CN106601331A - Low-TCR-value high-temperature lead-free ruthenium slurry and preparation method thereof - Google Patents
Low-TCR-value high-temperature lead-free ruthenium slurry and preparation method thereof Download PDFInfo
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- CN106601331A CN106601331A CN201610937979.4A CN201610937979A CN106601331A CN 106601331 A CN106601331 A CN 106601331A CN 201610937979 A CN201610937979 A CN 201610937979A CN 106601331 A CN106601331 A CN 106601331A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01C—RESISTORS
- H01C7/00—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material
- H01C7/003—Thick film resistors
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Abstract
The invention discloses a low-TCR-value high-temperature lead-free ruthenium slurry and a preparation method thereof. The low-TCR-value high-temperature lead-free ruthenium slurry specifically comprises the following components in parts by weight: 30-50% of glass powders, 25-39% of ruthenium oxide powders, 20-37% of organic phase and 1-3% of additives. The above materials are matched. The low-TCR-value high-temperature lead-free ruthenium slurry does not contain lead and is excellent in printing performance. The low-TCR-value high-temperature lead-free ruthenium slurry can be used for printing resistor patterns on the surfaces of ceramic substrates and stainless steel substrates, and is completely applicable to heating devices large in power density (larger than 40W/cm2). Meanwhile, the ruthenium slurry is low in TCR value. The preparation method of the low-TCR-value high-temperature lead-free ruthenium slurry comprises the following process steps of a, preparing glass powders; b, preparing an organic phase; c, preparing the slurry; d, conducting the screen printing, and sintering. Through the above design of process steps, the high-temperature lead-free ruthenium slurry can be effectively produced by the preparation method.
Description
Technical field
The present invention relates to technical field of electronic materials, more particularly to a kind of slurry of the high-temp leadless ruthenium with low tcr values and its
Preparation method.
Background technology
Oxidation ruthenio thick-film resistor paste has been widely used at present in various heatings and capacitor element.With thick film circuit
To multiple stratification, miniaturization and integrated development, the heat of substrate and thick film itself is easy to accumulation to element, causes substrate and thick film sheet
The temperature of body is raised, if radiating effect is not good, the service life of thick film can decline because of the lasting rising of temperature, while temperature
Rising often lead to the increase of thick film itself resistance, the power of device decreases.The resistance of TCR values reflection material becomes with temperature
The trend of change, the more big then resistance varying-ratio of absolute value is bigger, and device accumulated heat is more, the thermal efficiency is lower.For oxidation ruthenio thick film
For slurry, TCR values are generally larger, and the TCR in the range of low-resistance is bigger.In addition, at present overwhelming majority ruthenium starches all leaded component, it is right
Environmental and human health impacts are unfavorable.
The content of the invention
Present invention aims to the deficiencies in the prior art and a kind of high-temp leadless ruthenium with low tcr values is provided
Slurry, should not have high-temp leadless ruthenium slurry of low tcr values leaded and with excellent silk-screen performance, can be used to printing ceramic, stainless
The resistance pattern on steel substrate surface, it is entirely appropriate as high power density（>40W/cm2）Heater members, and TCR values are little.
Another object of the present invention is to provide a kind of preparation method of the slurry of the high-temp leadless ruthenium with low tcr values, the tool
The preparation method for having the high-temp leadless ruthenium slurry of low tcr values can effectively be produced and prepare above-mentioned high-temp leadless ruthenium slurry.
To reach above-mentioned purpose, the present invention is achieved through the following technical solutions.
A kind of slurry of the high-temp leadless ruthenium with low tcr values, includes the material of following weight portion, specially：
Glass dust 30%-50%
Ruthenium-oxide powder 25%-39%
Organic faciess 20%-37%
Auxiliary agent 1%-3%.
Wherein, the glass dust includes the material of following weight portion, specially：
Zinc Oxide 80%-85%
Boron oxide 10%-13%
Barium monoxide 1%-4%
Aluminium oxide 2%-5%.
Wherein, the granularity of the glass dust is less than 10 μm.
Wherein, the purity of the ruthenium-oxide powder is more than 99.9%, and the granularity of ruthenium-oxide powder is less than 8 μm.
Wherein, the organic faciess include the material of following weight portion, specially：
Terpineol 30%-40%
Butyl carbitol 20%-30%
Butyl carbitol acetate 25%-35%
Dibutyl phthalate 10%-20%
Ethyl cellulose 4%-8%.
Wherein, the viscosity of the organic faciess is 20 Pas -50Pas.
Wherein, the lead tolerance that the high-temp leadless ruthenium of low tcr values is starched should is 0, solid content is 63%-70%.
Wherein, the TCR values that high-temp leadless ruthenium of low tcr values is starched should are 50 ppm/ DEG C -150ppm/ DEG C.
A kind of preparation method of the slurry of the high-temp leadless ruthenium with low tcr values, includes following processing step, specially：
A, prepare glass dust：Weigh Zinc Oxide, boron oxide, Barium monoxide, aluminium oxide, then by the Zinc Oxide for weighing, boron oxide,
Barium monoxide, aluminium oxide are stirred mixing, after zinc to be oxidized, boron oxide, Barium monoxide, aluminium oxide mix homogeneously, by Zinc Oxide, oxygen
The compound that change boron, Barium monoxide, aluminium oxide are constituted is transferred in corundum crucible or platinum crucible and by compound with corundum
Crucible or platinum crucible are put into into chamber type electric resistance furnace, chamber type electric resistance furnace temperature programming to 1250 DEG C and be incubated 20min so that
Obtain compound and be fused into vitreous humour；After chamber type electric resistance furnace insulation is finished, vitreous humour is taken out and carried out from chamber type electric resistance furnace
Water quenching, the frit after water quenching is crushed successively, ball milling is processed to obtain glass dust of the granularity less than 10 μm；Wherein, glass
In powder Zinc Oxide, boron oxide, Barium monoxide, the weight portion of four kinds of materials of aluminium oxide be followed successively by 80%-85%, 10%-13%, 1%-4%,
2%-5%；
B, preparation organic faciess：Weigh terpineol, butyl carbitol, butyl carbitol acetate, dibutyl phthalate, ethyl
Cellulose, then puts terpineol, butyl carbitol, butyl carbitol acetate, dibutyl phthalate, ethyl cellulose
Dispersed with stirring 4h in dispersion tank, to obtain the organic faciess of transparent solution shape；Wherein, terpineol in organic faciess, butyl card must
Alcohol, butyl carbitol acetate, dibutyl phthalate, the weight portion of five kinds of materials of ethyl cellulose be followed successively by 30%-40%,
20%-30%、25%-35%、10%-20%、4%-8%；
C, prepare slurry：Weigh glass dust, ruthenium-oxide powder, organic faciess, auxiliary agent, then to glass dust, ruthenium-oxide powder, organic faciess,
Auxiliary agent is mixed successively, three rollers grind, filter, deaeration is processed, to obtain slurry；Wherein, glass dust, oxidation in slurry
Ruthenium powder, organic faciess, the weight portion of four kinds of materials of auxiliary agent are followed successively by 30%-50%, 25%-39%, 20%-37%, 1%-3%；
D, the slurry silk-screen for being obtained step c in ceramic base material or stainless steel substrate surface, and after 850 DEG C of temperature strip
Sinter 10min under part, with obtain TCR values as 50 ppm/ DEG C -150ppm/ DEG C high-temp leadless ruthenium slurry.
Beneficial effects of the present invention are：A kind of slurry of the high-temp leadless ruthenium with low tcr values of the present invention, it is included
The material of following weight portion, specially：Glass dust 30%-50%, ruthenium-oxide powder 25%-39%, organic faciess 20%-37%, auxiliary agent 1%-
3%；By above-mentioned material proportion, there should be the high-temp leadless ruthenium slurry of low tcr values not leaded and with excellent silk-screen performance, can
It is entirely appropriate as high power density for printing the resistance pattern on ceramics, stainless steel substrate surface（>40W/cm2）Heating element
Part, and TCR values are little.
The another of the present invention has the beneficial effect that：A kind of system of slurry of the high-temp leadless ruthenium with low tcr values of the present invention
Preparation Method, it includes following processing step：A, prepare glass dust；B, preparation organic faciess；C, prepare slurry；D, silk-screen, burning
Knot.Designed by above-mentioned processing step, there should be the preparation method that the high-temp leadless ruthenium of low tcr values is starched effectively to produce system
Standby above-mentioned high-temp leadless ruthenium slurry.
Specific embodiment
With reference to specific embodiment, the present invention will be described.
A kind of embodiment one, slurry of the high-temp leadless ruthenium with low tcr values, includes the material of following weight portion, specially：
Glass dust 49%
Ruthenium-oxide powder 25%
Organic faciess 25%
Auxiliary agent 1%.
Wherein, the glass dust includes the material of following weight portion, specially：
Zinc Oxide 80%
Boron oxide 12%
Barium monoxide 4%
Aluminium oxide 4%.
In addition, the organic faciess include the material of following weight portion, specially：
Terpineol 30%
Butyl carbitol 25%
Butyl carbitol acetate 20%
Dibutyl phthalate 20%
Ethyl cellulose 5%.
Need to be explained further, the granularity of the glass dust is less than 10 μm, and the purity of the ruthenium-oxide powder is more than 99.9%, oxygen
The granularity for changing ruthenium powder is less than 8 μm, and the viscosity of the organic faciess is 20 Pas-50Pas, should have the high temperature of low tcr values without
The lead tolerance of lead ruthenium slurry is 0, and solid content is 63%-70%.
It should further be noted that the slurry of the high-temp leadless ruthenium with low tcr values of the present embodiment one can adopt following preparation side
Method is prepared from, and specifically, a kind of preparation method of the slurry of the high-temp leadless ruthenium with low tcr values includes following processing step,
Specially：
A, prepare glass dust：Weigh Zinc Oxide, boron oxide, Barium monoxide, aluminium oxide, then by the Zinc Oxide for weighing, boron oxide,
Barium monoxide, aluminium oxide are stirred mixing, after zinc to be oxidized, boron oxide, Barium monoxide, aluminium oxide mix homogeneously, by Zinc Oxide, oxygen
The compound that change boron, Barium monoxide, aluminium oxide are constituted is transferred in corundum crucible or platinum crucible and by compound with corundum
Crucible or platinum crucible are put into into chamber type electric resistance furnace, chamber type electric resistance furnace temperature programming to 1250 DEG C and be incubated 20min so that
Obtain compound and be fused into vitreous humour；After chamber type electric resistance furnace insulation is finished, vitreous humour is taken out and carried out from chamber type electric resistance furnace
Water quenching, the frit after water quenching is crushed successively, ball milling is processed to obtain glass dust of the granularity less than 10 μm；Wherein, glass
Zinc Oxide, boron oxide, Barium monoxide, the weight portion of four kinds of materials of aluminium oxide are followed successively by 80%, 12%, 4%, 4% in powder；
B, preparation organic faciess：Weigh terpineol, butyl carbitol, butyl carbitol acetate, dibutyl phthalate, ethyl
Cellulose, then puts terpineol, butyl carbitol, butyl carbitol acetate, dibutyl phthalate, ethyl cellulose
Dispersed with stirring 4h in dispersion tank, to obtain the organic faciess of transparent solution shape；Wherein, terpineol in organic faciess, butyl card must
Alcohol, butyl carbitol acetate, dibutyl phthalate, the weight portion of five kinds of materials of ethyl cellulose are followed successively by 30%, 25%,
20%、20%、5%；
C, prepare slurry：Weigh glass dust, ruthenium-oxide powder, organic faciess, auxiliary agent, then to glass dust, ruthenium-oxide powder, organic faciess,
Auxiliary agent is mixed successively, three rollers grind, filter, deaeration is processed, to obtain slurry；Wherein, glass dust, oxidation in slurry
Ruthenium powder, organic faciess, the weight portion of four kinds of materials of auxiliary agent are followed successively by 49%, 25%, 25%, 1%；
D, the slurry silk-screen for being obtained step c in ceramic base material or stainless steel substrate surface, and after 850 DEG C of temperature strip
10min is sintered under part, to obtain high-temp leadless ruthenium slurry.
Sheet resistance value by high-temp leadless ruthenium prepared by above-mentioned material proportion and preparation method slurry be 19 Ω/
, TCR value is 116 ppm/ DEG C.So, the high-temp leadless ruthenium of the present embodiment one slurry is leaded and with excellent silk-screen performance,
Can be used to print ceramics, the resistance pattern on stainless steel substrate surface, it is entirely appropriate as high power density（>40W/cm2）Heating
Device, and TCR values are little；Wherein, above-mentioned excellent properties have benefited from following two aspect：1st, unleaded Zn-B-Ba-Al glass frits embody
Excellent high-temperature stability；2nd, the organic faciess of reasonable mixture ratio have good wettability to glass dust and ruthenium-oxide powder.
A kind of embodiment two, slurry of the high-temp leadless ruthenium with low tcr values, includes the material of following weight portion, specially：
Glass dust 46%
Ruthenium-oxide powder 26%
Organic faciess 27%
Auxiliary agent 1%.
Wherein, glass dust includes the material of following weight portion, specially：
Zinc Oxide 85%
Boron oxide 10%
Barium monoxide 3%
Aluminium oxide 2%.
In addition, organic faciess include the material of following weight portion, specially：
Terpineol 35%
Butyl carbitol 20%
Butyl carbitol acetate 30%
Dibutyl phthalate 10%
Ethyl cellulose 5%.
Need to be explained further, the granularity of glass dust is less than 10 μm, and the purity of ruthenium-oxide powder is more than 99.9%, ruthenium-oxide powder
Granularity is less than 8 μm, and the viscosity of organic faciess is 20 Pas-50Pas, is somebody's turn to do the leaded of the slurry of the high-temp leadless ruthenium with low tcr values
Measure as 0, solid content is 63%-70%.
It should further be noted that the slurry of the high-temp leadless ruthenium with low tcr values of the present embodiment two can adopt following preparation side
Method is prepared from, and specifically, a kind of preparation method of the slurry of the high-temp leadless ruthenium with low tcr values includes following processing step,
Specially：
A, prepare glass dust：Weigh Zinc Oxide, boron oxide, Barium monoxide, aluminium oxide, then by the Zinc Oxide for weighing, boron oxide,
Barium monoxide, aluminium oxide are stirred mixing, after zinc to be oxidized, boron oxide, Barium monoxide, aluminium oxide mix homogeneously, by Zinc Oxide, oxygen
The compound that change boron, Barium monoxide, aluminium oxide are constituted is transferred in corundum crucible or platinum crucible and by compound with corundum
Crucible or platinum crucible are put into into chamber type electric resistance furnace, chamber type electric resistance furnace temperature programming to 1250 DEG C and be incubated 20min so that
Obtain compound and be fused into vitreous humour；After chamber type electric resistance furnace insulation is finished, vitreous humour is taken out and carried out from chamber type electric resistance furnace
Water quenching, the frit after water quenching is crushed successively, ball milling is processed to obtain glass dust of the granularity less than 10 μm；Wherein, glass
Zinc Oxide, boron oxide, Barium monoxide, the weight portion of four kinds of materials of aluminium oxide are followed successively by 85%, 10%, 3%, 2% in powder；
B, preparation organic faciess：Weigh terpineol, butyl carbitol, butyl carbitol acetate, dibutyl phthalate, ethyl
Cellulose, then puts terpineol, butyl carbitol, butyl carbitol acetate, dibutyl phthalate, ethyl cellulose
Dispersed with stirring 4h in dispersion tank, to obtain the organic faciess of transparent solution shape；Wherein, terpineol in organic faciess, butyl card must
Alcohol, butyl carbitol acetate, dibutyl phthalate, the weight portion of five kinds of materials of ethyl cellulose are followed successively by 35%, 20%,
30%、10%、5%；
C, prepare slurry：Weigh glass dust, ruthenium-oxide powder, organic faciess, auxiliary agent, then to glass dust, ruthenium-oxide powder, organic faciess,
Auxiliary agent is mixed successively, three rollers grind, filter, deaeration is processed, to obtain slurry；Wherein, glass dust, oxidation in slurry
Ruthenium powder, organic faciess, the weight portion of four kinds of materials of auxiliary agent are followed successively by 46%, 26%, 27%, 1%；
D, the slurry silk-screen for being obtained step c in ceramic base material or stainless steel substrate surface, and after 850 DEG C of temperature strip
10min is sintered under part, to obtain high-temp leadless ruthenium slurry.
Sheet resistance value by high-temp leadless ruthenium prepared by above-mentioned material proportion and preparation method slurry be 15 Ω/
, TCR value is 92 ppm/ DEG C.So, the high-temp leadless ruthenium of the present embodiment two slurry is leaded and with excellent silk-screen performance,
Can be used to print ceramics, the resistance pattern on stainless steel substrate surface, it is entirely appropriate as high power density（>40W/cm2）Heating
Device, and TCR values are little；Wherein, above-mentioned excellent properties have benefited from following two aspect：1st, unleaded Zn-B-Ba-Al glass frits embody
Excellent high-temperature stability；2nd, the organic faciess of reasonable mixture ratio have good wettability to glass dust and ruthenium-oxide powder.
A kind of embodiment three, slurry of the high-temp leadless ruthenium with low tcr values, includes the material of following weight portion, specially：
Glass dust 40%
Ruthenium-oxide powder 30%
Organic faciess 29%
Auxiliary agent 1%.
Wherein, glass dust includes the material of following weight portion, specially：
Zinc Oxide 82%
Boron oxide 12%
Barium monoxide 4%
Aluminium oxide 2%.
In addition, organic faciess include the material of following weight portion, specially：
Terpineol 40%
Butyl carbitol 20%
Butyl carbitol acetate 15%
Dibutyl phthalate 20%
Ethyl cellulose 5%.
Need to be explained further, the granularity of glass dust is less than 10 μm, and the purity of ruthenium-oxide powder is more than 99.9%, ruthenium-oxide powder
Granularity is less than 8 μm, and the viscosity of organic faciess is 20 Pas -50Pas, is somebody's turn to do the leaded of the slurry of the high-temp leadless ruthenium with low tcr values
Measure as 0, solid content is 63%-70%.
It should further be noted that the slurry of the high-temp leadless ruthenium with low tcr values of the present embodiment three can adopt following preparation side
Method is prepared from, and specifically, a kind of preparation method of the slurry of the high-temp leadless ruthenium with low tcr values includes following processing step,
Specially：
A, prepare glass dust：Weigh Zinc Oxide, boron oxide, Barium monoxide, aluminium oxide, then by the Zinc Oxide for weighing, boron oxide,
Barium monoxide, aluminium oxide are stirred mixing, after zinc to be oxidized, boron oxide, Barium monoxide, aluminium oxide mix homogeneously, by Zinc Oxide, oxygen
The compound that change boron, Barium monoxide, aluminium oxide are constituted is transferred in corundum crucible or platinum crucible and by compound with corundum
Crucible or platinum crucible are put into into chamber type electric resistance furnace, chamber type electric resistance furnace temperature programming to 1250 DEG C and be incubated 20min so that
Obtain compound and be fused into vitreous humour；After chamber type electric resistance furnace insulation is finished, vitreous humour is taken out and carried out from chamber type electric resistance furnace
Water quenching, the frit after water quenching is crushed successively, ball milling is processed to obtain glass dust of the granularity less than 10 μm；Wherein, glass
Zinc Oxide, boron oxide, Barium monoxide, the weight portion of four kinds of materials of aluminium oxide are followed successively by 82%, 12%, 4%, 2% in powder；
B, preparation organic faciess：Weigh terpineol, butyl carbitol, butyl carbitol acetate, dibutyl phthalate, ethyl
Cellulose, then puts terpineol, butyl carbitol, butyl carbitol acetate, dibutyl phthalate, ethyl cellulose
Dispersed with stirring 4h in dispersion tank, to obtain the organic faciess of transparent solution shape；Wherein, terpineol in organic faciess, butyl card must
Alcohol, butyl carbitol acetate, dibutyl phthalate, the weight portion of five kinds of materials of ethyl cellulose are followed successively by 40%, 20%,
15%、20%、5%；
C, prepare slurry：Weigh glass dust, ruthenium-oxide powder, organic faciess, auxiliary agent, then to glass dust, ruthenium-oxide powder, organic faciess,
Auxiliary agent is mixed successively, three rollers grind, filter, deaeration is processed, to obtain slurry；Wherein, glass dust, oxidation in slurry
Ruthenium powder, organic faciess, the weight portion of four kinds of materials of auxiliary agent are followed successively by 40%, 30%, 29%, 1%；
D, the slurry silk-screen for being obtained step c in ceramic base material or stainless steel substrate surface, and after 850 DEG C of temperature strip
10min is sintered under part, to obtain high-temp leadless ruthenium slurry.
Sheet resistance value by high-temp leadless ruthenium prepared by above-mentioned material proportion and preparation method slurry be 11 Ω/
, TCR value is 79 ppm/ DEG C.So, the high-temp leadless ruthenium of the present embodiment three slurry is leaded and with excellent silk-screen performance,
Can be used to print ceramics, the resistance pattern on stainless steel substrate surface, it is entirely appropriate as high power density（>40W/cm2）Heating
Device, and TCR values are little；Wherein, above-mentioned excellent properties have benefited from following two aspect：1st, unleaded Zn-B-Ba-Al glass frits embody
Excellent high-temperature stability；2nd, the organic faciess of reasonable mixture ratio have good wettability to glass dust and ruthenium-oxide powder.
A kind of example IV, slurry of the high-temp leadless ruthenium with low tcr values, includes the material of following weight portion, specially：
Glass dust 36%
Ruthenium-oxide powder 32%
Organic faciess 30%
Auxiliary agent 2%.
Wherein, glass dust includes the material of following weight portion, specially：
Zinc Oxide 80%
Boron oxide 12%
Barium monoxide 4%
Aluminium oxide 4%.
In addition, organic faciess include the material of following weight portion, specially：
Terpineol 30%
Butyl carbitol 25%
Butyl carbitol acetate 20%
Dibutyl phthalate 20%
Ethyl cellulose 5%.
Need to be explained further, the granularity of glass dust is less than 10 μm, and the purity of ruthenium-oxide powder is more than 99.9%, ruthenium-oxide powder
Granularity is less than 8 μm, and the viscosity of organic faciess is 20 Pas -50Pas, is somebody's turn to do the leaded of the slurry of the high-temp leadless ruthenium with low tcr values
Measure as 0, solid content is 63%-70%.
It should further be noted that the slurry of the high-temp leadless ruthenium with low tcr values of the present embodiment four can adopt following preparation side
Method is prepared from, and specifically, a kind of preparation method of the slurry of the high-temp leadless ruthenium with low tcr values includes following processing step,
Specially：
A, prepare glass dust：Weigh Zinc Oxide, boron oxide, Barium monoxide, aluminium oxide, then by the Zinc Oxide for weighing, boron oxide,
Barium monoxide, aluminium oxide are stirred mixing, after zinc to be oxidized, boron oxide, Barium monoxide, aluminium oxide mix homogeneously, by Zinc Oxide, oxygen
The compound that change boron, Barium monoxide, aluminium oxide are constituted is transferred in corundum crucible or platinum crucible and by compound with corundum
Crucible or platinum crucible are put into into chamber type electric resistance furnace, chamber type electric resistance furnace temperature programming to 1250 DEG C and be incubated 20min so that
Obtain compound and be fused into vitreous humour；After chamber type electric resistance furnace insulation is finished, vitreous humour is taken out and carried out from chamber type electric resistance furnace
Water quenching, the frit after water quenching is crushed successively, ball milling is processed to obtain glass dust of the granularity less than 10 μm；Wherein, glass
Zinc Oxide, boron oxide, Barium monoxide, the weight portion of four kinds of materials of aluminium oxide are followed successively by 80%, 12%, 4%, 4% in powder；
B, preparation organic faciess：Weigh terpineol, butyl carbitol, butyl carbitol acetate, dibutyl phthalate, ethyl
Cellulose, then puts terpineol, butyl carbitol, butyl carbitol acetate, dibutyl phthalate, ethyl cellulose
Dispersed with stirring 4h in dispersion tank, to obtain the organic faciess of transparent solution shape；Wherein, terpineol in organic faciess, butyl card must
Alcohol, butyl carbitol acetate, dibutyl phthalate, the weight portion of five kinds of materials of ethyl cellulose are followed successively by 30%, 25%,
20%、20%、5%；
C, prepare slurry：Weigh glass dust, ruthenium-oxide powder, organic faciess, auxiliary agent, then to glass dust, ruthenium-oxide powder, organic faciess,
Auxiliary agent is mixed successively, three rollers grind, filter, deaeration is processed, to obtain slurry；Wherein, glass dust, oxidation in slurry
Ruthenium powder, organic faciess, the weight portion of four kinds of materials of auxiliary agent are followed successively by 36%, 32%, 30%, 2%；
D, the slurry silk-screen for being obtained step c in ceramic base material or stainless steel substrate surface, and after 850 DEG C of temperature strip
10min is sintered under part, to obtain high-temp leadless ruthenium slurry.
Sheet resistance value by the high-temp leadless ruthenium slurry prepared by above-mentioned material proportion and preparation method is 8 Ω/,
TCR values are 76 ppm/ DEG C.So, the high-temp leadless ruthenium of the present embodiment four slurry is leaded and with excellent silk-screen performance, can use
It is entirely appropriate as high power density in the resistance pattern for printing ceramics, stainless steel substrate surface（>40W/cm2）Heater members,
And TCR values are little；Wherein, above-mentioned excellent properties have benefited from following two aspect：1st, unleaded Zn-B-Ba-Al glass frits embody excellent
High-temperature stability；2nd, the organic faciess of reasonable mixture ratio have good wettability to glass dust and ruthenium-oxide powder.
A kind of embodiment five, slurry of the high-temp leadless ruthenium with low tcr values, includes the material of following weight portion, specially：
Glass dust 34%
Ruthenium-oxide powder 34%
Organic faciess 30%
Auxiliary agent 2%.
Wherein, glass dust includes the material of following weight portion, specially：
Zinc Oxide 85%
Boron oxide 10%
Barium monoxide 3%
Aluminium oxide 2%.
In addition, organic faciess include the material of following weight portion, specially：
Terpineol 35%
Butyl carbitol 20%
Butyl carbitol acetate 30%
Dibutyl phthalate 10%
Ethyl cellulose 5%.
Need to be explained further, the granularity of glass dust is less than 10 μm, and the purity of ruthenium-oxide powder is more than 99.9%, ruthenium-oxide powder
Granularity is less than 8 μm, and the viscosity of organic faciess is 20 Pas -50Pas, is somebody's turn to do the leaded of the slurry of the high-temp leadless ruthenium with low tcr values
Measure as 0, solid content is 63%-70%.
It should further be noted that the slurry of the high-temp leadless ruthenium with low tcr values of the present embodiment five can adopt following preparation side
Method is prepared from, and specifically, a kind of preparation method of the slurry of the high-temp leadless ruthenium with low tcr values includes following processing step,
Specially：
A, prepare glass dust：Weigh Zinc Oxide, boron oxide, Barium monoxide, aluminium oxide, then by the Zinc Oxide for weighing, boron oxide,
Barium monoxide, aluminium oxide are stirred mixing, after zinc to be oxidized, boron oxide, Barium monoxide, aluminium oxide mix homogeneously, by Zinc Oxide, oxygen
The compound that change boron, Barium monoxide, aluminium oxide are constituted is transferred in corundum crucible or platinum crucible and by compound with corundum
Crucible or platinum crucible are put into into chamber type electric resistance furnace, chamber type electric resistance furnace temperature programming to 1250 DEG C and be incubated 20min so that
Obtain compound and be fused into vitreous humour；After chamber type electric resistance furnace insulation is finished, vitreous humour is taken out and carried out from chamber type electric resistance furnace
Water quenching, the frit after water quenching is crushed successively, ball milling is processed to obtain glass dust of the granularity less than 10 μm；Wherein, glass
Zinc Oxide, boron oxide, Barium monoxide, the weight portion of four kinds of materials of aluminium oxide are followed successively by 85%, 10%, 3%, 2% in powder；
B, preparation organic faciess：Weigh terpineol, butyl carbitol, butyl carbitol acetate, dibutyl phthalate, ethyl
Cellulose, then puts terpineol, butyl carbitol, butyl carbitol acetate, dibutyl phthalate, ethyl cellulose
Dispersed with stirring 4h in dispersion tank, to obtain the organic faciess of transparent solution shape；Wherein, terpineol in organic faciess, butyl card must
Alcohol, butyl carbitol acetate, dibutyl phthalate, the weight portion of five kinds of materials of ethyl cellulose are followed successively by 35%, 20%,
30%、10%、5%；
C, prepare slurry：Weigh glass dust, ruthenium-oxide powder, organic faciess, auxiliary agent, then to glass dust, ruthenium-oxide powder, organic faciess,
Auxiliary agent is mixed successively, three rollers grind, filter, deaeration is processed, to obtain slurry；Wherein, glass dust, oxidation in slurry
Ruthenium powder, organic faciess, the weight portion of four kinds of materials of auxiliary agent are followed successively by 34%, 34%, 30%, 2%；
D, the slurry silk-screen for being obtained step c in ceramic base material or stainless steel substrate surface, and after 850 DEG C of temperature strip
10min is sintered under part, to obtain high-temp leadless ruthenium slurry.
Sheet resistance value by the high-temp leadless ruthenium slurry prepared by above-mentioned material proportion and preparation method is 6 Ω/,
TCR values are 65 ppm/ DEG C.So, the high-temp leadless ruthenium of the present embodiment five slurry is leaded and with excellent silk-screen performance, can use
It is entirely appropriate as high power density in the resistance pattern for printing ceramics, stainless steel substrate surface（>40W/cm2）Heater members,
And TCR values are little；Wherein, above-mentioned excellent properties have benefited from following two aspect：1st, unleaded Zn-B-Ba-Al glass frits embody excellent
High-temperature stability；2nd, the organic faciess of reasonable mixture ratio have good wettability to glass dust and ruthenium-oxide powder.
Above content is only presently preferred embodiments of the present invention, for one of ordinary skill in the art, according to the present invention's
Thought, will change in specific embodiments and applications, and this specification content should not be construed as to the present invention
Restriction.
Claims (9)
1. a kind of high-temp leadless ruthenium with low tcr values is starched, it is characterised in that include the material of following weight portion, specially：
Glass dust 30%-50%
Ruthenium-oxide powder 25%-39%
Organic faciess 20%-37%
Auxiliary agent 1%-3%.
2. a kind of high-temp leadless ruthenium with low tcr values according to claim 1 is starched, it is characterised in that the glass dust
The material of following weight portion is included, specially：
Zinc Oxide 80%-85%
Boron oxide 10%-13%
Barium monoxide 1%-4%
Aluminium oxide 2%-5%.
3. a kind of high-temp leadless ruthenium with low tcr values according to claim 2 is starched, it is characterised in that：The glass dust
Granularity be less than 10 μm.
4. a kind of high-temp leadless ruthenium with low tcr values according to claim 1 is starched, it is characterised in that：The ruthenium-oxide
The purity of powder is more than 99.9%, and the granularity of ruthenium-oxide powder is less than 8 μm.
5. a kind of high-temp leadless ruthenium with low tcr values according to claim 1 is starched, it is characterised in that：The organic faciess
The material of following weight portion is included, specially：
Terpineol 30%-40%
Butyl carbitol 20%-30%
Butyl carbitol acetate 25%-35%
Dibutyl phthalate 10%-20%
Ethyl cellulose 4%-8%.
6. a kind of high-temp leadless ruthenium with low tcr values according to claim 5 is starched, it is characterised in that：The organic faciess
Viscosity be 20 Pas -50Pas.
7. a kind of high-temp leadless ruthenium with low tcr values according to claim 1 to 6 any one is starched, it is characterised in that：
There should be the lead tolerance that the high-temp leadless ruthenium of low tcr values is starched to be 0, solid content is 63%-70%.
8. a kind of high-temp leadless ruthenium with low tcr values according to claim 7 is starched, it is characterised in that：There should be low TCR
The TCR values of the high-temp leadless ruthenium slurry of value are 50 ppm/ DEG C -150ppm/ DEG C.
9. the preparation method that a kind of high-temp leadless ruthenium with low tcr values is starched, it is characterised in that include following processing step,
Specially：
A, prepare glass dust：Weigh Zinc Oxide, boron oxide, Barium monoxide, aluminium oxide, then by the Zinc Oxide for weighing, boron oxide,
Barium monoxide, aluminium oxide are stirred mixing, after zinc to be oxidized, boron oxide, Barium monoxide, aluminium oxide mix homogeneously, by Zinc Oxide, oxygen
The compound that change boron, Barium monoxide, aluminium oxide are constituted is transferred in corundum crucible or platinum crucible and by compound with corundum
Crucible or platinum crucible are put into into chamber type electric resistance furnace, chamber type electric resistance furnace temperature programming to 1250 DEG C and be incubated 20min so that
Obtain compound and be fused into vitreous humour；After chamber type electric resistance furnace insulation is finished, vitreous humour is taken out and carried out from chamber type electric resistance furnace
Water quenching, the frit after water quenching is crushed successively, ball milling is processed to obtain glass dust of the granularity less than 10 μm；Wherein, glass
In powder Zinc Oxide, boron oxide, Barium monoxide, the weight portion of four kinds of materials of aluminium oxide be followed successively by 80%-85%, 10%-13%, 1%-4%,
2%-5%；
B, preparation organic faciess：Weigh terpineol, butyl carbitol, butyl carbitol acetate, dibutyl phthalate, ethyl
Cellulose, then puts terpineol, butyl carbitol, butyl carbitol acetate, dibutyl phthalate, ethyl cellulose
Dispersed with stirring 4h in dispersion tank, to obtain the organic faciess of transparent solution shape；Wherein, terpineol in organic faciess, butyl card must
Alcohol, butyl carbitol acetate, dibutyl phthalate, the weight portion of five kinds of materials of ethyl cellulose be followed successively by 30%-40%,
20%-30%、25%-35%、10%-20%、4%-8%；
C, prepare slurry：Weigh glass dust, ruthenium-oxide powder, organic faciess, auxiliary agent, then to glass dust, ruthenium-oxide powder, organic faciess,
Auxiliary agent is mixed successively, three rollers grind, filter, deaeration is processed, to obtain slurry；Wherein, glass dust, oxidation in slurry
Ruthenium powder, organic faciess, the weight portion of four kinds of materials of auxiliary agent are followed successively by 30%-50%, 25%-39%, 28%-37%, 1%-3%；
D, the slurry silk-screen for being obtained step c in ceramic base material or stainless steel substrate surface, and after 850 DEG C of temperature strip
Sinter 10min under part, with obtain TCR values as 50 ppm/ DEG C -150ppm/ DEG C high-temp leadless ruthenium slurry.
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