circuit that forms after the not only above-mentioned roasting, and the circuit that forms of roasting can not adopt the conductive paste that contains silver powder yet, sees it is preferred from this point.
As mentioned above, the silver powder that uses in the preferred conductive paste is within reason narrow in broad, silver powder that crystallite is big as particulate, good dispersion, size distribution.
Relative therewith, patent documentation 1 (TOHKEMY 2000-1706 communique) discloses a kind of, make when silver nitrate aqueous solution is mixed with the liquid of the L-aqueous ascorbic acid that is dissolved with acrylate copolymer and react, make the method for high crystalline solid silver granuel, according to this method, the size that can obtain crystallite is more than 400 , and particle size range is the highly crystalline silver powder of the close limit of 2～4 μ m.
Patent documentation 1:JP spy opens 2000-1706 communique (the 1st page)
Disclosure of an invention
The problem that invention will solve
But, the silver powder of record in the patent documentation 1, though be that particulate and crystallite are big, for example the percent thermal shrinkage in the high temperature about 700 ℃ is difficult to become very little.Though this silver powder crystallite is very big, the reason big in the elevated temperature heat shrinkage factor can be speculated as, because the particle size range of this silver powder is 2～4 μ m, size distribution is too narrow, forms the space each other by silver powder, due to the fillibility step-down of silver powder.Therefore, make conductive paste, when the formation that is used for silver thick film and when using the formation of circuit of ltcc substrate, change in size strengthens before and after the formation of circuit, at common ceramic substrate and ltcc substrate, in ltcc substrate, be easy to generate crooked problem especially on the contrary.
Therefore, the purpose of this invention is to provide a kind of for particulate, good dispersion, size distribution is within reason narrow and than broad, highly crystalline silver powder that crystallite is big and manufacture method thereof.
Solve the means of problem
According to above-mentioned actual conditions, what the inventor concentrated one's attention on to inquire into found that, if by the 1st aqueous solution that contains silver nitrate, dispersant and nitric acid with, contain the method that the 2nd aqueous solution of ascorbic acid mixed and make silver powder, then can obtain particulate, good dispersion, size distribution is within reason narrow and compare broad, crystallite is big, can make the good highly crystalline silver powder of heat-resisting shrinkage of the silver thick film that is obtained by conductive paste, thereby finish the present invention.
That is, the manufacture method of highly crystalline silver powder is characterized in that, the 1st aqueous solution that contains silver nitrate, dispersant and nitric acid is mixed with the 2nd aqueous solution that contains ascorbic acid.
In addition, provide a kind of manufacture method of highly crystalline silver powder, it is characterized in that, in the manufacture method of above-mentioned highly crystalline silver powder, above-mentioned dispersant is a PVP.
In addition, the invention provides a kind of manufacture method of highly crystalline silver powder, it is characterized in that, in the manufacture method of above-mentioned highly crystalline silver powder, above-mentioned dispersant is a gelatin.
In addition, the invention provides a kind of manufacture method of highly crystalline silver powder, it is characterized in that, in the manufacture method of above-mentioned highly crystalline silver powder, above-mentioned the 1st aqueous solution is, to silver nitrate 100 weight portions, cooperate the aqueous solution of PVP 5 weight portions～60 weight portions, nitric acid 35 weight portions～70 weight portions.
In addition, the invention provides a kind of manufacture method of highly crystalline silver powder, it is characterized in that, in the manufacture method of above-mentioned highly crystalline silver powder, above-mentioned the 1st aqueous solution is to silver nitrate 100 weight portions, to cooperate the aqueous solution of gelatin 0.5 weight portion～10 weight portions, nitric acid 35 weight portions～70 weight portions.
The invention provides a kind of manufacture method of highly crystalline silver powder, it is characterized in that, in the manufacture method of above-mentioned highly crystalline silver powder, with above-mentioned the 1st aqueous solution and above-mentioned the 2nd aqueous solution, according to silver nitrate 100 weight portions to cooperating in above-mentioned the 1st aqueous solution, the ascorbic acid that cooperates in the 2nd aqueous solution is that the ratio of 30 weight portions～90 weight portions is mixed.
The invention provides a kind of manufacture method of highly crystalline silver powder, it is characterized in that, in the manufacture method of above-mentioned highly crystalline silver powder, with above-mentioned the 1st aqueous solution and above-mentioned the 2nd aqueous solution, according to ascorbic acid 100 weight portions to cooperating in above-mentioned the 2nd aqueous solution, the nitric acid that cooperates in the 1st aqueous solution is that the ratio of 40 weight portions～150 weight portions is mixed.
The invention provides a kind of highly crystalline silver powder, it is characterized in that, make with the manufacture method of above-mentioned highly crystalline silver powder.
In addition, the highly crystalline silver powder so that the manufacture method of highly crystalline silver powder of the present invention is made is characterized in that little footpath particle diameter is more than 300 .
In addition, this highly crystalline silver powder is characterized in that, average grain diameter D
50Be 0.5 μ m～10 μ m.
In addition, this highly crystalline silver powder is characterized in that, 700 ℃ percent thermal shrinkage is in ± 3%.
In addition, this highly crystalline silver powder is characterized in that, D
90/ D
10Be 2.1～5.0.
In addition, this highly crystalline silver powder is characterized in that, the crystallite particle diameter is more than 300 , average grain diameter D
50Being 0.5 μ m～10 μ m, is in ± 3% at the percent thermal shrinkage of 700 ℃ length directions.
In addition, this highly crystalline silver powder is characterized in that, D
90/ D
10Be 2.1～5.0.
The effect of invention
The highly crystalline silver powder that the present invention relates to, be particulate, good dispersion, size distribution is within reason narrow and compare broad, crystallite is big, and when therefore being used as the raw material of conductive paste, dispersiveness and silver powder the fillibility in conductive paste of silver powder in cream is good, can make granular more such as the electrode that formed by silver thick film and circuit, it is good heat-resisting inotropic lower than resistance simultaneously that the silver thick film that is obtained by conductive paste is had.In addition, according to the highly crystalline silver powder manufacture method that the present invention relates to, can effectively make the highly crystalline silver powder that the invention described above relates to.
The preferred plan that carries out an invention
(highly crystalline silver powder that the present invention relates to)
The highly crystalline silver powder that the present invention relates to is essentially granular powder.The average grain diameter D of the highly crystalline silver powder that the present invention relates to
50Be 0.5 μ m～10 μ m, be preferably 1 μ m～5 μ m.As average grain diameter D
50When being in this scope, when using in conductive paste, the fillibility of silver powder in conductive paste is good, and simultaneously, the circuit that is formed by silver thick film etc. are granular more, so be preferred.On the other hand, as average grain diameter D
50When being lower than 0.5 μ m, the recovery difficulty of silver powder, so not preferred, when greater than 10 μ m, silver powder condenses many each other, so not preferred.Here, so-called average grain diameter D
50, mean the volume average particle size that adopts the laser diffraction and scattering method to obtain, i.e. the particle diameter of cumulative distribution 50%.
The crystallite particle diameter of the highly crystalline silver powder that the present invention relates to is that 300 are above, preferred 350 ～600 .In the time of in the crystallite particle diameter is in this scope, the conductive paste that contains this silver powder is coated on the ceramic substrate, carry out roasting, during circuit that formation is made of silver thick film etc., the percent thermal shrinkage of the silver thick film before and after the roasting reaches the percent thermal shrinkage that approaches ceramic substrate, suppress silver thick film from ceramic substrate peel off or ceramic substrate along with the effect of the distortion that change in size produced of silver thick film is big, so be preferred.
On the other hand, when crystallite particle diameter during less than 300 , the conductive paste that contains this silver powder is coated on the ceramic substrate, carry out roasting, during circuit that formation is made of silver thick film, the contraction of the shrinkage ratio ceramic substrate of the silver thick film before and after the roasting is big, and silver thick film is easy to peel off or ceramic substrate is easy to change along with the size of silver thick film from ceramic substrate, so for not preferred.Here, so-called crystallite particle diameter, mean to the silver powder sample carry out the X line spread out diffusing, from each crystal plane that obtains mean value of the wide crystallite particle diameter of obtaining of half value of peak value at angle of loosing that spreads out.
The D of the highly crystalline silver powder that the present invention relates to
90/ D
10Be generally 2.1～5.0, be preferably 2.5～4.7.Also have, in the present invention, D
10, D
90Be respectively the cumulative distribution 10 volume % that obtain by laser diffraction and scattering particle size distribution method and the median particle diameter (μ m) of 90 volume %.D
90/ D
10Be the index of expression deviation, work as D
90/ D
10When big, expression size distribution deviation is big.Work as D
90/ D
10When being in above-mentioned scope, the size distribution of silver powder is too narrow and than broad, when the conductive paste that adopts this silver powder forms circuit, because the fillibility of silver powder is good, the heat-resisting shrinkage of circuit is good, and promptly the change in size of circuit is little before and after roasting, is preferred.
On the other hand, work as D
90/ D
10Be lower than at 2.1 o'clock, the size distribution of silver powder is too narrow, and when the conductive paste that adopts this silver powder formed circuit, because the fillibility of silver powder is poor, the heat-resisting shrinkage of circuit worsened, and promptly the change in size of circuit is big easily before and after roasting, is not preferred.In addition, work as D
90/ D
10Surpass at 5.0 o'clock, the size distribution of silver powder is too wide, and when the conductive paste that adopts this silver powder formed circuit, the fillibility of silver powder was poor, and the heat-resisting shrinkage of circuit worsens, that is, the change in size of circuit becomes big easily before and after roasting, is not preferred.
The highly crystalline silver powder that the present invention relates to, be generally at 700 ℃ length direction percent thermal shrinkages ± 3% in, in preferred ± 2%.Also have, among the present invention in what is called ± X%, mean-X%～+ X%.In the present invention, so-called 700 ℃ length direction percent thermal shrinkage means silver powder being formed the sample of particle, uses the percent thermal shrinkage of the particle length direction of thermo-mechanical analysis (TMA) mensuration.
The highly crystalline silver powder that the present invention relates to, under lower temperature, for example the resistivity of filming at 300 ℃ of silver that carry out roasting is low.That is, even make highly crystalline silver powder at low-temperature bake, the resistivity of sinter diminishes easily.In addition, the low reason of resistivity of filming like this at 300 ℃ of silver that carry out roasting, supposition is because the crystallite particle diameter is big, the electron motion in the silver powder become level and smooth due to.
The specific area of the highly crystalline silver powder that the present invention relates to is generally 0.10m
2/ g～1.0m
2/ g is preferably 0.20m
2/ g～0.90m
2/ g.When amassing than table, this is lower than 0.10m
2During/g,, be not preferred because of the granular of the electrode of silver thick film and the circuit difficulty that becomes.In addition, when specific area greater than 1.0m
2During/g, it is difficult that the livering of silver powder is easy to become, and is not preferred.So-called specific area among the present invention means the BET specific area.
The tap density of the highly crystalline silver powder that the present invention relates to (tap density) is usually at 3.8g/cm
3More than, preferred 4.0～6.0g/cm
3When tap density is in this scope, when making conductive paste, the fillibility of silver powder in highly crystalline silver powder cream is good, and the making of conductive paste is easy, in addition, when conductive paste formation is filmed, owing between highly crystalline silver powder, form suitable space, when filming roasting, carry out oil removing (taking off バ イ) easily from filming, improve the density of roasting film, its result reduces the resistance of silver thick film easily, is preferred.The highly crystalline silver powder that the present invention relates to, for example, available following method manufacturing.
(manufacture method of the highly crystalline silver powder that the present invention relates to)
The manufacture method of the highly crystalline silver powder that the present invention relates to is for being mixed the 1st aqueous solution that contains silver nitrate, dispersant and nitric acid with the 2nd aqueous solution that contains ascorbic acid.
The 1st aqueous solution among so-called the present invention means the aqueous solution that contains silver nitrate, dispersant and nitric acid.As the water that is used to prepare the 1st aqueous solution, because pure water, ion exchange water, ultra-pure water etc., can prevent that impurity from sneaking into silver powder, so preferably.Silver nitrate as using among the present invention is not particularly limited, can adopt solid and make the aqueous solution any.
As the dispersant that uses among the present invention, for example, can enumerate PVP (PVP), gelatin, polyethylene glycol, polyvinyl alcohol etc.Also have, in the present invention, so-called gelatin comprises gelatine.In the dispersant that the present invention uses,, the heat-resisting shrinkage of silver powder is improved, so preferred owing to PVP, gelatin.In the present invention,, the dispersiveness of silver powder is improved, simultaneously, have the silver powder that makes to particulate, the too narrowless and effect of broad of its size distribution by in the 1st aqueous solution, cooperating dispersant.
Nitric acid as using among the present invention is not particularly limited, and any of red fuming nitric acid (RFNA), rare nitric acid all can adopt.In the present invention,, can control that to generate the reaction speed of silver from silver ion slower,, and the big effect of crystallite change be arranged so it is too narrow and than broad to have the silver powder of making size distribution by in the 1st aqueous solution, cooperating nitric acid.Also have, when mismatching nitric acid and make silver powder, because it is too fast to generate the reaction speed of silver from silver ion, reaction takes place immediately, thus with the present invention in comparing of making of cooperation nitric acid, the little and crystallite particle diameter of resulting silver powder particle diameter diminishes easily.
The 1st aqueous solution when dispersant is PVP, to silver nitrate 100 weight portions, contains PVP 5 weight portions～60 weight portions, preferred 15 weight portions～50 weight portions, more preferably 20 weight portions～40 weight portions usually.When the use level of PVP is in this scope, improve the dispersiveness of silver powder, simultaneously, the too narrowless and easy broad of silver powder size distribution is so be preferred.On the other hand, when the use level of PVP was lower than 5 weight portions, resulting silver powder condensed easily, be not preferred, when being higher than 60 weight portions, impurity concentration raises easily in the resulting silver powder, easy contaminated environment, production cost raises easily, so be not preferred.
The 1st aqueous solution when dispersant is gelatin, to silver nitrate 100 weight portions, contains gelatin 0.5 weight portion～10 weight portions, preferred 1 weight portion～8 weight portions, more preferably 2 weight portions～6 weight portions usually.When the use level of gelatin is in this scope, improve the dispersiveness of silver powder, simultaneously, the too narrowless and broad that becomes easily of silver powder size distribution is so be preferred.On the other hand, when the use level of gelatin was lower than 0.5 weight portion, resulting silver powder condensed easily, be not preferred, when being higher than 10 weight portions, impurity concentration raises easily in the resulting silver powder, easy contaminated environment, production cost raises easily, is not preferred.
The 1st aqueous solution when dispersant is PVP, to water 100 weight portions, contains PVP 1 weight portion～10 weight portions, preferred 2 weight portions～4 weight portions usually.When the use level of PVP is in this scope, improve the dispersiveness of silver powder, simultaneously, the silver powder size distribution is too narrowless and the broad that becomes easily is preferred.On the other hand, when the use level of PVP was lower than 1 weight portion, resulting silver powder condensed easily, be not preferred, when being higher than 10 weight portions, impurity concentration raises easily in the resulting silver powder, easy contaminated environment, production cost raises easily, is not preferred.
The 1st aqueous solution when dispersant is gelatin, to water 100 weight portions, contains gelatin 0.1 weight portion～5 weight portions, preferred 0.4 weight portion～2 weight portions usually.When the use level of gelatin is in this scope, improve the dispersiveness of silver powder, simultaneously, the too narrowless and broad that becomes easily of silver powder size distribution is so be preferred.On the other hand, when the use level of gelatin was lower than 0.1 weight portion, resulting silver powder condensed easily, be not preferred, when being higher than 5 weight portions, impurity concentration raises easily in the resulting silver powder, easy contaminated environment, production cost raises easily, is not preferred.
The 1st aqueous solution to silver nitrate 100 weight portions, contains nitric acid 35 weight portions～70 weight portions, preferred 40 weight portions～60 weight portions, more preferably 48 weight portions～54 weight portions usually.When the use level of nitric acid is in this scope, improve the dispersiveness of silver powder, simultaneously, and the too narrowless and broad that becomes easily of silver powder size distribution, simultaneously, the effect that crystallite is strengthened is big, is preferred.On the other hand, when the use level of nitric acid was lower than 35 weight portions, the easy step-down of the crystallinity of silver powder was not preferred, and when being higher than 70 weight portions, resulting silver powder condenses easily, is not preferred.Also have, the use level of so-called nitric acid among the present invention means the use level of the red fuming nitric acid (RFNA) that is converted into concentration 61%.
What is called the 2nd aqueous solution among the present invention means aqueous ascorbic acid.The water that uses during as the preparation of the 2nd aqueous solution, pure water, ion exchange water, ultra-pure water etc. are sneaked into silver powder owing to can prevent impurity, are preferred.As the ascorbic acid that uses among the present invention, any of L type, D type all can adopt.
In the manufacture method that the present invention relates to, above-mentioned the 1st aqueous solution is mixed with the 2nd aqueous solution, highly crystalline silver powder is separated out.As mixed style, for example, can enumerate and stir the 1st aqueous solution, toward the method for wherein adding the 2nd aqueous solution.Adding method as the 2nd aqueous solution at this moment both can once be added into whole the 2nd aqueous solution in the 1st aqueous solution, also slowly added the 2nd aqueous solution gradually in the 1st aqueous solution in the past.Also have, when the dispersant in the 1st aqueous solution is PVP, if adopt the 2nd aqueous solution all once is added into method in the 1st aqueous solution, then obtain particulate easily, size distribution is too narrow and than the silver powder of broad, be preferred.If when the dispersant in the 1st aqueous solution is gelatin, adopt the method that the 2nd aqueous solution slowly is added into gradually the 1st aqueous solution, then control the particle diameter of silver powder easily, be preferred.
In the mixing of the 1st aqueous solution and the 2nd aqueous solution, according to being engaged in silver nitrate 100 weight portions in the 1st aqueous solution, the ascorbic acid that cooperates in the 2nd aqueous solution is generally 30 weight portions～90 weight portions, preferred 40 weight portions～80 weight portions, more preferably the ratio of 50 weight portions～75 weight portions is mixed.When ascorbic acid is in this scope to the use level of silver nitrate, improve the yield of silver powder easily, be preferred.On the other hand, when ascorbic acid is lower than 30 weight portions to the use level of silver nitrate 100 weight portions, reduce insufficient, reduce the silver powder yield easily, be not preferred, when ascorbic acid is higher than 90 weight portions to the use level of silver nitrate 100 weight portions, contaminated environment easily, production cost raises easily, is not preferred.
In addition, in the mixing of the 1st aqueous solution and the 2nd aqueous solution, according to the concentration of silver ions in the resulting mixed liquor, the ratio that is generally 10g/l～80g/l, preferred 30g/l～65g/l is mixed.In the time of in the concentration of silver ions in the mixed liquor is in this scope, the yield height of silver powder, and the cohesion difficulty of resulting silver powder are preferred.On the other hand, when concentration of silver ions was lower than 10g/l, the easy variation of the production efficiency of silver powder was not preferred, and when concentration of silver ions surpassed 80g/l, resulting silver powder condensed easily, is not preferred.
In addition, in the mixing of the 1st aqueous solution and the 2nd aqueous solution, according to ascorbic acid 100 weight portions to cooperating in the 2nd aqueous solution, the nitric acid that cooperates in the 1st aqueous solution is generally 40 weight portions～150 weight portions, preferred 50 weight portions～120 weight portions, more preferably the ratio of 65 weight portions～100 weight portions is mixed.When nitric acid is in this scope to the use level of ascorbic acid, improve the yield of silver powder easily, be preferred.On the other hand, when nitric acid is lower than 40 weight portions to the use level of ascorbic acid 100 weight portions, be difficult to make the crystallite particle diameter of resulting silver powder enough big, be not preferred, when nitric acid is higher than 150 weight portions to the use level of ascorbic acid 100 weight portions, resulting silver powder condenses easily, is not preferred.
By mixing of the 1st aqueous solution and the 2nd aqueous solution, the silver powder of in mixed liquor, separating out, after the 1st aqueous solution and mixing of the 2nd aqueous solution stop, usually continue mixed liquor to mix more than 3 minutes again, preferred 5 minutes～10 minutes, silver powder in the mixed liquor is grown up, and the particle diameter of silver powder and size distribution also have the dispersed particular range that reaches the silver powder that the present invention relates to easily like this, so be preferred.Resulting silver powder in the mixed liquor for example, after filters such as employing suction filter filter, washs filter residue with pure water, carries out drying, the highly crystalline silver powder that can obtain the present invention relates to.
The highly crystalline silver powder that the invention described above relates to, for example, can be as the raw material of the conductive paste that can form the electrode of chip part, plasm display panel, glass ceramics assembly, ceramic filter etc. and circuit, particularly utilize the very little characteristics of percent thermal shrinkage of silver powder, not only be suitable for as the common ceramic substrate of substrate that forms circuit, and can be suitable for use as the raw material of ltcc substrate with conductive paste.In addition, the manufacture method of the highly crystalline silver powder that the present invention relates to can be used for making the highly crystalline silver powder that the present invention relates to.
Embodiment is shown below, but the invention is not restricted to the explanation of these embodiment.
Embodiment 1
(the K value: 30) 10g, silver nitrate 50g and red fuming nitric acid (RFNA) (concentration 61%) 24.6g, stirring and dissolving is mixed with the 1st aqueous solution (the 1st water solution A) to add PVP in the pure water 500g of normal temperature.On the other hand, add ascorbic acid 35.8g in the pure water 500g of normal temperature, stirring and dissolving is mixed with the 2nd aqueous solution (the 2nd water solution A).The composition of the 1st aqueous solution and the 2nd aqueous solution is shown in table 1 and table 2.
Secondly, the 1st water solution A is under the stirring, the 2nd water solution A once is added in the 1st water solution A, interpolation was stirred 5 minutes after stopping again, and the particle in the mixed liquor is grown up.Then, stop to stir, make the particle precipitation in the mixed liquor after, discard the supernatant of mixed liquor, filter mixed liquor with suction filter, wash filter residue with pure water, carry out drying, obtain highly crystalline silver powder.
Resultant highly crystalline silver powder is measured D with following method
10, D
50, D
90, D
100, SD, crystallite particle diameter, specific area, tap density, percent thermal shrinkage and resistivity, calculate D
90/ D
10It is the results are shown in table 3～table 6.
(D
10, D
50, D
90, D
100, SD): the diameter of particle distribution recognizer made from Nikkiso Company Limited (マ イ Network ロ ト ラ Star Network HRA), the cumulative distribution of obtaining by the laser diffraction and scattering method be 10%, 50%, 90% and 100% o'clock particle diameter respectively as D
10(μ m), D
50(μ m), D
90(μ m), D
100(μ m), with the standard deviation of resulting size distribution as SD.
(diameter of particle): the X-ray diffraction device RINT2000PC that adopts リ ガ Network Co., Ltd. (Rigaku Corporation) to make, carry out powder X-ray line diffraction, from the wide crystallite particle diameter of obtaining of half value of the peak value of the angle of diffraction of each crystal plane of obtaining.
(specific area): adopt ユ ア サ ア イ オ ニ Network ス Co., Ltd. (YUASA-IONICSCOMPANY, the BET specific area of the dynamic flow specific surface analyzer of LIMITED) making (Monosorb) mensuration.
(tap density): the tap density meter that adopts the Tibetan to hold the manufacturing of science machinery production carries out sample jolt ramming, measures tap density thus.
(percent thermal shrinkage): compacting silver powder, make cylindrical pellet, the TMA/SS6300 that adopts セ イ コ one イ Application ス Star Le メ Application Star Co., Ltd. (Seiko Instruments Inc) to make, to this particle, in air, rise to 850 ℃ scope from normal temperature and carry out TMA and analyze, measure the percent thermal shrinkage of particle length direction with 10 ℃/min of programming rate.Measuring temperature is 300 ℃, 500 ℃ and 700 ℃.
(resistivity): terpineol 95 weight portions are mixed with ethyl cellulose 5 weight portions, the preparation mixed solvent mixes these mixed solvent 15 weight portions with sample powder 85 weight portions, make cream, this cream is carried out roasting in 300 ℃, make silver and film with several microns left and right thicknesses.In addition, except that replacing 300 ℃, film with the above-mentioned same silver of having made with 400 ℃ of sintering temperatures and 500 ℃.
Below, the numerical digit that adopts Hewlett-Packard Co., Ltd. the to make ohmer (MILLIOHM METER) that declines, measure the resistance (Ω) that above-mentioned silver films with four-terminal method after, length is asked electricalresistivity (Ω m) between sectional area of filming from silver and terminal.
Embodiment 2
(the K value: 30) 20g, silver nitrate 50g and red fuming nitric acid (RFNA) (concentration 61%) 24.6g, stirring and dissolving is prepared the 1st aqueous solution (the 1st aqueous solution B) to add PVP in the pure water 500g of normal temperature.On the other hand, add ascorbic acid 35.8g in the pure water 500g of normal temperature, stirring and dissolving is prepared the 2nd aqueous solution (the 2nd water solution A).The composition of the 1st aqueous solution and the 2nd aqueous solution is shown in table 1 and table 2.
Secondly, the 1st aqueous solution B is under the stirring, the 2nd water solution A once all is added among the 1st aqueous solution B, interpolation was stirred 5 minutes after stopping again, and the particle in the mixed liquor is grown up.Then, stop to stir, make the particle precipitation in the mixed liquor after, discard the supernatant of mixed liquor, filter mixed liquor with suction filter, wash filter residue with pure water, carry out drying, obtain highly crystalline silver powder.
To resulting silver powder, similarly to Example 1, measure D with said method
10, D
50, D
90, D
100, SD, crystallite particle diameter, specific area, tap density, percent thermal shrinkage and resistivity, calculate D
90/ D
10It is the results are shown in table 3～table 6.
Comparative example 1
(the K value: 30) 10g and silver nitrate 50g, stirring and dissolving is prepared the 1st aqueous solution (the 1st aqueous solution C) to add PVP in the pure water 500g of normal temperature.On the other hand, add ascorbic acid 26g in the pure water 500g of normal temperature, stirring and dissolving is prepared the 2nd aqueous solution (the 2nd aqueous solution B).The composition of the 1st aqueous solution and the 2nd aqueous solution is shown in table 1 and table 2.
Secondly, the 1st aqueous solution C is under the stirring, the 2nd aqueous solution B once all is added among the 1st aqueous solution C, interpolation was stirred 5 minutes after stopping again, and the particle in the mixed liquor is grown up.Then, stop to stir, make the particle precipitation in the mixed liquor after, discard the supernatant of mixed liquor, filter mixed liquor with suction filter, wash filter residue with pure water, carry out drying, obtain silver powder.
To resulting silver powder, similarly to Example 1, measure D with said method
10, D
50, D
90, D
100, SD, crystallite particle diameter, specific area, tap density, percent thermal shrinkage and resistivity, calculate D
90/ D
10It is the results are shown in table 3～table 6.
Embodiment 3
In the pure water 250g of normal temperature, add gelatin (new field gelatin Co., Ltd. makes) 1.0g, silver nitrate 50g and red fuming nitric acid (RFNA) (concentration 61%) 26.4g, be heated to 50 ℃ of stirring and dissolving, prepare the 1st aqueous solution (the 1st aqueous solution D).On the other hand, add ascorbic acid 26.4g in the pure water 250g of normal temperature, stirring and dissolving is prepared the 2nd aqueous solution (the 2nd aqueous solution C).The composition of the 1st aqueous solution and the 2nd aqueous solution is shown in table 1 and table 2.
Secondly, 50 ℃ the 1st aqueous solution D are under the stirring, with 30 minutes the 2nd aqueous solution D of normal temperature slowly are added among the 1st aqueous solution D, interpolation was stirred 5 minutes after stopping again, and the particle in the mixed liquor is grown up.Then, stop to stir, make the particle precipitation in the mixed liquor after, discard the supernatant of mixed liquor, filter mixed liquor with suction filter, wash filter residue with pure water, carry out drying, obtain highly crystalline silver powder.
To resultant silver powder, similarly to Example 1, measure D with said method
10, D
50, D
90, D
100, SD, crystallite particle diameter, specific area, tap density, percent thermal shrinkage and resistivity, calculate D
90/ D
10It is the results are shown in table 3～table 6.
Embodiment 4
In the pure water 500g of normal temperature, add gelatin (new field gelatin Co., Ltd. makes) 3.0g, silver nitrate 50g and red fuming nitric acid (RFNA) (concentration 61%) 26.4g, be heated to 50 ℃ of stirring and dissolving, prepare the 1st aqueous solution (the 1st aqueous solution E).On the other hand, add ascorbic acid 25.9g in the pure water 500g of normal temperature, stirring and dissolving is prepared the 2nd aqueous solution (the 2nd aqueous solution D).The composition of the 1st aqueous solution and the 2nd aqueous solution is shown in table 1 and table 2.
Secondly, 50 ℃ the 1st aqueous solution E are under the stirring, with 30 minutes the 2nd aqueous solution D of normal temperature slowly are added among the 1st aqueous solution E, interpolation was stirred 5 minutes after stopping again, and the particle in the mixed liquor is grown up.Then, stop to stir, make the particle precipitation in the mixed liquor after, discard the supernatant of mixed liquor, filter mixed liquor with suction filter, wash filter residue with pure water, carry out drying, obtain highly crystalline silver powder.
To resultant silver powder, similarly to Example 1, measure D with said method
10, D
50, D
90, D
100, SD, crystallite particle diameter, specific area, tap density, percent thermal shrinkage and resistivity, calculate D
90/ D
10It is the results are shown in table 3～table 6.
Table 1
| Water (g) | The kind of dispersant | Dispersant (g) | Silver nitrate (g) | Red fuming nitric acid (RFNA) (g) | The kind of first aqueous solution | |
| Embodiment 1 | 500 | PVP | 10 | 50 | 24.6 | A |
| Embodiment 2 | 500 | PVP | 20 | 50 | 24.6 | B |
| Comparative example 1 | 500 | PVP | 10 | 50 | 0 | C |
| Embodiment 3 | 250 | Gelatin | 1.0 | 50 | 26.4 | D |
| Embodiment 4 | 500 | Gelatin | 3.0 | 50 | 24.6 | E |
Table 2
| Water (g) | Ascorbic acid (g) | The kind of second aqueous solution | |
| Embodiment 1 | 500 | 35.8 | A |
| Embodiment 2 | 500 | 35.8 | A |
| Comparative example 1 | 500 | 26.0 | B |
| Embodiment 3 | 250 | 26.4 | C |
| Embodiment 4 | 500 | 25.9 | D |
Table 3
| D 10 (μm) | D 50 (μm) | D 90 (μm) | D 100 (μm) | D 90/D 10 | SD | |
| Embodiment 1 | 2.97 | 6.35 | 10.75 | 22.0 | 3.6 | 3.01 |
| Embodiment 2 | 1.30 | 3.03 | 5.67 | 15.6 | 4.4 | 1.59 |
| Comparative example 1 | 2.14 | 2.83 | 4.08 | 9.3 | 1.9 | 0.71 |
| Embodiment 3 | 2.72 | 4.36 | 7.33 | 18.5 | 2.7 | 1.71 |
| Embodiment 4 | 0.76 | 1.27 | 2.28 | 4.6 | 3.0 | 0.57 |
Table 4
| Size of microcrystal () | Specific area (m 2/g) | Tap density (g/cm 3) | |
| Embodiment 1 | 441 | 0.30 | 4.1 |
| Embodiment 2 | 377 | 0.62 | 4.0 |
| Comparative example 1 | 258 | 0.62 | 3.8 |
| Embodiment 3 | 545 | 0.20 | 4.4 |
| Embodiment 4 | 441 | 0.72 | 4.8 |
Table 5
| 300 ℃ percent thermal shrinkage (%) | 500 ℃ percent thermal shrinkage (%) | 700 ℃ percent thermal shrinkage (%) | |
| Embodiment 1 | 0.13 | -2.13 | -2.2 |
| Embodiment 2 | 0.09 | -2.68 | -2.9 |
| Comparative example 1 | 0.84 | -4.02 | -7.82 |
| Embodiment 3 | 0.27 | 1.08 | 1.13 |
| Embodiment 4 | -0.58 | -1.51 | -1.35 |
Table 6
| The electricalresistivity that silver after 300 ℃ of roastings is filmed (Ω m) | The electricalresistivity that silver after 400 ℃ of roastings is filmed (Ω m) | The electricalresistivity that silver after 500 ℃ of roastings is filmed (Ω m) | |
| Embodiment 1 | 4.1×10 -5 | 2.0×10 -5 | 9.9×10 -6 |
| Embodiment 2 | 5.2×10 -5 | 1.5×10 -5 | 1.2×10 -5 |
| Comparative example 1 | 7.2×10 -4 | 8.9×10 -6 | 4.8×10 -5 |
| Embodiment 3 | 9.4×10 -6 | 8.3×10 -6 | 9.9×10 -6 |
| Embodiment 4 | 1.0×10 -5 | 8.8×10 -6 | 4.8×10 -5 |
From table 1～table 5 as can be known, with the silver powder that dispersant and nitric acid are made, the crystallite particle diameter is big, has high crystalline, and is little at 700 ℃ percent thermal shrinkage.In addition, when adopting gelatin to make dispersant, particularly the percent thermal shrinkage at 700 ℃ is little as can be known.In addition, as known from Table 6, with the silver powder that dispersant and nitric acid are made, compare with the silver powder of making without nitric acid, the electricalresistivity who films at the silver of 300 ℃ of roastings is low.Its reason can be speculated as because the crystallite particle diameter is big, due to the electron motion in the silver powder is level and smooth.
Industrial utilizability
The highly crystalline silver powder that the present invention relates to and the manufacture method of highly crystalline silver powder, for example, can as the raw material of the conductive paste of the electrode that forms chip part, plasm display panel, glass ceramics assembly, ceramic filter etc. and circuit, particularly be applicable to as the raw material of ltcc substrate with conductive paste.
Claims (14)
1. the manufacture method of a highly crystalline silver powder is characterized in that, will contain the 1st aqueous solution of silver nitrate, dispersant and nitric acid, is mixed with the 2nd aqueous solution that contains ascorbic acid.
2. according to the manufacture method of the highly crystalline silver powder described in the claim 1, it is characterized in that above-mentioned dispersant is a PVP.
3. according to the manufacture method of the highly crystalline silver powder described in the claim 1, it is characterized in that above-mentioned dispersant is a gelatin.
4. according to the manufacture method of the highly crystalline silver powder described in the claim 2, it is characterized in that, above-mentioned the 1st aqueous solution is to silver nitrate 100 weight portions, to cooperate the aqueous solution of PVP 5 weight portions～60 weight portions, nitric acid 35 weight portions～70 weight portions.
5. according to the manufacture method of the highly crystalline silver powder described in the claim 3, it is characterized in that above-mentioned the 1st aqueous solution is to silver nitrate 100 weight portions, to cooperate the aqueous solution of gelatin 0.5 weight portion～10 weight portions, nitric acid 35 weight portions～70 weight portions.
6. according to the manufacture method of the highly crystalline silver powder described in the claim 1, it is characterized in that, with above-mentioned the 1st aqueous solution and above-mentioned the 2nd aqueous solution, according to silver nitrate 100 weight portions to cooperating in above-mentioned the 1st aqueous solution, the ascorbic acid that cooperates in the 2nd aqueous solution is that the ratio of 30 weight portions～90 weight portions is mixed.
7. according to the manufacture method of the highly crystalline silver powder described in the claim 1, it is characterized in that, with above-mentioned the 1st aqueous solution and above-mentioned the 2nd aqueous solution, according to ascorbic acid 100 weight portions to cooperating in above-mentioned the 2nd aqueous solution, the nitric acid that cooperates in the 1st aqueous solution is that the ratio of 40 weight portions～150 weight portions is mixed.
8. a highly crystalline silver powder is characterized in that, adopts the method manufacturing of record in the claim 1.
9. according to the highly crystalline silver powder described in the claim 8, it is characterized in that its crystallite particle diameter is more than 300 .
10. according to the highly crystalline silver powder described in the claim 8, it is characterized in that average grain diameter D
50Be 0.5 μ m～10 μ m (still, D
50The median particle diameter (μ m) of the cumulative distribution 50 volume % that expression employing laser diffraction and scattering formula particle size distribution method obtains).
11. the highly crystalline silver powder according to described in the claim 8 is characterized in that, at 700 ℃ percent thermal shrinkages in ± 3%.
12. the highly crystalline silver powder according to described in the claim 8 is characterized in that, D
90/ D
10Be 2.1～5.0 (still, in the following formula, D
10And D
90Cumulative distribution 10 volume % that laser diffraction and scattering formula particle size distribution method obtains and the median particle diameter (μ m) of 90 volume % are adopted in expression respectively).
13. a highly crystalline silver powder is characterized in that, the crystallite size of microcrystal is more than 300 , average grain diameter D
50Be 0.5 μ m～10 μ m, at 700 ℃ length direction percent thermal shrinkages in ± 3%.
14. the highly crystalline silver powder according to described in the claim 13 is characterized in that, D
90/ D
10Be 2.1～5.0 (still, in the following formula, D
10And D
90Cumulative distribution 10 volume % that laser diffraction and scattering formula particle size distribution method obtains and the median particle diameter (μ m) of 90 volume % are adopted in expression respectively).
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004034121A JP4976642B2 (en) | 2004-02-10 | 2004-02-10 | High crystalline silver powder and method for producing the same |
| JP034121/2004 | 2004-02-10 |
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| CN1925941A true CN1925941A (en) | 2007-03-07 |
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| CNA2005800063565A Pending CN1925941A (en) | 2004-02-10 | 2005-02-04 | Highly crystalline silver powder and method for production thereof |
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|---|---|
| US (1) | US20090023007A1 (en) |
| EP (1) | EP1721690A1 (en) |
| JP (1) | JP4976642B2 (en) |
| KR (1) | KR101215458B1 (en) |
| CN (1) | CN1925941A (en) |
| TW (1) | TWI286090B (en) |
| WO (1) | WO2005075133A1 (en) |
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2004
- 2004-02-10 JP JP2004034121A patent/JP4976642B2/en not_active Expired - Lifetime
-
2005
- 2005-02-04 CN CNA2005800063565A patent/CN1925941A/en active Pending
- 2005-02-04 US US10/588,970 patent/US20090023007A1/en not_active Abandoned
- 2005-02-04 WO PCT/JP2005/001660 patent/WO2005075133A1/en not_active Application Discontinuation
- 2005-02-04 EP EP05709726A patent/EP1721690A1/en not_active Withdrawn
- 2005-02-04 TW TW094103609A patent/TWI286090B/en not_active IP Right Cessation
- 2005-02-04 KR KR1020067018248A patent/KR101215458B1/en not_active IP Right Cessation
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| TWI286090B (en) | 2007-09-01 |
| WO2005075133A1 (en) | 2005-08-18 |
| KR20070018025A (en) | 2007-02-13 |
| JP2005226094A (en) | 2005-08-25 |
| EP1721690A1 (en) | 2006-11-15 |
| US20090023007A1 (en) | 2009-01-22 |
| JP4976642B2 (en) | 2012-07-18 |
| TW200536636A (en) | 2005-11-16 |
| KR101215458B1 (en) | 2012-12-26 |
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