Glaze resistor composition

This invention relates to a glaze resistor composition. Glaze resistor compositions for coating suitable heatresistant substrates and firing in air to form glaze resistors are well known, for example, RuO.sub.2, Ag, and Ag-Pd glaze etc. Particularly, RuO.sub.2 glaze resistor is often used commercially, because it has good resistor characteristics.
Glaze resistors containing a mixture of several silicides are also known, for example, molybdenum disilicide, molybdenum boride and tungsten disilicide (as disclosed in British Pat. No. 1,263,728), or molybdenum disilicide, tantalum disilicide and a glass frit containing alumina (as disclosed in U.S. Pat. No. 3,027,332).
However, such compositions have a temperature coefficient of resistivity which is too high for many purposes, a relatively unstable resistivity, too large a current noise a limited resistivity range.
It is an object of this invention to provide a glaze resistor composition having a satisfactory temperature coefficient of resistivity, a high resistivity stability, small current noises and usable in a wide resistivity range.
This object is achieved according to this invention by providing a glaze resistor composition which consists essentially of 95 to 50% by weight of a glass frit and 5 to 50% by weight of a mixture of silicides comprising molybdenum disilicide, tantalum disilicide, magnesium silicide and aluminium, the molar ratio of molybdenum disilicide plus tantalum disilicide plus magnesium silicide to aluminium being from 90:10 to 60:40.
This invention will be described in detail hereinafter.
According to a first aspect of the present invention, there is provided a glaze resistor composition which consists essentially of 95 to 50% by weight of a glass frit and 5 to 50% by weight of a mixture of silicides and aluminium. The silicides are magnesium silicide, molybdenum disilicide and tantalum disilicide. The molar ratio of molybdenum disilicide plus tantalum disilicide to magnesium silicide is from 30:70 to 90:10, and molybdenum disilicide plus tantalum disilicide plus magnesium silicide to aluminium being from 90:10 to 60:40% by molar.
The addition of aluminium to a mixture of molybdenum disilicide, tantalum disilicide and magnesium silicide in the composition according to the invention stabilizes the resistivity of the resulting resistor over a wide range of resistivity and improves the temperature coefficient of resistivity, stability under load and current noises. These properties are believed to result from aluminium acting as a conductor and providing intimate connection between a conductor and glass by oxidation during the composition.
If aluminium is used in a too large amount, the resistivity of the resistor increases, but current noises also increase. If magnesium silicide is used in a too large amount, the stability of the resulting resistor is lowered, because magnesium silicide would be converted to magnesium hydroxide by hydrolysis. If tantalum disilicide is used in a too small amount, the homogeneity of the resistor film may be impaired by the presence of bubbles therein. If molybdenum disilicide is used in a too small amount, a load test stability is impaired.
It is preferred that the mixture of silicide and aluminium in the composition according to the invention contains the silicides in amounts such that the molar ratio of molybdenum disilicide plus tantalum disilicide to magnesium silicide is from 60:40 to 80:20 and the molar ratio of molybdenum disilicide plus tantalum disilicide plus magnesium silicide to aluminium is from 85:15 to 65:35.
In one embodiment of the present invention, the resistivity of the resulting resistor increases by the inclusion of aluminium in the mixture of silicides, preferably in an amount of from 10 to 40 molar ratio. Too much aluminium is undesirable because of current noises and load test characteristics which would result therefrom. Also, too much magnesium silicide is undesirable because of the current noises and humidity characteristics which would result therefrom.
The conductor consisting of a mixture of silicides and aluminium according to the invention is made as described below. A suitable amount of molybdenum, tantalum, magnesium, silicon and aluminium are mixed by a mixing machine, and pressed to a tablet of a suitable size. The tablets are fired at a temperature of 800.degree. to 1300.degree. C. in an inert gas such as argon or in an active gas such as hydrogen. Each fired tablet is crushed roughly using a crushing machine, and ground into fine granules, having an average particle size of 0.1 micron, by a ball mill. Any suitable glass frit may be included in the composition according to the invention, but a preferred glass frit is a barium borate series glass, especially containing niobium oxide Nb.sub.2 O.sub.5. A preferred barium borate series glass has the following composition, by weight:
______________________________________ BaO 25 to 55 B.sub.2 O.sub.3 30 to 60% SiO.sub.2 0 to 10% Al.sub.2 O.sub.3 0 to 16% CaO 0 to 5% MgO 0 to 5% Nb.sub.2 O.sub.5 0 to 3%______________________________________
The glass frit is necessary for obtaining superior resistance to humidity and heat, suitable reaction with conductive powder in the firing of the resistor, and to distribute the conduction powder evenly therein. The SiO.sub.2, Al.sub.2 O.sub.3, MgO and CaO components in the glass frit improve resistance to humidity and heat. Nb.sub.2 O.sub.5 improves the distribution of the conduction powder in the glass together with magnesium silicide and aluminium in the conduction powder. As a result, the resistor has a higher resistivity value and good stability characteristics.
Materials used for making the glass frits are described below.
A material for BaO is BaCO.sub.3, which by firing, is reduced to BaO (and CO.sub.2). A material for B.sub.2 O.sub.3 is H.sub.3 BO.sub.3, which by firing is reduced to B.sub.2 O.sub.3 (and H.sub.2 O). A material for Al.sub.2 O.sub.3 is Al.sub.2 O.sub.3 or aluminium hydroxide Al.sub.2 (OH).sub.3, which by firing is reduced to Al.sub.2 O.sub.3 (and H.sub.2 O). A material for CaO is CaCO.sub.3, which by firing is reduced to CaO (and CO.sub.2). SiO.sub.2, MgO and Nb.sub.2 O.sub.5 used are oxide metals. The glass frits are made e.g. in a manner as follows. The respective materials of the glass are mixed in a ratio e.g. as follows:
BaCO.sub.3 :H.sub.3 BO.sub.3 :SiO.sub.2 :Al.sub.2 0.sub.3 :CaCO.sub.3 :MgO:Nb.sub.2 O.sub.5 =34.2:51.3:3.4:6.0:2.15:2.70:0.25 in weight %. The mixed powders are melted at 1200.degree. C. for 30 minutes in air in an alumina crucible. In heating, the molten material is converted to glass, and the generated CO.sub.2 and H.sub.2 O evaporates off. Next, the molten glass is cooled and roughly crushed with water. Further, the roughly crushed glass particles are ground through a screen mesh of 400 mesh. And finally this ground glass particles are ground by a ball mill into fine granules, having an average particle size of 3 microns.
A typical method of making a glaze resistor using a glaze resistor composition according to the invention will now be described. A glaze resistor composition including an appropriate amount of glass frit and a suitable organic liquid vehicle (such as terpineol having 10% ethylcellulose dissolved therein) are mixed to a paste. The paste is applied to a refractory substrate such as a ceramic plate, and is then heated or fired in air in, for example, a tunnel furnace, at a temperature such that the glass frit is adequately fused thereto and to form a stable glaze resistor film on the refractory substrate.
A typical heating temperature is from 750.degree. to 1000.degree. C., more preferably from 800.degree. to 900.degree. C., for time of from 3 to 30 minutes. During the heat treatment, the liquid vehicle evaporates off or burns off, and does not substantially affect the resistivity or other characteristics of the resultant glaze resistor.

A typical method of making a glaze resistor using a glaze resistor composition according to the invention will be described below. In order that the invention may be more fully understood, the following Examples are given by way of illustration only. In the Examples, reference will be made to the accompanying drawings, in which:
FIG. 1 is a graph showing the relation between the resistivities and temperature coefficients of resistivity of two types of glaze resistors;
FIG. 2 is a graph showing the relation between the resistivities and current noises of two types of glaze resistors; and
FIG. 3 is a graph showing the relation between the resistivities and the change of resistivities of two types of glaze resistors after a load test.

EXAMPLE 1
Sixty different glaze resistor compositions without aluminium, for comparison, were prepared, having a composition shown in Table 1. Each composition was made as follows:
Mixtures of silicides in the form of a powder having an average particle size of 0.2 micron and glass frit were made up in the percentage shown in Table 1. The glass frit used had an average particle size of 3 microns, and composed of a barium borate glass frit. Each mixture of silicides and the glass frit was well dispersed in an appropriate amount of liquid vehicle to make a paste suitable for screen printing. Each paste was applied on a ceramic substrate by screen printing and dried, followed by heating in air at a temperature of 850.degree. C. for 10 minutes to obtain sixty glaze resistors each in the form of a film.
The sheet resistivity R (.OMEGA./sq), temperature coefficient of resistivity TCR (ppm/.degree.C.), current noise (dB) and load test characteristics (percent change of resistivity after load test) of each of the sixty resistors were measured. The load test was carried out by applying an electric power of 625 mW/mm.sup.2 to the glaze resistor for 5 seconds at room temperature, and the load characteristics were calculated from the difference between the resistivities of the glaze resistor before and after the load test divided by the resistivity before the load test.
The results of all these measurements are shown in Table 1. It will be apparent from Table 1 that various resistivities in a range from 20.OMEGA./sq with small temperature coefficients of resistivity, low current noises and good load test characteristics can be obtained. As the amount of magnesium silicide increases, the resistivity becomes higher, and the temperature coefficient of resistivity increases. However, most of the values of the temperature coefficients of resistivity are less than 200 ppm/.degree.C., except for the case of very low resistivities. The load test characteristics are good, particularly in a lower resistivity range.
However, a disadvantage of the results of this Example 1 is that a high resistivity higher than 40 or 50 or 100 k.OMEGA./sq is difficult to obtain without deteriorating other characteristics.
EXAMPLE 2
Fifty-six different glaze resistor compositions according to the invention (Sample Nos. 61 to 116) were prepared having the compositions shown in Table 2. Each composition was made as follows:
Mixtures of silicides containing aluminium, in the form of a powder, having an average particle size of 0.2 micron, and glass frit the same as the glass frit used in Example 1 were made up in the percentages shown in Table 2. Each mixture of silicides containing aluminium and a glass frit was well dispersed in an appropriate amount of liquid vehicle to make a paste suitable for screen printing. Each paste was applied on a ceramic substrate by screen printing and dried, followed by heating in air at a temperature of 850.degree. C. for 10 minutes to obtain fifty-six different glaze resistors each in the form of a film.
The sheet resistivity, temperature coefficient of resistivity, current noise and load test characteristics of each of fifty-six resistors were measured in the same manner as in Example 1. The results of measurments are shown in Table 2.
These measured results are also plotted in FIGS. 1 to 3.
It will be apparent from Table 2 and FIGS. 1 to 3 that various resistivities in a wide resistivity range, particularly up to a very high resistivity as compared with those in Example 1, with small temperature coefficients of resistivity, low current noise and good load test characteristics can be obtained according to the invention.
TABLE 1__________________________________________________________________________ G/ Load Mg.sub.2 Si MoSi.sub.2 TaSi.sub.2 Al C + G R TCR Noise TestNo. mol % mol % mol % mol % weight % .OMEGA./sq ppm/C..degree. db .DELTA.R/R (%)__________________________________________________________________________1 10 81 9 -- 93 3.0.sup.k +50 -15 0.12 90 700 +80 -23 03 80 120 +160 -25 04 50 15 +300 -26 05 10 72 18 -- 93 3.2.sup.k +45 -14 0.156 90 950 +60 -22 07 80 160 +130 -26 08 50 17 +280 -20 09 10 63 27 -- 93 6.5.sup.k +25 -10 0.1510 90 2.0.sup.k +35 -14 011 80 250 +100 - 22 012 50 23 +200 -24 013 20 72 8 -- 93 3.8.sup.k +45 -15 0.1214 90 1.2.sup.k +60 -20 015 80 200 +95 -25 016 50 18 +165 -25 017 20 64 16 -- 93 4.1.sup.k +20 -14 0.1018 90 1.7.sup.k +35 -18 019 80 220 +80 -26 020 50 20 +150 -27 021 20 56 24 -- 93 16.0.sup.k -10 -6 0.2122 90 5.1.sup.k 0 -15 0.0823 80 480 +15 -25 024 50 34 +50 -26 025 40 50 10 -- 93 13.sup.k -20 -1 0.526 90 4.2.sup.k -5 -10 0.227 80 520 +10 -25 028 50 41 +72 -25 029 40 45 15 -- 93 18.5.sup.k +45 +5 0.730 90 7.0.sup.k -30 -8 0.231 80 820 -2 -25 032 50 79 +83 -26 033 40 35 20 -- 93 22.sup.k -78 +10 0.934 90 10.sup.k -40 -17 0.435 80 970 -8 -22 036 50 102 +99 -20 037 55 40 5 -- 93 28.sup.k -60 +5 0.4238 90 8.2.sup.k -14 -10 0.2039 80 580 +6 -25 040 50 39 +90 -25 041 55 35 10 -- 93 32.sup.k -80 +8 0.8242 90 10.sup.k -20 -12 0.1843 80 708 +2 -21 044 50 45 +85 -20 045 55 30 15 -- 93 42.sup.k -100 +15 1.2046 90 13.sup.k -32 -10 0.4347 80 1.02.sup.k -13 -18 048 50 86 -72 -23 049 70 27 3 -- 93 41.sup.k -50 +10 2.150 90 15.sup.k 015 -6 0.8051 80 900 -10 -11 052 50 42 +60 -25 053 70 24 6 -- 93 51.sup.k -75 +13 3.054 90 17.sup.k -20 -2 0.3255 80 930 -15 -7 056 50 51 +55 -25 057 70 21 9 -- 93 71.sup.k -120 +19 5.558 90 20.sup.k -30 + 2 0.5059 80 1.0.sup.k -20 -7 060 50 55 +43 -26 0__________________________________________________________________________
TABLE 2__________________________________________________________________________ G/ Load Mg.sub.2 Si MoSi.sub.2 TaSi.sub.2 Al C + G R TCR Noise TestNo. mol % mol % mol % mol % weight % .OMEGA./sq ppm/C..degree. db .DELTA.R/R (%)__________________________________________________________________________61 40 40 10 10 95 42.sup.k -150 -8 0.0762 90 18.sup.k -80 -15 063 80 2.2.sup.k +5 -25 064 50 430 +17 -25 065 30 48 12 10 95 35.sup.k -100 -10 0.0766 90 15.sup.k -25 -18 067 80 1.8.sup.k +10 -25 068 50 370 +25 -25 069 20 56 14 10 95 30.sup.k -50 -12 0.0370 90 12.sup.k -5 -20 071 80 1.2.sup.k + 23 -25 072 50 400 +31 -25 073 40 32 8 20 95 78.sup.k -290 0 0.0974 90 35.sup.k -100 -10 075 80 2.7.sup.k -10 -20 076 50 170 +2 -25 077 30 40 10 20 95 63.sup.k -236 -2 0.0578 90 31.sup.k -78 -13 079 80 2.2.sup.k -2 -20 080 50 152 +13 -25 081 20 48 12 20 95 55.sup.k -184 -5 0.0682 90 26.sup.k -47 -15 083 80 1.9.sup.k +3 -23 084 50 130 +22 -25 085 40 24 6 30 95 350.sup.k -470 +15 0.4786 90 108.sup.k -190 -2 0.1587 80 23.sup.k -20 -12 088 50 850 +4 -20 089 30 32 8 30 95 302.sup.k -400 +13 0.4090 90 98.sup.k -160 -3 0.1291 80 20.sup.k -0.5 -13 092 50 720 +3 -20 093 20 40 10 30 95 270.sup.k -380 +20 0.4094 90 83.sup.k -157 -5 0.1095 80 17.sup.k -18 -15 096 50 560 +12 -23 097 40 16 4 40 95 1.1.sup.M -700 +25< 3.5098 90 210.sup.k -300 +10 0.5099 80 53.sup.k -150 +7 0.10100 50 2.4.sup.k -3 -20 0101 30 24 6 40 95 740.sup.k -630 +25 2.70102 90 160.sup.k -252 +6 0.30103 80 42.sup.k -70 -5 0.05104 50 1.6.sup.k +7 -23 0105 20 32 8 40 95 630.sup.k -605 +25 1.80106 90 97.sup.k -156 +2 0.35107 80 23.sup.k -17 -10 0.05108 50 1.1.sup.k +13 -25 0109 30 16 4 50 95 3.4.sup.M -1000 +25< 15.6110 90 450.sup.k -500 +25< 4.5111 80 180.sup.k -160 +13 0.75112 50 58.sup.k -60 0 0.1113 20 20 10 50 95 1.8.sup.M -850 +25< 12114 90 260.sup.k -320 +25< 1.25115 80 110.sup.k -160 +10 0.3116 50 51.sup.k -60 -0.5 0.05__________________________________________________________________________

Number	Name	Date
3027332	Media	Mar 1962
3119717	Veres	Jan 1964
4119573	Ishida et al.	Oct 1978
4183830	Chester	Jan 1980

Glaze resistor composition

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