CN1572746A - Glass particle, glass particle aggregation and manufacturing method for glass particle - Google Patents

Abstract

The inventionrelates to easily obtaining glass particles in each of which a metal particle is included in advance so as to avoid the mixing process in an application where glass particles and a metal powder or the like are mixed and used. A method for producing the glass particles comprises a process for coating the surface of each metal particle to be included with an oxide film, a process for preparing a raw material slurry by dispersing the metal particles, each being coated with the oxide film, into a raw material solution containing glass constituent elements, and a process for making the raw material slurry into droplets, then introducing the droplets into a high temperature furnace, and thermally decomposing the droplets.

Description

The manufacture method of glass particle, glass particle aggregate and glass particle

Technical field

The present invention relates to the manufacture method of glass particle, glass particle aggregate and glass particle, more particularly, the manufacture method that belongs to glass particle, glass particle aggregate and the glass particle of particle covered with gold leaf in relating to.

Background technology

All the time, glass material is used to form the grafting material, insulation processing of the low-temperature sintering used additives of ceramic electronic components aspect, pottery or baseplate material, electrode with in the multiple fields such as protective membrane material.For example, in multi-layer ceramic capacitor, the material that has added glass particle is used as sintering aid, or externally mix use as frit (glass frit) in the electrode.In addition, in resistive material, be used to form the insulation resistance part.

Though glass material is when mixing use like this or utilizing its insulation characterisitic to use separately with pottery or metal etc., can be used for a lot of fields, but, glass material in the past mostly be to the structural glass of making of the fusion quench carry out that mechanical disintegration is handled and material.So, following feature is arranged, that is, the particle diameter of the microminiaturization that can reach is limited, and broad particle distribution, and its shape is heterogeneity also, forms many aggregates etc.

When this glass material is used for described purposes, with material mechanically mixing such as pottery or metallic substance, organism and use.In the application of using like this glass material of fusion quench being mixed with other materials, can be because its shape heterogeneity, aggregate is more and produce the problem that is difficult to obtain highdensity homogeneous dispersion state.

At these problems, proposed to have enclosed the technical scheme (for example with reference to patent documentation 2) that has formed the metal-powder of glass film on the glass granules (for example with reference to patent documentation 1) of oxide particle and at least a portion at metal-powder in the inside of glass particle.

[patent documentation 1] spy opens the 2001-302282 communique

[patent documentation 2] spy opens flat 10-330802 communique

But, in the patent documentation 1, owing to need to prepare the operation of glass powder as raw material powder, so operation quantity increases.In addition, enclose glass owing to form oxide compound through the gas phase state that utilizes plasma body to form, therefore can't use can solid solution in glass the metal crystal seed, perhaps can't in covered with gold leafly belong to particle, thereby be necessary to limit the composition of glass.

In addition, in the patent documentation 2, announce utilizing spray heating decomposition to make the metal-powder that covers by glass coating.Specifically, the pyrolytic solution of metal compound that will contain more than a kind or 2 kinds is sprayed, and forms small drop, by under than the higher temperature of the decomposition temperature of metallic compound to this drop heating carrying out thermolysis, precipitating metal powder.At this moment, by in metal compound solution, adding oxide precursor etc. in advance, just can when generate metal-powder, carry out glass and coat.

But, in spray heating decomposition, in the employed material solution, use the mixing solutions or the mixed gel of mineral compound (nitrate, muriate etc.) or organic compound (metal alkoxides alkoxide etc.), gel (silica gel or alumina gel etc.) etc.In general, consider the factor of raw materials cost and production efficiency, at least a portion element that glass constitutes element will use soluble salts such as nitrate or vitriol, acetate, muriate are dissolved in material in the solvent.So, consider stability of solution, be necessary the pH of solution is adjusted into acidity, thereby will use strong acid such as nitric acid or sulfuric acid.During the metallics of bag, metal can be dissolved in the solution in add wanting in this material solution, thereby the composition of the composition that belongs to covered with gold leaf or glass is with to design composition different in causing.

In addition, when in atmosphere, this material solution being sprayed thermolysis, have also that metallics is exposed in the pyritous atmosphere and the problem of oxidation.

Summary of the invention

In view of above problem, the objective of the invention is to, glass powder and metal-powder are being mixed in the application of using the mixed processes of cancellation glass powder and metal-powder.

Other purpose is, is provided at the kind of the metal of interior bag in the glass particle or unqualified, the interior manufacture method of having wrapped glass particle, glass particle aggregate and the glass particle of the metal of wideer compositing range in composition aspect of glass.

And, the present invention also aims to, the manufacture method of following glass particle, glass particle aggregate and glass particle is provided, promptly, even use the material solution of strong acid such as nitric acid or sulfuric acid as spray heating decomposition, metallics can be not dissolved yet, even contact with atmosphere when the spraying thermolysis, can prevent oxidized yet.

The present invention adopts following formation in order to reach described purpose.

That is, the feature of glass particle of the present invention is, is the interior glass particle that wraps metallics, and the surperficial oxide film of described metallics covers.

Described oxide film preferably contains the formation element of described glass particle.

Described oxide film preferably contains in the middle of silicon oxide, boron oxide and the phosphorus oxide any at least a kind.

The particle diameter of described glass particle is preferably by more than 2 times below 200,000 times of the particle diameter of the described metallics of interior bag.

In addition, the feature of glass particle of the present invention is, a plurality of described metallicss under dispersed state by interior bag.

In addition, the feature of glass particle of the present invention is, has the stacked laterally a plurality of glass coatings that are made of the different glass composition from the center of described glass particle and the multi-ply construction that forms.

In addition, glass particle aggregate of the present invention is the glass particle aggregate that described glass particle set forms, and it is characterized in that median size is below 10 μ m more than the 0.01 μ m.

In addition, the feature of the manufacture method of glass particle of the present invention is, be interior manufacture method of having wrapped the glass particle of metallics, this manufacture method comprises covering to mix by the operation on the surface of the described metallics of interior bag, in the solution of the formation element that contains glass by oxide film with oxide film and has covered the described metallics on surface and make the operation of raw material slip, described raw material slip is formed drop and import pyritous body of heater inside and carry out the pyrolysated operation.

Described pyrolysated temperature preferably is higher than the second-order transition temperature of described glass.

In addition, the feature of the manufacture method of glass particle of the present invention is, comprises that also glass particle with gained is blended in the solution that contains the glass ingredient different with described glass particle and makes the operation of raw material slip, the described raw material slip of made is formed drop and imports pyritous body of heater inside and carry out the pyrolysated operation.

If use glass particle of the present invention, because when making glass particle be dispersed in the solvent, glass particle has suppressed moving of metallics, thereby can prevent the cohesion of metallics, thereby can produce glass particle and metallics dispersive slip equably.

In addition, if adopt the manufacture method of glass particle of the present invention, just do not need to prepare the more operation of the raw material powder separately, mixing, fusion, pulverizing and so on of glass powder and metal-powder, thereby can be with less operation high-level efficiency and the glass particle of metallics has been provided in providing in advance at low cost.And, can also be provided at hard-core changeful glass particle or glass particle aggregate on the composition of the kind of metallics and glass particle.

Description of drawings

Fig. 1 is the skeleton diagram of expression manufacturing process of an example of the manufacture method that belongs to glass particle covered with gold leaf in of the present invention.

Fig. 2 has carried out the nickel particles that silica-coated is handled.

Fig. 3 is the spraying apparatus for thermal analysis that uses among the present invention.

Fig. 4 is the of the present invention interior XRD figure that belongs to the glass particle aggregate covered with gold leaf of making under the condition of embodiment 1.

Fig. 5 is the XRD figure of glass particle aggregate in the past.

Fig. 6 is the of the present invention interior XRD figure that belongs to the glass particle aggregate covered with gold leaf of making under the condition of embodiment 2～4.

Fig. 7 is the TG-DTA figure that belongs to the glass particle aggregate of the present invention interior covered with gold leaf that makes under the condition of embodiment 1.

Fig. 8 is the TG-DTA figure of glass particle aggregate in the past.

Fig. 9 is 2 electronic images and the reflected electron image of the SEM photo that belongs to glass particle covered with gold leaf in make under the condition of expression embodiment 1 of the present invention.

Figure 10 is 2 electronic images and a reflected electron image of representing the SEM photo of glass particle in the past.

Figure 11 is 2 electronic images and the reflected electron image of the SEM photo that belongs to glass particle covered with gold leaf in make under the condition of expression embodiment 2 of the present invention.

Figure 12 is the of the present invention interior TEM photo and the EDX point of observation that belongs to glass particle covered with gold leaf of making under the condition of expression embodiment 2.

Figure 13 is the EDX figure of TEM photo integral body shown in Figure 12.

Figure 14 is the EDX figure of the EDX measuring point 1 among Figure 12.

Figure 15 is the EDX figure of the EDX measuring point 2 among Figure 12.

Among the figure, the production process of 1-metallics, 2-apply the operation of oxide film, the operation of 3-making spray solution, the blending dispersion treatment process of 4-solution, 6-spraying pyrolosis operation

Embodiment

Below embodiments of the present invention are described in detail.

Glass particle of the present invention is the interior glass particle (hereinafter referred to as " the interior glass particle that belongs to covered with gold leaf ") that belongs to particle covered with gold leaf.In addition, so-called glass particle aggregate of the present invention is meant a plurality of described interior materials that the glass particle set forms that belong to covered with gold leaf, specifically, and the expression glass powder.

As the formation element of the glass of glass particle, can comprise any one element at least of Si, B, P, Li, Na, K, Mg, Ca, Ti, Cu, Al, Ba, Zn, Ga, Ge, Pb, Bi.Specifically, preferably include in silicon oxide, boron oxide and the phosphorus oxide as network forming oxide any at least a kind.Glass particle both can only be made of noncrystal glass so long as have second-order transition temperature and the material of glass transition temperature, also can comprise crystal glass.In addition, also can be included in the sintered glass ceramics of crystallization when glass particle heated.

Though the particle diameter of glass particle is as long as the interior particle that belongs to covered with gold leaf just has no particular limits preferred 0.1 μ m～1000 μ m in practicality.When the particle diameter of glass particle is too small, for example when utilizing spray heating decomposition described later to make glass particle, just is necessary to slow down the feed speed of raw material slip etc., thereby can causes production efficiency to reduce.On the other hand, when the particle diameter of glass particle is excessive, in the formation of glass particle, can spend the more time, perhaps need large-scale device.

In addition, the particle diameter of glass particle is preferably more than 2 times below 200,000 times of particle diameter of metallics.When the particle diameter of glass particle the particle diameter of metallics more than 2 times the time, the particle that belongs to covered with gold leaf in just being easy to.In addition, because the amount of glass particle is many with respect to the relative change of metallics, so glass particle is strengthened as the effect of wedding agent, joint compound.Therefore, if use the more relatively glass particle that belongs to interior covered with gold leaf of amount of glass like this, then do not need to add in addition wedding agent, joint compounds such as frit.And the upper limit below 200,000 times is to derive from the usage range of the particle diameter of the usage range of the particle diameter of the glass particle that has illustrated and metallics described later.

In addition, though the shape of glass particle is preferably spherical, also can be approximate spherical, so long as the shape that the purposes as purpose is not counteracted gets final product.

In addition, glass particle also can have the multi-ply construction of the stacked laterally a plurality of glass coatings that are made of the different glass composition from the center of described glass particle.Here said " different glass composition " not only means the element difference that constitutes glass." different glass composition " is meant, even it is identical to constitute the element of glass, second-order transition temperature, glass transition temperature or melt temperature etc. are also different as the characteristic of glass.So when the glass particle that will have this multi-ply construction was cut into disk, otch will be as the annual ring of tree, as so-called Baumkuhen, therefrom the mind-set outside forms the different layer of a plurality of characteristics.

By adopting this kind multi-ply construction, for example just can make the characteristic graded at the outside and the central part of glass particle, therefore just can obtain following characteristic, that is, the glass ingredient in the outside is softening at low temperatures, and the glass ingredient of central part can not reach a high temperature.

By forming the glass particle that belongs to interior covered with gold leaf that this kind has multi-ply construction, glass ingredient with different thermal propertys is existed as a particle, by in glass ingredient, selecting suitable material, just can at random design second-order transition temperature or various characteristicses such as crystallized temperature, melt temperature.

The number of plies of glass coating will suitably be selected according to purpose.In addition, the glass of each glass coating is formed will suitably select to meet the composition of its characteristic according to employed purposes such as sintering aid or mashed prod, thereby is not what be specially limited.

As metallics, as long as in the middle of metals such as Cu, Ni, Ag, Pt, Au, Pd, Al, contain more than a kind.In addition, can also use monometallic composition or contain the alloy of many metal ingredients, the mixture of mixture, monometallic and alloy between the monometallic composition or the mixture between the alloy.In ceramic electronic components such as multi-layer ceramic capacitor, owing to use monometallic nickel or copper as electrode materials more, so metallics is preferably nickel, copper or nickelalloy, copper alloy.

Though metallics preferably fully is included in the inside of glass particle, its part also can reveal from the surface of glass particle.In this manual, the connotation of " interior bag " part that also comprises metallics like this situation about revealing from the surface of glass particle.

Metallics has oxide film on the surface.Like this, even for example when in the solvent that glass particle is blended in strong acid, metallics can not dissolve yet, and can stably exist.Oxide film also can contain nitride or carbide.In addition, oxide film preferably is made of the material that the glass ingredient with glass particle has an intermiscibility, more preferably contains the formation element of glass particle.By forming this kind oxide film, just can obtain to form the irrelevant glass particle that belongs to changeful interior covered with gold leaf with the kind or the glass of metal.

The particle diameter of metallics is preferred 5nm～100 μ m in practicality.When the particle diameter of metallics was too small, being manufactured on of metallics technically will become very difficult.On the other hand, when the particle diameter of metallics was excessive, the interior weight that belongs to glass particle covered with gold leaf increased, and is easy to sedimentation in the time of in being mixed into solvent, thereby dispersed the reduction.

In addition, also can be under the state that makes after a plurality of metallicss disperse be wrapped in the glass particle in it.This kind structure is for example very effective when making a lot of metallicss be dispersed in the solvent.

In addition, the interior glass particle that belongs to covered with gold leaf can be used as the aggregate use.Specifically, each particle is represented by the glass powder that glass particle forms etc. that belongs to covered with gold leaf in of the present invention.

Though should in the glass particle that belongs to covered with gold leaf be used alone also and can have identical characteristic, also can with have a different qualities interior covered with gold leafly belong to that glass particle mix and as the aggregate use of glass particle.

Should can use with various forms by the interior glass particle aggregate that belongs to covered with gold leaf.For example, can use with forms such as film, block molding, thin slice, mashed prod.

In addition, the interior median size that belongs to the glass particle aggregate covered with gold leaf is preferably in the following scope of the above 10 μ m of 0.01 μ m.In order to obtain to have interior covered with gold leaf the belong to glass particle aggregate of median size less than the particle diameter of 0.01 μ m, need to reduce strength of solution, adopt electrostatic spray or ultrasonic atomization method etc. can form the atomising method of small drop, therefore, the formation efficiency variation of particle is arranged, production efficiency is produced dysgenic situation.On the other hand, when median size surpasses 10 μ m, will to the mixing or printing or surface smoothing generation detrimentally affect when using of pottery as mashed prod.

So, in the application that internally production efficiency that belongs to glass particle covered with gold leaf or printing, surface smoothing do not exert an influence, also can be outside this average particle size range.Here said median size is the mean value of the particle dia of being tried to achieve by the particle picture that the viewing tool that utilizes scanning electronic microscope etc. can observe particle shape obtains.

To narrate the manufacture method that belongs to glass particle interior covered with gold leaf below, simultaneously bag glass metal particle in of the present invention will be described in detail as an embodiment of the invention.

Fig. 1 is the skeleton diagram of the operation of expression an embodiment of the invention the interior covered with gold leaf manufacture method that belongs to glass particle.

The manufacture method that belongs to glass particle interior covered with gold leaf of this embodiment has: the operation 1 that is wrapped in the metallics in the glass particle in the making, operation 2 with the surface of oxide film metallizing, making contains the operation 3 of spray solution of the formation element of glass, in this spray solution the metallics that has applied oxide film being carried out blending dispersion handles and the operation 4 of making raw material slip, this raw material slip is made small droplet profile to import in the already heated body of heater, by being used to radiant heat from body of heater with the thermolysis of raw material slip, chilling obtains the interior spraying pyrolosis operation 6 that belongs to glass particle 5 covered with gold leaf then.

Spray heating decomposition is the method that is suitable for making the globular glass particle, be that the solution of formation element that can be by will containing glass is made small droplet profile and imported in the already heated body of heater, be used to radiant heat from body of heater with the material solution thermolysis, chilling obtains the method as the glass particle of object then.

But, material solution as spray heating decomposition, the general element that the soluble salt of nitrate or vitriol, acetate, muriate etc. is constituted at least a portion of element as glass that uses is dissolved in solution in the solvent, therefore, consider stability of solution, be necessary the pH value of solution is adjusted into acidity, thereby need to use strong acid such as nitric acid or sulfuric acid.

So when being wrapped in the metallics in the glass particle in add to mix wanting in this material solution, metal will dissolve, thereby the problem that changes of the composition of the contact part of metallic surface and glass.In addition, when in atmosphere this material solution being sprayed thermolysis, the particle of metal is exposed in the pyritous atmosphere, thereby also can produce the problem of oxidation.

Consider this problem,, the operation that modification is carried out on the surface that internally is wrapped in the metallics in the glass particle is set as this embodiment.That is, preferably the dissolubility resistent of acid and/or the oxide film of scale resistance are carried out modification to the surface of metallics with having.

The producing device that uses in the embodiments of the present invention, the thermal decomposer of promptly spraying can use known device, and the Heating temperature of body of heater or particle transfer rate, spray method or spray condition can suitably be selected according to the kind of spraying material solution, the composition or the characteristic of glass.By using spray heating decomposition like this, just can be through use glass powder monomer as the conventional art and metal-powder monomer as raw material, carry out the operation of the pulverizing of raw material or mixing and so on, and the glass particle that belongs to covered with gold leaf in can directly forming from the raw material slip that glass solution, has disperseed metallics, the glass particle that belongs to covered with gold leaf in therefore just can obtaining in short time with low cost.

In addition, because the formation element that belongs to glass particle covered with gold leaf mixes in making with the slip state, the composition that therefore also has a glass particle is the feature of homogeneous more.In this kind spray heating decomposition, as long as can supply with the heat that makes the slip thermolysis and produce particle, not only can be used to radiant heat heating from body of heater, can also adopt the known heating means such as direct-fired method of utilizing flame.

The Heating temperature of the raw material slip in this spray heating decomposition needs the second-order transition temperature that likens to purpose higher at least, more preferably, by being set at the temperature more than the glass melting temperature, just can easily make glass particle.

In addition, general in the making of glass, carry out the chilling of melten glass, utilization has used the high temperature gas phase field of thermal plasma to carry out the synthetic of glass particle, the chilling that also will carry out glass particle is with the supply of gas etc., but utilizes in the method for the present invention, because very steep to the thermograde of the transport path of retrieving arrangement from carrying out the pyrolysated body of heater, therefore there is no need to carry out especially the supply of chilling, and can come easily synthetic by the transfer rate of regulating glass particle with gas.Certainly, form, need the gradient steeper sometimes, thereby just need the cooling ways such as supply of cooling gas, but be to use this cooling way also to be fine than design temperature gradient according to glass.

Though the atomising method of raw material slip can use two-fluid spray nozzle spray method or known method such as ultrasonic atomization method, electrostatic spray method, but consider production efficiency and the metallics of spray solution and suspension is atomized equably, preferably use the two-fluid spray nozzle spray method as the method that atomizes.

The particle diameter of making that belongs to glass particle interior covered with gold leaf can obtain the particle diameter as purpose by concentration, the atomization condition of adjusting the raw material slip.That is, when using the two-fluid spray nozzle spray method,, increase spraying and use the flow of gas to get final product if the particle diameter of genus glass particle covered with gold leaf in dwindling as long as reduce the concentration of raw material slip, and slows down the feed speed of the raw material slip of supplying with to nozzle.In addition, on the contrary, when gold filled belongs to the particle diameter of glass particle in will increasing, if the concentration of increase raw material slip, and quickening reduces spraying and uses the flow of gas to get final product to the feed speed of the raw material slip of nozzle supply.

In any case, as long as the size of the raw material slip of this droplet-like is reached make metallics by in be wrapped in the size of state of the inside of glass particle, for this reason, the getting final product more than 2 times of the particle diameter of the metallics of bag in the quilt that the size of the raw material slip of droplet-like is reached for example add in the raw material slip is wrapped in the state of the inside of glass particle in metallics promptly becomes.

Owing to can like this raw material slip be formed in the stage of droplet, the particle diameter of making of spray heating decomposition that belongs to glass particle interior covered with gold leaf is adjusted, therefore just need not be pulverized after synthetic or aftertreatment such as screening for the particle diameter that belongs to glass particle covered with gold leaf in controlling.Thereby just can utilize less operation to obtain the interior glass particle that belongs to covered with gold leaf with high-level efficiency.Certainly, this will be according to purpose, is not will limit to pulverize or processing such as screening.

In addition, utilize the interior glass particle that belongs to covered with gold leaf of spray heating decomposition synthetic to reclaim by retrieving arrangements such as strainers.For this recovery method also without limits.

In addition, feature of the present invention is, use has mixed the raw material slip of particle of the metal of interior bag in the solution of the formation element that contains glass particle, and it is characterized in that, import pyritous body of heater inside and make it thermolysis manufacturing by the material behind the state that this raw material slip is formed drop.

So, utilizing described method to form the inside of vaporific drop, existed with the dispersive state by the metallics of interior bag, thereby, if in advance with in the raw material slip in the bag metallics be adjusted to required particle diameter and concentration, then do not need to implement annealing and wait thermal treatment that metal is separated out, the glass particle that belongs to covered with gold leaf in just can obtaining.In addition, even in the reactions such as volumetric shrinkage that the thermolysis because of the raw material slip causes, owing to do not changed by the particle diameter of the metallics of interior bag and concentration, therefore just can be implemented in the interior bag of the inside of glass particle, make it the particle diameter and the concentration that reach required.

Here, what is called is meant volumetric concentration by the concentration of the metallics of interior bag.

Among the present invention, such as described to the metallics of the interior bag usefulness that suspends in the described raw material slip, carried out the surface modification that its surface is covered with the oxide film of the formation element that contains glass.By carrying out the surface modification of this dissolubility resistent, even the particle suspension of the metal of bag can not be dissolved in the strong acid solvent yet, thereby can make it stably to exist in the raw material slip in wanting.

In addition, preferably like this, gold filled belongs in the manufacture method of glass particle in of the present invention, the operation that the metallic surface of utilization bag in wanting forms oxide film invests dissolubility resistent, like this, just can not cause restriction in itself to the kind of the metal of bag in wanting or the characteristic of metals such as shape, particle diameter, can also in the metal of formation element of bag glass.

Oxide film as the formation element of the glass that contains glass particle, though can use the silicon oxide that constitutes element as the net structure of glass suitably, but, so long as have material to the dissolubility resistent of acidic solution, just have no particular limits, also can contain nitride, carbide etc.The formation method of oxide compound that contains the formation element of this glass can be utilized the hydrolysis of metal alkoxides alkoxide and easily obtain.To narrate an example of the formation method of concrete surface modification oxide compound below.

At first, weigh the metallics of bag in the wanting of aequum exactly, make it to be dispersed in the non-aqueous solvent such as ethanol.Weigh the metal alkoxides alkoxide such as tetraethyl orthosilicate as the raw material of surface modification material of the amount that reaches required coating thickness exactly, and add in this non-aqueous solvent that has disperseed metallics, carry out dispersion treatment.

Then, adding in non-aqueous solvents such as ethanol can be with the water of the amount of the abundant hydrolysis of tetraethyl orthosilicate.Then, in the solution that has disperseed metal and metal alkoxides alkoxide,,, form the surface modification oxide compound on the surface of metallics Yi Bian the hydrolysis solution that drips and added water makes the metal alkoxides hydrolysis of alkoxide Yi Bian carry out dispersion treatment.

This kind method is an example of the formation method of surface modification oxide compound, certainly, also can use other the method that forms the surface modification oxide compound on the surface of metallics.The formation method of this surface modification oxide compound also can be used as the CVD method of the cladding process in the gas phase or sputtering method, other liquid phase method.

The feature of this method is, by like this modification being carried out on the surface of wanting the interior metallics that wraps, form oxide film, the oxidizing reaction that belongs to interior covered with gold leaf that produces in the time of just can being suppressed at the thermolysis of raw material slip, therefore the atmosphere in the time of just can adopting air atmosphere as the spraying thermolysis need not used special adjustment such as reducing atmosphere for the oxidation that suppresses metal.So,, and under the situation of the mixture of use organometallic compound or gel mixture, preferably also carry out this surface modification even in the raw material slip, do not use acidic solution.

And, though the formation element of the acidic solution of the genus glass particle interior covered with gold leaf that use acidic solution and organometallic compound etc. make as raw material slip of the present invention and organometallic compound etc., for example nitrogen or carbon might have residual from several ppm to the following degree of 1.0wt%, but, can residual quantity suitably be adjusted according to the purposes of using glass particle of the present invention.

By the glass particle of making like that as described that belongs to interior covered with gold leaf is suspended in the raw material slip that contains the glass ingredient with different qualities, utilize required spray pattern to form small drop, and make it thermolysis, make the glass ingredient of raw material slip be formed at the surface that belongs to glass particle interior covered with gold leaf of suspension, just can obtain to have with interior genus glass particle covered with gold leaf and be nuclear, covered the glass particle of the structure on its surface with other glass ingredient.

In addition, by having the manufacturing process that belongs to glass particle interior covered with gold leaf of this structure repeatedly, just can make the multi-ply construction more than at least 2 layers, thereby can more critically control each characteristic.For example, use the raw material slip that contains glass ingredient with fusing point lower than the fusing point of this glass composition, identical when belonging to glass particle with the interior gold filled of making, utilize spray heating decomposition, just can make interior gold filled genus glass particle.

[embodiment]

To describe detailed content of the present invention based on embodiment below.

(embodiment 1)

The interior making that belongs to covered with gold leaf

The method of evaporation of utilization in gas made the nickel particles as the metallics of bag in wanting.Helium-atmosphere air pressure is being adjusted in the reactor of 6.65kPa, in the magnesium oxide crucible, is adding nickel ingot 80g, utilizing the induction heating of the faradic ruhmkorff coil that has applied 54A, be heated to about 1800 ℃, making it evaporation.In the helium flow of supplying with the speed of 4 liters of per minutes,, utilize strainer to reclaim with the nickel cooling of evaporation.The specific surface area diameter of the nickel particles aggregate of making is 30nm.

Accessory covered with gold leaf has the oxide-coated thing ethanolic soln of dissolubility resistent in being used for making, add the nickel particles aggregate that utilizes described method to make, and add the tetraethyl orthosilicate (TEOS) of the amount of the silicon oxide film can form thick 2nm, 6nm, 8nm on the surface of nickel particles aggregate, utilize ultrasonic dispersing machine to carry out 30 minutes dispersion treatment.Then, in ethanol, add the water of the amount of the ammonia of 5 times amount of TEOS and 10 times, carried out sufficient stir process.Then,, in the ethanolic soln that has added nickel particles aggregate and TEOS, drip and mixed the ethanolic soln of ammonia and water, carry out the hydrolysis reaction of TEOS with the speed of per second 1cc.After this hydrolysis, utilize and filter the nickel particles aggregate and the separated from solvent that will form silicon oxide film, and then add ethanol, by carrying out ultrasonic cleaning, removed unreacted TEOS, ammonia., carry out vacuum-drying, formed the nickel particles aggregate of the silicon oxide film of 2nm, 6nm, 8nm respectively thereafter.

Fig. 2 represents with the observed result who utilizes the nickel particles aggregate of this hydrolysis treatment making of transmission electron microscope (TEM).

The thickness of the silicon oxide film on surface is 2nm, 6nm, the 8nm identical with design, formation shown in Fig. 2 (a) in the nickel particles aggregate of silicon oxide film of 2nm, the surface of silicon oxide film concavo-convex bigger, do not form homogeneous thickness, but the formation among Fig. 2 (b), (c) shown in respectively in the nickel particles aggregate of silicon oxide film of 6nm, 8nm, its surface does not have concavo-convex, has the thickness of homogeneous on the particle all surfaces.

Then, this nickel particles aggregate that has formed silicon oxide film is added in the nitrose spraying material solution that is adjusted to pH2, utilize the nickel ion detector to confirm dissolved state, found that, the silicon oxide thickness is that the nickel particles aggregate of 2nm after back 30 minutes, has detected nickel ion in input.But, even the silicon oxide thickness be each nickel particles aggregate of 6nm and 8nm after dropping into 16 hours, do not detect nickel ion yet, demonstrate enough functions that invests the dissolubility resistent of acidic solution.Its result shows that the thickness of formed silicon oxide film is preferably in more than the 5nm on the nickel particles aggregate, and when carrying out synthesizing for a long time, the dissolubility resistent material that is attached to the nickel particles surface must form silicon oxide film at the particle all surfaces.

And, as a comparative example, the nickel particles aggregate that does not form oxide film on the surface is added in the nitrose spraying material solution that is adjusted to pH2, utilize the nickel particles detector to confirm dissolved state, found that, after dropping into 5 minutes, produce bubble, dissolve the nickel ion of 25ppm.In addition, after the input through 16 hours state under, the nickel particles aggregate dissolves fully.

The making of raw material slip

As the starting raw material in the acidic solution, weighing silica gel (particle diameter＜5nm), boric acid, barium carbonate, Quilonum Retard exactly respectively, they are converted in oxide compound reach 28: 21: 43: 8 ratio, add in the beaker, to wherein adding water, make oxide concentration reach 4wt%, each is constituted the element dissolving, obtained spraying material solution A.

Then, weighing has formed the nickel particles aggregate of silicon oxide film according to the thickness of 8nm, the feasible conversion with metallic nickel reaches the concentration of 1.2vol%, and in water, carried out 30 minutes ultrasonic dispersing, it is added among the spraying material solution A, adjust in the mode that the oxide compound conversion reaches 2.5wt% according to the concentration that makes integral body, and stir fully, obtained being dispersed with the raw material slip B of nickel particles aggregate.This raw material slip B was stirred 2 hours, measured the nickel ion concentration in the solution, but do not detect nickel ion.

At this moment, the concentration 1.2vol% of metallic nickel is under the situation of the glass particle of anticipation particle diameter 1 μ m, has approximately disperseed the concentration of the nickel particles of 100 particle diameter 30m.In addition, be to be under the situation of 5 μ m as the 2.5wt% of the concentration of raw material slip B at the particle diameter that makes raw material slip B form vaporific back drop, obtain the concentration of the glass particle of 1 μ m.

The making that belongs to glass particle interior covered with gold leaf that utilizes spray heating decomposition to carry out

Fig. 3 represents the interior spraying thermal decomposer that uses in the manufacture method of glass particle that belongs to covered with gold leaf of the present invention.This spraying thermal decomposer is a known device as implied above.

In the temperature of utilizing electric heater with body of heater portion is adjusted to 900 ℃ the erect type spraying thermal decomposition furnace of radiant heat type of heating, with described raw material slip B utilize speed that feedstock pump divides with 10mL/, with 2kgf/cm ²The air of pressure supply with to two-fluid spray nozzle respectively with the flow that 20L/ divides, the drop of making is imported in the body of heater, make it to take place pyrolysis.And, in the furnace core tube of internal diameter 200mm, long 1000mm, heated length 1000mm, carry out with delivering gas flow 35L/min, atomization quantity 100mL/h, in 8.6 seconds residence times, made it to take place pyrolysis.The spraying atmosphere of this moment is air.And, here, thermal treatment such as anneal.Interior covered with gold leaf belong in the glass particle aggregate imports the product collector with bag filter by air-flow the recoverer of utilizing that this pyrolysis makes and being recovered.

(embodiment 2～4)

Use making method that belongs to interior covered with gold leaf and the order shown in the embodiment 1, in will making the reactor that atmosphere pressures is adjusted to 1.13kPa, the nickel ingot is evaporated, obtained the nickel particles aggregate of specific surface area diameter 15nm.On this nickel particles aggregate, use the oxide-coated method shown in the embodiment 1, obtained having formed the nickel particles aggregate of the silicon oxide film of 8nm on the nickel particles surface.

Weighing has formed the nickel particles aggregate of this silicon oxide film, make it to convert with metallic nickel in the spraying material solution A shown in the embodiment 1, reach 1.2,2.4, the concentration of 3.6vol%, with its ultrasonic dispersing after 30 minutes in water, add among the spraying material solution A, adjust in the mode that the oxide compound conversion reaches 2.5wt% according to making whole concentration, stir fully, obtained making metallic nickel particle assembly body to disperse the raw material slip that forms.

To the thermolysis of under the condition identical, spraying of this raw material slip that contains the metallic nickel particle, obtained the glass particle that belongs to interior covered with gold leaf of embodiment 2～4 with embodiment 1.

(comparative example 1)

In order to compare with the interior characteristic that belongs to glass particle covered with gold leaf, according to described identical condition, sequentially built use the glass particle aggregate of not nickeliferous spraying material solution A.

Use X-ray diffraction (XRD) that the crystalline form that belongs to the glass particle aggregate of glass particle aggregate and comparative example 1 interior covered with gold leaf of making among the embodiment 1 is measured, found that, in interior covered with gold leaf the genus in the glass particle aggregate, as shown in Figure 4, observed the peak that produces because of metallic nickel, also have near the broad peak 20 °～40 ° that see in the not nickeliferous glass particle aggregate shown in Figure 5, the nickel of bag exists with metallic state in illustrating, and glass ingredient forms glass particle.

In addition, according to change shown in Figure 6 the XRD figure that belongs to the glass particle aggregate interior covered with gold leaf of making among the embodiment 2～4 of metallic nickel concentration, along with the metallic nickel concentration in the raw material slip uprises gradually, the peak that produces because of metallic nickel on the XRD figure also becomes big gradually, and explanation can utilize the amount that is blended in the metallics in the raw material slip to control the interior amount of metal that belongs in the glass particle aggregate covered with gold leaf.And, among Fig. 6, also show comparative example 1 simultaneously.

The guide look situation of each characteristic of expression embodiment 1～4 and comparative example 1 in the table 1.

Table 1

	Nickel shot footpath (nm)	Nickel concentration (vol%)	The nickel peak	Nickel peak intensity (cps)	Second-order transition temperature (℃)	Crystallized temperature (℃)	Temperature of fusion (℃)	Particle diameter (μ m)
									Comparative example 1	??-	??0	Do not have	??0	??455	??621	??883	??0.44
Embodiment 1	??30	??1.2	Have	??424	??456	??617	??883	??0.48
									Embodiment 2	??15	??1.2	Have	??50	??460	??623	??863	??0.52
Embodiment 3	??15	??2.4	Have	??130	??461	??617	??867	??0.43
									Embodiment 4	??15	??3.6	Have	??205	??463	??615	??874	??0.42

In addition, utilize differential thermal analysis balance (TG-DTA) that the glass performance of the glass particle aggregate of making in embodiment 1 and the comparative example 1 is estimated.Its result for two samples, has confirmed to follow glass transition, vitrifying, fusing and the peak that produces, even interior nickel coat also demonstrates and the equal characteristic of glass particle aggregate that does not contain nickel respectively as shown in Figures 7 and 8 under uniform temp.

In addition, can find from described table 1, the glass particle aggregate that belongs to glass particle aggregate and comparative example 1 interior covered with gold leaf that changes the metallic nickel concentration in the raw material slip and make has equal glass performance, even increase the metallic nickel concentration in the raw material slip, in the glass particle aggregate, also do not demonstrate tangible influence.So explanation can utilize the glass of raw material slip to form the characteristic as the glass particle of one of effect of the glass particle of making according to method of the present invention is controlled.

Utilize scanning electron microscope, the glass particle of embodiment 1, comparative example 1 and embodiment 2 is observed.Its result is illustrated respectively among Fig. 9, Figure 10, Figure 11.And, in each figure, (a) expression secondary electron image, (b) the SEM photo of expression reflected electron image.

The result who utilizes this scanning electron microscope that particle shape and median size are estimated is, as shown in Figure 9, the interior glass particle that has wrapped nickel have and shown in Figure 10 in the identical spherical shapes of glass particle of bag.In addition, its median size is, interior covered with gold leaf to belong to glass particle be 0.48 μ m, in the glass particle of bag be not 0.44 μ m, the two is in peer-level.In addition, the median size as the interior nickel that belongs to covered with gold leaf is 15nm.

In addition, as can be seen from Table 1, the particle diameter of the genus glass particle interior covered with gold leaf that changes the metallic nickel concentration in the raw material slip and make and the glass particle of comparative example 1 are equal size, even increase the concentration of the metallic nickel in the raw material slip, particle diameter for glass particle does not demonstrate tangible influence yet, and the glass ingredient concentration that explanation can utilize the raw material slip is controlled the particle diameter as the glass particle of one of effect of the glass particle of making according to method of the present invention.

In addition, in using the observation of scanning electron microscope, when Fig. 9 and Figure 10 are compared, as shown in figure 10, the sample of interior nickel coat is not seen tangible contrast in 2 electronic images and reflected electron image, and in contrast, as shown in Figure 9, the glass particle of the interior nickel coat of making among the embodiment 1 can be observed the tangible contrast of the existence of expression metal in reflected electron image, illustrate that nickel exists with metallic state in glass particle.

In addition, as shown in figure 11, according to 2 electronic images that in material solution A, mixed the sample of making under the state of the embodiment 2 that obtains than the littler nickel particles of embodiment 1 particle diameter with same concentrations, compare with Fig. 9, tangible contrast big or small less of the existence of expression metal, the less nickel particles of bag particle diameter in showing, explanation can utilize the particle diameter of blended nickel particles in the raw material slip, to controlling as the particle diameter that is wrapped in the nickel in the glass particle in one of effect of the glass particle of making according to method of the present invention.

Use transmission electron microscope (TEM) and energy dispersion type X-ray microanalysis instrument (EDX), the interior composition of particle that belongs to the glass particle aggregate internally covered with gold leaf is estimated.Figure 12 represents the TEM image of the sample made under the condition of embodiment 3 and the measuring point of EDX.In addition, Figure 13 represents the EDX figure of whole field of view.

As shown in figure 13,, detect, illustrate and contain metal ingredient in the glass particle by as the silicon of the main composition element of glass, peak that barium produces with as the peak of the interior nickel that belongs to covered with gold leaf in observed interior covered with gold leaf the genus in the glass particle aggregate.In addition, the peak of the copper among Figure 13 is the peak of tem observation net.

Figure 14 and Figure 15 are illustrated respectively in the position of measuring point 1 and measuring point 2, to the result of the detailed compositional analysis of the particle inside of genus glass particle covered with gold leaf in this.At measuring point 1, as shown in figure 14, can confirm to contain nickel and,, as shown in figure 15, can confirm not contain nickel, and have as the silicon of the main component of glass particle and the peak of barium at measuring point 2 as the silicon of the main component of glass particle and the peak of barium.According to this result, the glass particle that belongs to interior covered with gold leaf of made is in a particle, and glass is to be present in the particle with the isolating state of metallic nickel.That is, explanation is the glass particle that is wrapped in the metallic nickel quilt in the glass particle.

The present invention is very useful as the middle glass materials that use such as manufacturing of electronic unit.

Claims (12)

1. a glass particle is characterized in that, is the interior glass particle that wraps metallics, and the surperficial oxide film of described metallics covers.

2. glass particle according to claim 1 is characterized in that, described oxide film contains the formation element of described glass particle.

3. glass particle according to claim 1 is characterized in that, described oxide film contains in the middle of silicon oxide, boron oxide and the phosphorus oxide any at least a kind.

4. glass particle according to claim 1 is characterized in that, the particle diameter of described glass particle is by more than 2 times below 200,000 times of the particle diameter of the described metallics of interior bag.

5. glass particle according to claim 1 is characterized in that, a plurality of described metallicss under dispersed state by interior bag.

6. glass particle according to claim 1 is characterized in that, described glass particle has the stacked laterally a plurality of glass coatings that are made of the different glass composition from the center of described glass particle and the multi-ply construction that forms.

7. a glass particle aggregate is characterized in that, is the glass particle aggregate that the described glass particle set of claim 1 forms, and median size is below 10 μ m more than the 0.01 μ m.

8. a glass particle aggregate is characterized in that, is the glass particle aggregate that the described glass particle set of claim 5 forms, and median size is below 10 μ m more than the 0.01 μ m.

9. a glass particle aggregate is characterized in that, is the glass particle aggregate that the described glass particle set of claim 6 forms, and median size is below 10 μ m more than the 0.01 μ m.

10. the manufacture method of a glass particle, it is characterized in that, be interior manufacture method of having wrapped the glass particle of metallics, this method comprises covering to mix by the operation on the surface of the described metallics of interior bag, in the solution of the formation element that contains glass by oxide film with oxide film and has covered the described metallics on surface and make the operation of raw material slip, described raw material slip is made drop and import pyritous body of heater inside and carry out the pyrolysated operation.

11. the manufacture method of glass particle according to claim 10 is characterized in that, described pyrolysated temperature is higher than the second-order transition temperature of described glass.

12. the manufacture method of glass particle according to claim 10, it is characterized in that, comprise that also glass particle with gained is blended in the solution that contains the glass ingredient different with described glass particle and makes the operation of raw material slip, the described raw material slip of made is made drop and imports pyritous body of heater inside and carry out the pyrolysated operation.

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