CN1826198A - Fine-grain silver powder and process for producing the same - Google Patents
Fine-grain silver powder and process for producing the same Download PDFInfo
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- CN1826198A CN1826198A CNA2004800209882A CN200480020988A CN1826198A CN 1826198 A CN1826198 A CN 1826198A CN A2004800209882 A CNA2004800209882 A CN A2004800209882A CN 200480020988 A CN200480020988 A CN 200480020988A CN 1826198 A CN1826198 A CN 1826198A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C5/00—Alloys based on noble metals
- C22C5/06—Alloys based on silver
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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
- 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
Abstract
Fine-grain silver powder that has a grain size of minuteness not known in the prior art, exhibiting dispersion close to monodispersion with reduced grain aggregation and exhibiting a low impurity content. For obtaining the fine-grain silver powder, an aqueous solution of silver ammine complex (S1) is caused to flow through given flow channel (hereinafter referred to as 'first flow channel'). Second flow channel (b) is disposed so as to join the middle of the first flow channel (a), and an organic reducing agent optionally together with an additive (S2) is caused to flow through the second flow channel (b). At confluence (m) of the first flow channel (a) and the second flow channel (b), contact and mixing is carried out so as to effect reduction deposition, followed by washing with excess alcohol. Thus, there is obtained fine-grain silver powder of such powder characteristics not known in the prior art that the average diameter of primary grain (D1A) obtained by an image analysis of scanning electron microscope images is 0.6 mum or less (a), the crystallite diameter 10 nm or less (b), the sintering initiation temperature 240 DEG C or below (c), and the carbon content 0.25 wt.% or less (d).
Description
Technical field
The present invention relates to the manufacture method of a kind of particulate silver powder and particulate silver powder thereof, particularly relate to the few particulate silver powder of a kind of impurity content.
Background technology
As the record of patent documentation 1, during silver powder is in the past made, adopt with liquor argenti nitratis ophthalmicus and ammoniacal liquor always and make the silver ammonia complex aqueous solution, in this silver ammonia complex aqueous solution, add the wet type reducing process of organic reducing agent.In recent years, these silver powder are mainly used in the formation of the electrode of chip element, plasma display panel etc. or circuit.
Patent documentation 1: the spy opens the 2001-107101 communique
Therefore, in above-mentioned electrode and circuit, require the significantly miniaturization of formed circuit and electrode etc., require to have very high reliability when requiring densification, the high precision int of distribution.
But, the powder of the silver powder that usefulness manufacture method in the past obtains, in fact the average grain diameter D of its primary particle
IAUsually surpass 0.6 μ m, according to the average grain diameter D of laser inflection formula particle size distribution at random method mensuration
50Surpass 1.0 μ m, use D
50/ D
IAThe condensation degree of expression surpasses 1.7.Therefore, be not suitable for the circuit formation of fine compartmentation in recent years etc., become the main cause that the yield rate of product declines to a great extent.
On the other hand, from the using method of silver powder, there is following problem.All the time, in the circuit that uses elargol forms, heating-up temperature non-below 300 ℃ burn till or the purposes of low-temperature sintering type many, in order to obtain high sintering character at low temperatures, preferably use the silver powder of low frit.But, in order to obtain the silver powder of low frit, on creating conditions, having to adopt and reduce reaction system rapidly, its result though it is low to obtain crystallinity, condenses tangible silver powder.
Thus, on market, it is outstanding that the cohesion that requirement provides the particulate that did not in the past have silver powder, this silver powder to have powder approaches monodispersed dispersiveness and low-temperature sintering less and more.
On the other hand, require the impurity content of silver powder few.That is, above-mentioned wet type reducing process has been adopted in the manufacturing of silver powder, and the reducing agent that uses in this technology etc. remains on the powder surface of silver powder.Therefore, if employing manufacture method in the past, unavoidable problem that Here it is.If the impurity content of silver powder increases, then use the resistance of the formed conductor of this silver powder to increase.
Its result, market requires particulate, high dispersive always, and the few silver powder of impurity content.
Summary of the invention
So, the inventor etc., in the past make silver nitrate aqueous solution and ammoniacal liquor hybrid reaction are obtained the silver ammonia complex aqueous solution, by in this silver ammonia complex aqueous solution, adding reducing agent the silver particles reduction is separated out, filter, wash, dry manufacture method is the basis, in this manufacture method, inject intention, carried out deep research.Its result can obtain the particulate silver powder of the level that can't obtain with in the past manufacture method, and obviously reduces the impurity content of this particulate silver powder, thereby can access the particulate silver powder that did not in the past have.Especially, relevant manufacture method of the present invention can be accomplished the yield rate height of its particulate silver powder, and can stably be made.Below, about the present invention, divide " particulate silver powder " and " manufacture method " to be illustrated.
" particulate silver powder "
At first, particulate silver powder of the present invention is described.The feature of the maximum of particulate silver powder of the present invention is the powder characteristics with following a.～c..These powder characteristics are to be set forth in the present powder determination techniques, particulate silver powder of the present invention show the most outstanding feature, and the characteristic of setting up simultaneously.Below each characteristic is described.
A. characteristic is, the average grain diameter D of the primary particle that the graphical analysis by the scanning electron microscope image obtains
IABe below the 0.6 μ m.At this, so-called " the average grain diameter D of the primary particle that the graphical analysis by the scanning electron microscope image obtains
IA" be, by the observation image that uses the observable silver powder of surface sweeping type electron microscope (SEM) (use 10000 times multiplying power during preferred view particulate silver powder of the present invention, adopt 3000～5000 times multiplying power when observing silver powder in the past) is carried out the average grain diameter that graphical analysis obtains.In addition, use the graphical analysis of the observed particulate silver powder of scanning electron microscope (SEM) to be meant the IP-1000PC that uses rising sun engineering (エ Application ジ ニ ア リ Application グ) Co., Ltd.'s system in this manual, be 10 in the circularity threshold value, degree of overlapping is to carry out round particle 20 times to resolve, and the average grain diameter D that obtains
IAHandle the average grain diameter D that obtains owing to carry out image by observation image to this particulate silver powder
IAObserve image from SEM and directly obtain, therefore, can accurately capture the average grain diameter of primary particle.The D of said in the present invention particulate silver powder
IA, wait to observe nearly all in the scope of 0.01 μ m～0.6 μ m according to inventor, but in fact also have when can confirm finer diameter, therefore specially do not stipulate its lower limit.
B. characteristic is, because particulate silver powder of the present invention demonstrates the polymolecularity that silver powder does not in the past have, has therefore used " condensation degree " as this dispersed index of expression.
Said in this manual condensation degree is meant the average grain diameter D that utilizes above-mentioned primary particle
IAWith the average grain diameter D that measures according to laser inflection formula particle size distribution at random method
50, use D
50/ D
IAThe value of expression.Here, D
50Be meant and utilize resulting, the particle diameter under weight accumulative total 50% of laser inflection formula particle size distribution at random method, this average grain diameter D
50Value be not the value of directly diameter of each powder being observed, and be meant will cohesion powder as a particle (aggregated particle), the average grain diameter of calculating.That is, this is because consider that in fact the particulate of silver powder is not so-called single branch loose powder that each particle separates fully, and normally form the state of a plurality of powder cohesions.But, in general, the state of aggregation of powder more less, approaching more single dispersion the, then average grain diameter D
50Value more little.The average grain diameter D of the particulate silver powder that uses among the present invention
50In the scope about 0.25 μ m～0.80 μ m, become average grain diameter D with usefulness not getable scope of manufacture method in the past
50Particulate silver powder.In addition, laser inflection formula particle size distribution at random method in this manual is meant that the silver powder with 0.1g mixes with ion exchange water, after 5 minutes, utilize laser inflection formula particle size distribution device at random MicroTrac HRA 9320-X100 type (manufacturing of Leeds+Northrup society) to measure with ultrasonic homogenizer (Japanese smart mechanism is made made US-300T) dispersion.
Compare " the average grain diameter D of the primary particle that the graphical analysis by the scanning electron microscope image obtains in this
IA" be meant by the observation image that uses the observed silver powder of scanning electron microscope (SEM) is carried out the resulting average grain diameter of image analysis, be not consider the average grain diameter that accurately captures under the state of aggregation.
Its result, the average grain diameter D that decisions such as the inventor utilize laser inflection formula particle size distribution at random method to measure
50With the D that obtains by image analysis
IA, use D
50/ D
IAThe value of calculating is as condensation degree.That is, in the particulate silver powder of same batch, suppose and to go out D by enough same precision determinations
50And D
IAValue, if consider by above-mentioned theory, reflection has the measured value D of state of aggregation
50Value just greater than D
IAValue.At this moment, if the state of aggregation of the powder of particulate silver powder is more little, D
50Value just be infinitely close to D
IAValue, as the D of condensation degree
50/ D
IAValue approach 1.When condensation degree is 1, can be described as single branch loose powder of the state of aggregation that does not have powder fully.
Therefore, the inventor etc. are about condensation degree with utilize the viscosity, sintering processing of the particulate silver powder glue that the particulate silver powder of each condensation degree produces and the dependency relation of the surface of conductors smoothness that obtains etc. is investigated.Its result has found to access the fact of extremely good dependency relation.Can judge thus,, just can adjust the viscosity of the particulate silver powder glue that this particulate silver powder of use produces arbitrarily if adjust the condensation degree that particulate silver powder is had.And, found if condensation degree is adjusted into below 1.5, the variation of the surface smoothness after the viscosity of particulate silver powder glue, the sintering processing etc. can be controlled at extremely in the narrow region.In addition, it is many more that state of aggregation is removed, and utilizes this particulate oxide silver powder sintering and the film density of the conductor that obtains is high more, and its result can reduce the resistance of formed sintering conductor.
In addition, actual condensation degree of calculating is when also having demonstration less than 1 value.This is because the D that uses in the calculating of condensation degree
IABe assumed to real ball, therefore 1 the value of should not arriving in theory, but in fact owing to be not real ball has obtained the value less than 1 condensation degree.
C. characteristic is, the crystallite diameter is below the 10nm, and this crystallite diameter and sintering begin temperature very confidential relation.That is, the silver powder that equates with average grain diameter compares each other, and the crystallite diameter is more little, and the sintering under the low temperature is possible more.Therefore, the microparticle surfaces energy as particulate silver powder of the present invention is big, and, owing to have the following little crystallite diameter of 10nm, sintering can be begun temperature low temperatureization.At this, the crystallite diameter is not set limit value, this is because produce certain evaluated error according to determinator, condition determination etc.In addition, being difficult to the demanding reliability of measured value in the crystallite diameter is scope below the 10nm, if leave no choice but the regulation lower limit, is about 2nm according to inventor's etc. result of study.
D. characteristic is that the content of organic impurities is scaled below the 0.25wt% with the carbon amount.At this, use the index of carbon content, as the benchmark of weighing attached to the impurity level on the silver powder powder as organic impurity content.The mensuration of the carbon content of this moment is to use the hole field to make the EMIA-320V of manufacturing, mixes the particulate silver powder of 0.5g, the tungsten powder of 1.5g, the glass putty of 0.3g, puts it in the magnetic crucible, by the value of burning-infrared absorption determining.The carbon content of the silver powder that obtains with in the past manufacture method is strengthened washing in any case, all contains the carbon content above 0.25wt%.
Because particulate silver powder of the present invention has the powder characteristics of aforesaid a.～d., can be the silver powder that did not have certainly in the past.And the characteristic particulate silver powder of the present invention that begins temperature from sintering can be described as the particulate silver powder that can begin sintering under the low temperature below 240 ℃.In addition, this sintering is begun temperature does not have its lower limit of special provision yet, if but the consideration inventor's etc. research and general technology general knowledge, the sintering that may obtain hardly below 170 ℃ begins temperature, thinks to be equivalent to the temperature of lower limit.
Especially as having the effect of above-mentioned powder characteristics, the jolt ramming packed density of particulate silver powder of the present invention is 4.0g/cm
3Above high density.In this said jolt ramming packed density is particulate silver powder by accurate weighing 200g, puts into 150cm
3Graduated cylinder in, with the stroke be carry out repeatedly under the 40mm 1000 times fall bump after, measure the value that the method for the volume of particulate silver powder is measured.This jolt ramming packed density has fine particle diameter, has the dispersed high state that does not have cohesion between the powder in theory, just can obtain high more value.The tap density of considering silver powder in the past is less than 4.0g/cm
3, can prove that particulate silver powder of the present invention is very fine and dispersed outstanding particulate silver powder.
" manufacture method of particulate silver powder "
Manufacture method of the present invention is, silver nitrate aqueous solution and ammoniacal liquor hybrid reaction are obtained the silver ammonia complex aqueous solution, make this silver ammonia complex aqueous solution and organic reducing agent haptoreaction, thereby silver particles is separated out in reduction, by the method for filtering, washing, drying being made silver powder, it is characterized in that, use the reduction dosage, silver nitrate amount, the ammonia vol that become thin concentration after adding.In the past, generally the reductant solution and the silver ammonia complex aqueous solution are mixed in groove in batch, therefore, be the concentration more than the 10g/l for silver concentration is reconciled, if do not add a lot of silver nitrate amounts, reduction dosage and ammonia vol, just can't guarantee productivity ratio with respect to equipment scale.
First of manufacture method of the present invention is characterised in that, the organic reducing agent concentration that the silver ammonia complex aqueous solution and organic reducing agent carry out after the haptoreaction is low, can reduce absorption and remain in the powder surface of the silver powder that is generated or enter the organic reducing material of silt interior in the developmental process of powder.Therefore, in this mixed solution, silver concentration is maintained 1g/l～6g/l, the organic reducing agent concentration is maintained 1g/l～3g/l for most preferably.
At this, proportional relation between silver concentration and the organic reducing dosage, certainly, silver concentration high energy more obtains the silver powder of volume more.But if silver concentration surpasses 6g/l, the tendency of the silver particles seedyization of then separating out becomes and in the past the silver powder particle diameter without any difference, can't obtain the said particulate silver powder with polymolecularity of the present invention.In contrast to this, if the not enough 1g/l of silver concentration, though could obtain and fine particulate silver powder, but thereby the increase of too fine oil absorption causes the rising of adhesiveness, is necessary to increase the amount of organic paint vehicle, finally cause the film density of formed sintering conductor to reduce the tendency that has a resistance and rise.Add, can not satisfy necessary industrial productivity.
Therefore, above-mentioned silver concentration is maintained 1g/l～6g/l, the organic reducing agent concentration is maintained 1g/l～3g/l is the only condition that can obtain particulate silver powder of the present invention with good yield rate.At this, with organic reducing agent concentration regulation 1g/l～3g/l be with the relation of the silver concentration of the silver ammonia complex aqueous solution in, selected as the most suitable scope that can access particulate silver powder.If the organic reducing agent concentration surpasses 3g/l, though can reduce the reducing agent liquid measure of adding with respect to the silver ammonia complex aqueous solution, but the cohesion of the silver powder powder that reduction is separated out begins obviously to carry out, and impurity level (in this manual impurity content being represented with the carbon content) beginning that is included in the powder sharply increases.On the other hand, if the not enough 1g/l of organic reducing agent concentration, then total liquid measure of employed reducing agent increases, and wastewater treatment capacity also increases, and can not satisfy industrial economy.
At this said " organic reducing agent " is quinhydrones, ascorbic acid, glucose etc.Wherein, the preferred quinhydrones that uses in organic reducing agent.In the present invention, quinhydrones is with respect to other organic reducing agent, has to access the reactive more outstanding and necessary only reaction speed of the silver powder low-crystalline that the crystallite diameter is little.
In addition, also other additive and above-mentioned organic reducing agent can be used in combination.At this said additive glue class, amine polymeric agent, cellulose family of gelatin etc. etc., the reduction that preferably can stablize silver powder is separated out technology, is played the additive of certain dispersant function simultaneously, suitably selects to use to get final product according to the kind of organic reducing agent, operation etc.
In addition, separate out the method for particulate silver powder about making the reduction of the resulting as stated above silver ammonia complex aqueous solution and reducing agent haptoreaction, in the present invention, as shown in Figure 1, the preferred employing makes silver ammonia complex aqueous solution S
1The stream of the regulation of flowing through (above and below be referred to as " first stream "), the second stream b of interflow in the way of this first stream is set, by this second stream b with organic reducing agent and additive S as required
2Flow in the first stream a, on the junction of two streams m of the first stream a and the second stream b, contact mixing, and the method (below, this method is referred to as " interflow hybrid mode ") of silver particles is separated out in reduction.
By adopting aforesaid interflow hybrid mode, being blended in the shortest time of two kinds of liquid finished, and reacts by uniform state in the system, therefore, can form the powder of uniform state.In addition, the organic reducing dosage when all seeing by mixed solution is few, and it is few to mean that absorption remains in the lip-deep organic reducing dosage of powder of the reduction particulate silver powder of separating out.Its result can reduce attached to through the impurity level in filtration, the dry resulting particulate silver powder, also can reduce the resistance of the sintering conductor that forms by elargol.
Especially, when silver nitrate aqueous solution and ammoniacal liquor haptoreaction obtained the silver ammonia complex aqueous solution, preferably adopting silver nitrate concentration was the silver nitrate aqueous solution of 2.6g/l～48g/l, and obtaining silver concentration is the silver ammonia complex aqueous solution of 2g/l～12g/l.Concentration at this said regulation silver nitrate aqueous solution has identical meaning with the liquid measure of regulation silver nitrate aqueous solution, for the silver concentration that makes the silver ammonia complex aqueous solution reaches 2g/l～12g/l, the concentration and the liquid measure that are added on ammoniacal liquor wherein must be the amounts of regulation.In present stage, also do not understand clear and definite technology reason, but, can access and demonstrate better manufacturing stability and stay-in-grade particulate silver powder by using the silver nitrate aqueous solution of above-mentioned silver nitrate concentration as 2.6g/l～48g/l.
And the 2nd feature of manufacture method of the present invention is that the washing of finally carrying out is very important feature.The washing of this moment promptly can be carried out water washing and ethanol washing combination, also can only carry out the ethanol washing, but strengthens the washing when washing with ethanol.That is, the particulate silver powder with respect to the reduction of 40g is separated out washs with the pure water about 100ml usually, afterwards, carries out the ethanol washing with the ethanol about 50ml.With respect to this, among the present invention, when carrying out the ethanol washing, use the above excess ethyl alcohol of 200ml particulate silver powder 5L above, relative 1kg to wash.
Can reduce impurity level by above-mentioned reinforcement washing, be that the organic reducing dosage when having adopted the reaction system of thin concentration and having adopted mixed solution all is controlled at the cause of the method for low amount because in the haptoreaction of the silver ammonia complex aqueous solution when making particulate silver powder and reducing agent.
The effect of invention
Can confirm that particulate silver powder of the present invention has the fine degree that did not in the past have, for have the particulate silver powder that polymolecularity, impurity content are few, do not have in the past.In addition, by adopting aforesaid manufacture method, can effectively make particulate silver powder of the present invention.
Description of drawings
Fig. 1 is the figure of the hybrid concept of the expression silver ammonia complex aqueous solution and reducing agent.
Fig. 2 is the sem observation image of particulate silver powder of the present invention.
Fig. 3 is the sem observation image of particulate silver powder of the present invention.
Fig. 4 is the sem observation image of the particulate silver powder of manufacture method in the past.
Fig. 5 is the sem observation image of the particulate silver powder of manufacture method in the past.
The specific embodiment
Below, comparative examples describes the preferred embodiments of the present invention in detail.
Embodiment 1
In the present embodiment, make particulate silver powder, and measured the powder characteristics of resulting particulate silver powder with above-mentioned manufacture method.And, further use particulate silver powder to make elargol, the formation hookup has been measured conductor resistance and sintering begins temperature.
At first, the silver nitrate of 63.3g is dissolved in 9.7 liters the pure water, the preparation silver nitrate aqueous solution adds the ammoniacal liquor that 235ml concentration is 25wt% once in this silver nitrate aqueous solution, obtain the silver ammonia complex aqueous solution by stirring.
Is among the first stream a of 13mm with this silver ammonia complex aqueous solution with the internal diameter that the flow of 1500ml/sec imports to as shown in Figure 1, from the flow inflow reducing agent of the second stream b with 1500ml/sec, contact under 20 ℃ the temperature in junction of two streams m, particulate silver powder is separated out in reduction.The reducing agent that use this moment is for being dissolved in the 21g quinhydrones 10 liters of quinhydrones aqueous solution in the pure water.Therefore, the quinhydrones concentration of mixing when finishing is about 1.04g/l, is very thin concentration.
In order to separate the particulate silver powder 40g that so obtains, use filter, wash with 100ml water and 600ml methyl alcohol, further carry out 70 ℃ * 5 hours drying, thereby obtain particulate silver powder.The scanning electron microscope image of the particulate silver powder that so obtains is shown in Fig. 2.
The powder characteristics of the particulate silver powder that so obtains is documented in the table 1 with the powder characteristics of the silver powder that is obtained by embodiment 2 and comparative example.Here, indefinite assay method in the above-described explanation etc. is described.Sintering in the table 1 begins temperature, with the accurate weighing 0.5g of balance particulate silver powder, it is used 2t/cm
3Exert pressure made graininess in 1 minute, thermo-mechanical analysis device (TMA device) TMA/SS6000 with the manufacturing of セ イ コ one イ Application ス Star Le メ Application Star society, with air mass flow 200cc/ minute, 2 ℃/minute of programming rates, retention time is 0 minute a condition, measures in the scope of normal temperature～900 ℃.The copper bulk resistor of record is made elargol for using each silver powder in the table 1, forms circuit on ceramic substrate, the value of utilizing the width that processes at 180～250 ℃ sintering temperature to measure for the circuit of 1mm.In addition, consisting of by particulate silver powder 85wt%, ethyl cellulose 0.75wt%, terpineol 14.25wt% of elargol constitutes.It is to measure to separate out the size of crystal grain that FIB analyzes, and is used for the mensuration of crystallite diameter.
Embodiment 2
In the present embodiment, utilize and make particulate silver powder, and resulting particulate silver powder is measured powder characteristics with embodiment 1 different creating conditions.And, further use particulate silver powder to make elargol, form hookup, carry out the mensuration that conductor resistance and sintering begin temperature.
At first, the silver nitrate of 63.3g is dissolved in 3.1 liters the pure water, the preparation silver nitrate aqueous solution, disposable interpolation 235ml concentration is the ammoniacal liquor of 25wt% in this silver nitrate aqueous solution, obtains the silver ammonia complex aqueous solution by stirring.
Is among the first stream a of 13mm with this silver ammonia complex aqueous solution with the internal diameter that the flow of 1500ml/sec imports to as shown in Figure 1, from the flow inflow reducing agent of the second stream b with 1500ml/sec, contact under 20 ℃ the temperature in junction of two streams m, particulate silver powder is separated out in reduction.The reducing agent that use this moment is for being dissolved in the 21g quinhydrones 3.4 liters of quinhydrones aqueous solution in the pure water.Therefore, the quinhydrones concentration of mixing when finishing is about 3.0g/l, is very thin concentration.
With the particulate silver powder 40g that so obtains similarly to Example 1, use filter to filter, wash, further carry out 70 ℃ * 5 hours drying, thereby obtain particulate silver powder with 100ml water and 600ml methyl alcohol.The scanning electron microscope image of the particulate silver powder that so obtains is shown in Fig. 3.And,, be documented in the table 1 with the powder characteristics of the silver powder that obtains by embodiment 1 and comparative example with the powder characteristics of the particulate silver powder that so obtains.
Comparative example 1
In this comparative example, only changed the wash conditions among the embodiment 1, for fear of repeat specification, only wash conditions is illustrated.
With the particulate silver powder 40g that obtains among the embodiment 1, use filter to filter, wash with the water of 100ml and the methyl alcohol of 50ml, further carry out 70 ℃ * 5 hours drying, thereby obtain particulate silver powder.The scanning electron microscope image of the particulate silver powder that so obtains is same as shown in Figure 2.And,, be documented in the table 1 with the powder characteristics of the silver powder that obtains by other embodiment and comparative example with the powder characteristics of the particulate silver powder that so obtains.
Comparative example 2
In this comparative example, only changed the wash conditions of embodiment 2, for fear of repeat specification, only wash conditions is illustrated.
With the particulate silver powder 40g that obtains among the embodiment 2, use filter to filter, wash with the water of 100ml and the methyl alcohol of 50ml, further carry out 70 ℃ * 5 hours drying, thereby obtain particulate silver powder.The scanning electron microscope image of the particulate silver powder that so obtains is same as shown in Figure 3.And, the powder characteristics of the particulate silver powder that so the obtains powder characteristics with the silver powder that is obtained by other embodiment and comparative example is documented in the table 1.
Comparative example 3
In this comparative example, make particulate silver powder with the manufacture method shown in following, and measured the powder characteristics of resulting particulate silver powder.And, further use particulate silver powder to make elargol, the formation hookup has been measured conductor resistance and sintering begins temperature.
At first, the silver nitrate of 63.3g is dissolved in 1.0 liters the pure water, the preparation silver nitrate aqueous solution adds the ammoniacal liquor that 235ml concentration is 25wt% once in this silver nitrate aqueous solution, obtain the silver ammonia complex aqueous solution by stirring.
This silver ammonia complex solution is joined in the reactive tank, in this reactive tank disposable interpolation as reducing agent, the 21g quinhydrones is dissolved in 1.3 liters of quinhydrones aqueous solution in the pure water, keep 20 ℃ liquid temperature, separate out silver powder by stirring reaction reduction.Quinhydrones concentration when this mixing finishes is about 8.23g/l, is high concentration.
With the particulate silver powder that so obtains similarly to Example 1, use filter to filter, wash, further carry out 70 ℃ * 5 hours drying, thereby obtain particulate silver powder with the water of 100ml and the methyl alcohol of 50ml.The scanning electron microscope image of the particulate silver powder that so obtains is shown among Fig. 4.And, the powder characteristics of the particulate silver powder that so the obtains powder characteristics with the silver powder that is obtained by the foregoing description and comparative example 2 is documented in the table 1.
Comparative example 4
In this comparative example, make particulate silver powder with the manufacture method shown in following, and measured the powder characteristics of resulting particulate silver powder.And, further use particulate silver powder to make elargol, the formation hookup has been measured conductor resistance and sintering begins temperature.
At first, the silver nitrate of 63.3g is dissolved in the 300ml pure water, the preparation silver nitrate aqueous solution, disposable interpolation 235ml concentration is the ammoniacal liquor of 25wt% in this silver nitrate aqueous solution, obtains the silver ammonia complex aqueous solution by stirring.
This silver ammonia complex solution is joined in the reactive tank, disposable putting into is added on the solution of 200ml pure water with the 3g gelatin and as the quinhydrones aqueous solution that the 21g quinhydrones is dissolved in the 700ml pure water of reducing agent in this reactive tank again, keep 20 ℃ liquid temperature, separate out silver powder by the stirring reaction reduction.Quinhydrones concentration when this mixing finishes is about 14.5g/l, is high concentration.
With the particulate silver powder that so obtains similarly to Example 1, use filter to filter, wash, further carry out 70 ℃ * 5 hours drying, thereby obtain particulate silver powder with the water of 100ml and the methyl alcohol of 50ml.The scanning electron microscope image of the silver powder that so obtains is shown among Fig. 5.And, the powder characteristics of the particulate silver powder that so the obtains powder characteristics with the silver powder that is obtained by the foregoing description and comparative example 2 is documented in the table 1.
Comparative example 5
In this comparative example, make particulate silver powder with the manufacture method shown in following, and measured the powder characteristics of resulting particulate silver powder.And, further use particulate silver powder to make elargol, the formation hookup has been measured conductor resistance and sintering begins temperature.
At first, the polyvinylpyrrolidone of dissolving 20g further dissolves the 50g silver nitrate in the 260ml pure water, the preparation silver nitrate aqueous solution, and disposable interpolation 25g nitric acid obtains argentiferous nitrose solution by stirring in this silver nitrate aqueous solution.Ascorbic acid concentrations when this mixing finishes is about 36.0g/l.
On the other hand, as reducing agent the ascorbic acid of 35.8g is added and be dissolved in the 500ml pure water preparation reducing solution.
And, this argentiferous nitrose solution is put into reactive tank, and in this reactive tank the above-mentioned reducing solution of disposable interpolation, keep 25 ℃ liquid temperature, separate out silver powder by stirring reaction reduction.
With the particulate silver powder that so obtains similarly to Example 1, use filter to filter, wash, further carry out 70 ℃ * 5 hours drying, thereby obtain particulate silver powder with the water of 100ml and the methyl alcohol of 50ml.And, the powder characteristics of the particulate silver powder that so the obtains powder characteristics with the silver powder that is obtained by the foregoing description and comparative example is documented in the table 1.
" comparative analysis of embodiment and comparative example "
Compare with reference to table 1 pair the various embodiments described above and comparative example.In addition, by Fig. 2～scanning electron microscope image shown in Figure 5, can know the particle diameter of understanding primary particle.
Table 1
| Test portion | Powder characteristics | The sintering conductor characteristics | |||||||
| SSA m 2/g | Jolt ramming packed density g/cm 3 | D 50 | D IA | D 50/D IA | Crystallite diameter nm | Carbon content % | Conductor resistance μ Ω cm | Sintering begins temperature ℃ | |
| μm | |||||||||
| Embodiment 1 | 2.54 | 4.2 | 0.31 | 0.3. | 1.03 | 7 | 0.15 | 4.6 | 160 |
| Embodiment 2 | 1.68 | 4.7 | 0.55 | 0.49 | 1.12 | 7 | 0.21 | 5.9 | 190 |
| Comparative example 1 | 2.89 | 4.3 | 0.29 | 0.28 | 1.04 | 7 | 0.28 | 8.5 | 160 |
| Comparative example 2 | 0.55 | 4.0 | 3.90 | 2.20 | 1.77 | 7 | 0.32 | 7.9 | 190 |
| Comparative example 3 | 1.18 | 4.3 | 1.78 | 1.02 | 1.75 | 9 | 0.88 | Can't measure | 250 |
| Comparative example 4 | 0.55 | 4.0 | 3.90 | 2.20 | 1.77 | 8 | 0.89 | Can't measure | 250 |
| Comparative example 5 | 0.62 | 4.0 | 3.03 | 1.20 | 2.53 | 38 | 0.30 | Can't measure | 350 |
As can be known clear and definite from table 1, even compare each powder characteristics value, with respect to the silver powder made from manufacture method in the past, the particulate silver powder that obtains with the foregoing description is extremely fine silver powder, dispersed high, impurity content is low, is the particulate silver powder that does not have in silver powder in the past.In addition, about the sintering conductor characteristics, the film density height when using particulate silver powder of the present invention to form circuit, impurity content is few, so resistance is also low.In each comparative example, conductor resistance height as can be known has unmeasured the time.
The possibility of industrial utilization
Particulate silver powder of the present invention can't imagine that by silver powder in the past the fine powder of degree consists of, and the condensation degree of this powder is low, though with the contrast of in the past silver powder, demonstrate very outstanding dispersiveness. In addition, by adopting the manufacture method of particulate silver powder of the present invention, can reduce the organic matter that remains in resulting particulate silver powder, the high film density overlap action that particulate silver powder causes, its result helps to reduce the resistance of resulting conductor.
Claims (8)
1. particulate silver powder, the particulate silver powder that the coherency that this particulate silver powder is powder is low is characterized in that, has the powder characteristics of following a.～c.:
A. the average grain diameter D of the primary particle that obtains of the graphical analysis by the scanning electron microscope image
IABe below the 0.6 μ m;
B. utilize the average grain diameter D of above-mentioned primary particle
IAWith the average grain diameter D that measures according to laser inflection formula particle size distribution at random method
50, use D
50/ D
IAThe condensation degree of expression is below 1.5;
C. the crystallite diameter is below the 10nm;
D. the content of the organic impurities that converts with the carbon amount is below the 0.25wt%.
2. particulate silver powder as claimed in claim 1 is characterized in that, sintering begins temperature below 240 ℃.
3. the manufacture method of a particulate silver powder, make silver nitrate aqueous solution and ammoniacal liquor hybrid reaction obtain the silver ammonia complex aqueous solution, separate out silver particles by in this silver ammonia complex aqueous solution, adding the reducing agent reduction, filter, washing, drying obtains particulate silver powder, it is characterized in that, make the above-mentioned silver ammonia complex aqueous solution contact mixing with organic reducing agent, and silver concentration maintains 1g/l～6g/l in the solution that mixes Hou, the organic reducing agent concentration maintains 1g/l～3g/l and reduces and separate out silver particles, and this silver particles is filtered, washing, use the excess ethyl alcohol solution washing.
4. the manufacture method of particulate silver powder as claimed in claim 3, it is characterized in that, when the above-mentioned silver ammonia complex aqueous solution contacts mixing with organic reducing agent, make the stream (below be referred to as " first stream ") of above-mentioned silver ammonia complex water solution flow through regulation, second stream of interflow in the way of this first stream is set, flow into organic reducing agent by this second stream, contact mixing in the junction of two streams of first stream and second stream.
5. as the manufacture method of claim 3 or 4 described particulate silver powder, it is characterized in that, use silver nitrate concentration as the silver nitrate aqueous solution of 2.6g/l～48g/l and ammoniacal liquor hybrid reaction, silver concentration is the silver ammonia complex aqueous solution of 2～12g/l.
6. as the manufacture method of any described particulate silver powder in the claim 3 to 5, it is characterized in that employed organic reducing agent contains dispersant.
7. as the manufacture method of any described particulate silver powder in the claim 3 to 6, it is characterized in that organic reducing agent uses quinhydrones.
8. as the manufacture method of any described particulate silver powder in the claim 3 to 7, it is characterized in that with respect to resulting 1kg silver particles, the use amount of ethanol is more than the 5L.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP281660/2003 | 2003-07-29 | ||
| JP2003281660A JP4489389B2 (en) | 2003-07-29 | 2003-07-29 | Method for producing fine silver powder |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1826198A true CN1826198A (en) | 2006-08-30 |
| CN100500333C CN100500333C (en) | 2009-06-17 |
Family
ID=34100960
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004800209882A Expired - Fee Related CN100500333C (en) | 2003-07-29 | 2004-07-15 | Fine-grain silver powder and process for producing the same |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US20070079665A1 (en) |
| JP (1) | JP4489389B2 (en) |
| KR (1) | KR101132283B1 (en) |
| CN (1) | CN100500333C (en) |
| CA (1) | CA2534108A1 (en) |
| DE (1) | DE112004001403T5 (en) |
| TW (1) | TW200503961A (en) |
| WO (1) | WO2005009652A1 (en) |
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-
2003
- 2003-07-29 JP JP2003281660A patent/JP4489389B2/en not_active Expired - Lifetime
-
2004
- 2004-06-28 TW TW093118758A patent/TW200503961A/en not_active IP Right Cessation
- 2004-07-15 WO PCT/JP2004/010102 patent/WO2005009652A1/en active Application Filing
- 2004-07-15 CA CA002534108A patent/CA2534108A1/en not_active Abandoned
- 2004-07-15 KR KR1020067001514A patent/KR101132283B1/en not_active IP Right Cessation
- 2004-07-15 CN CNB2004800209882A patent/CN100500333C/en not_active Expired - Fee Related
- 2004-07-15 DE DE112004001403T patent/DE112004001403T5/en not_active Withdrawn
- 2004-07-15 US US10/566,353 patent/US20070079665A1/en not_active Abandoned
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Also Published As
| Publication number | Publication date |
|---|---|
| JP2005048237A (en) | 2005-02-24 |
| KR20060040712A (en) | 2006-05-10 |
| TWI295666B (en) | 2008-04-11 |
| CN100500333C (en) | 2009-06-17 |
| WO2005009652A1 (en) | 2005-02-03 |
| CA2534108A1 (en) | 2005-02-03 |
| JP4489389B2 (en) | 2010-06-23 |
| DE112004001403T5 (en) | 2006-06-29 |
| TW200503961A (en) | 2005-02-01 |
| US20070079665A1 (en) | 2007-04-12 |
| KR101132283B1 (en) | 2012-04-02 |
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