CN100465131C - Niobic acid sodium potassium lithium radical leadless piezo-electric ceramic and preparation method thereof - Google Patents

Niobic acid sodium potassium lithium radical leadless piezo-electric ceramic and preparation method thereof Download PDF

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CN100465131C
CN100465131C CNB2007100996756A CN200710099675A CN100465131C CN 100465131 C CN100465131 C CN 100465131C CN B2007100996756 A CNB2007100996756 A CN B2007100996756A CN 200710099675 A CN200710099675 A CN 200710099675A CN 100465131 C CN100465131 C CN 100465131C
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acid sodium
sintering
potassium
niobic acid
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CN101062864A (en
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张波萍
赵培
李松杰
丁小年
张海龙
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University of Science and Technology Beijing USTB
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Abstract

The invention discloses a preparing method of niobic acid sodium potassium lithium group leadless piezoelectric ceramic in green energy source material domain, which comprises the following steps: expressing component of niobic acid sodium potassium lithium group as non-stoichiometric ratio general formula (NaaKbLic)(NbxTaySbz)O3 or -nM; expressing a, b, c as A bit element; expressing x, y, z as mole fraction of B bit element; setting the selective rage as (0<=a<=1. 5, 0<=b<=1. 5, 0<c<=1. 5, 1<a+b+c<=3, 0<x<=1. 5, 0<=y<=1. 5, 0<=z<=1. 5, 1<(a+b+c)/(x+y+z)<=3 or 0. 2<(a+b+c)/(x+y+z)<1, 0<n<=1); choosing M from the oxide or composite oxide of calcium, copper, manganese, barium, yttrium, strontium, titanium, zirconium, lanthanum, magnesium, aluminum, silicon, ferric, cobalt, nickel, silver, tin, antimony and wolfram; adopting commercial raw material; balling; baking; caking under normal pressure; getting the product. This invention possesses good ferro-electricity property, which electromechanical coupling factor Kp can reach 10-50%.

Description

A kind of niobic acid sodium potassium lithium radical leadless piezo-electric ceramic and preparation method thereof
Technical field
The invention belongs to environmentally friendly field of energy source materials, a kind of potassium-sodium niobate lithium radical leadless piezo-electric ceramic material and preparation method thereof particularly is provided.
Background technology
The piezoceramic material of widespread use at present is Pb (Ti, Zr) O 3(PZT), PbTiO 3-PbZrO 3-ABO 3(ABO 3Be the composite perofskite type ferroelectrics) and PbTiO 3On the lead base pottery, wherein Qian massfraction is approximately 70%.This class pottery produce, use and discarded last handling process in cause serious harm all can for the mankind and ecotope, the exploitation leadless piezoelectric material material is imperative.The leadless piezoelectric ceramics of having reported at present has tungsten bronze structure ceramic systems, potassium niobate base ceramic systems, bismuth laminated ceramic systems and barium titanate ceramics system, and wherein the columbate leadless piezoelectric ceramics is to be hopeful to replace one of system that contains lead piezoelectric ceramics most.2004 document 1 (Nature, 2004 Vol 432, p 84-87) reported the piezoelectric property of the niobate base lead-free piezoelectric ceramic of lithium, tantalum and the common modification of antimony, can reach 416pC/N through the piezoelectric constant of the textured ceramic of template preparation.But for normal pressure-sintered and without the potassium-sodium niobate pottery of any modification, (Applied Physics Letter.2004, Vol 85, report that p412) its piezoelectric constant has only 97pC/N according to document 3.Document 4 (Applied Physics Letter.2005, Vol 59, p241-244) and document 5 (Applied Physics Letter.2006, Vol 88, p212) reported by adding the piezoelectric property that modifying element can improve potassium-sodium niobate base pottery effectively, document 7 (Journal of American Society.1962, Vol 45, p209-13) and document 8 (MaterialsScience Forum.2005, p475-479) report advanced preparation technologies such as utilizing hot pressed sintering and discharge plasma sintering, obtained well behaved dense ceramic material.By means such as element modified and optimal preparation technology, the piezoelectric property of unleaded potassium-sodium niobate base pottery is significantly improved, and is constantly approaching actual application level, and the patent content published of this field is as follows at present.Patent CN1609047A discloses crystallization orientation ceramic and preparation method, and this ceramic general formula is: { Li x(K 1-yNa y) 1-x{ Nb 1-z-wTa zSb wO 3, 0≤x≤0.2,0≤y≤1,0≤z≤0.4 wherein, 0≤w≤0.2, x+z+w〉0, it is characterized in that based on potassium-sodium niobate, add modifying elements such as lithium, tantalum, antimony, and be made into stupalith on this basis, do not comprise polycrystalline ceramic with texture structure.Patent CN1810711A discloses a kind of high curie point niobic acid sodium potassium lithium radical leadless piezo-electric ceramic and preparation method, and the general formula of pottery can be expressed as: (1-u) [(1-z) (Li xNa yK 1-x-y) NbO 3+ zMTiO 3]+uMnO 2Wherein x, y, z represent respective element material shared atomic percent in each constituent element in the compound ion, and all total atom numbers and be 1,0.01≤x≤0.2,0.2≤y≤0.7,0.01≤z≤0.25,0≤u≤0.05, it is characterized in that on the basis of niobic acid sodium potassium lithium the titanate or the oxide compound that add one or more Mg, Ca, Sr, Ba carry out modification.Patent CN1884198A discloses niobium tantalic acid sodium potassium based leadless piezoelectric ceramics and preparation method, its feature with based on niobium tantalic acid sodium potassium, the general formula of base-material is: (K 1-xNa x) (Nb 1-yTa y) O 3X=0.1～0.9 wherein, y=0.01～0.30), add Cu on this basis 2+, Sb 5+, Sn 4+, Li +In any or appoint several modifications of carrying out.Patent CN1511802A discloses a class multi constituent niobate lead-free piezoelectric ceramics, and its claim composition is: (Li xNa yK 1-x-y) (Nb 1-zR z) O 3Or add one or more LMnO on this basis 3, in the formula, 0＜x≤0.3,0＜y＜1,0＜(x+y)＜1,0≤z≤0.4, R is Ta or Sb or both compound ions, L is Y, Er, Ho, Dy, Tm, Lu, Yb, Lu, Nd, Sm rare earth metals element, LMnO 3Adding proportion be 0-17wt%, (Li xNa yK 1-x-y) (Nb 1-zR z) O 3Ratio be 83-17wt%.The feature of this patent is based on niobic acid sodium potassium lithium, at first by Ta, Sb Nb is carried out the B position and replaces, and carries out the rare earth metals element doping then.Patent CN1644562A discloses potassium-sodium niobate system leadless piezoelectric ceramics and preparation method thereof.Though patent CN1388089A has reported that with Na, Li, Nb and O element be the perovskite structure compound that main component constitutes, its general formula is: (1-u) [(1-z) Na 1-xLi x) 1-yK y] (Nb 1-zTa z) O 3-nM1M2O 3, wherein, 0.02≤x≤0.3,0≤y≤0.2,0≤z≤0.2,0≤n≤0.1, M1 is a divalent metal, M2 is a tetravalent metal, but its interpolation element not only has tantalum, also have other metallic elements, and the molar fraction of potassium is between 0～0.2.Up to the present the common trait of disclosed patent be exactly the general formula of stupalith be ABO 3, A position atomic mole fraction sum is 1, that is to say that they all belong to the stoichiometric ratio category.Patent CN1919791A discloses potassium-sodium niobate based leadless piezoelectric ceramics and the intermediate frequency resonator thereof of a kind of high Qm, it is characterized in that based on potassium-sodium niobate, and its general formula is (Na xK 1-x+ δ) Nb 1+zO 3+ wmolCuO, 0≤x in the formula≤1,0≤δ≤0.1,0≤z≤0.2,0≤w≤0.1, doped with Cu O realizes high resonance then.Though the disclosure patent is the patent that present unique A of relating to position atomic mole fraction sum comprises a part of non-stoichiometric composition, does not contain elemental lithium, its piezoelectric constant is on the low side only to be 90～120.
Summary of the invention
The object of the present invention is to provide a kind of niobic acid sodium potassium lithium radical pottery and preparation method thereof with high piezoelectric constant.Patent is at the niobate base lead-free piezoelectric ceramic piezoelectric constant d of present ordinary sinter method preparation 33Lower defective provides a kind of composition design with niobic acid sodium potassium lithium radical leadless piezo-electric ceramic of high piezoelectric constant, and this composition relates to the non-stoichiometric category, its piezoelectric constant d 33Be not less than 150pC/N.
The moiety of a kind of niobic acid sodium potassium lithium radical pottery provided by the invention can be used general formula (Na aK bLi c) (Nb xTa ySb z) O 3Expression, wherein a, b, c represent that A position composition element, x, y, z represent the molar fraction of B position composition element, the range of choice of numerical value is: 0≤a≤1.5,0≤b≤1.5,0＜c≤1.5,1＜a+b+c≤3,0＜x≤1.5,0≤y≤1.5,0≤z≤1.5,1＜(a+b+c)/(x+y+z)≤3 or 0.2＜(a+b+c)/(x+y+z)＜1.
The present invention also provides a kind of piezoelectric ceramics that a kind of or a kind of hotchpotch is formed that adds on the basis of above-mentioned general formula, with general formula (Na aK bLi c) (Nb xTa ySb z) O 3-nM represents, 0≤a≤1.5,0≤b≤1.5,0＜c≤1.5 wherein, 1＜a+b+c≤3,0＜x≤1.5,0≤y≤1.5,0≤z≤1.5,1＜(a+b+c)/(x+y+z)≤3 or 0.2＜(a+b+c)/(x+y+z)＜1,0＜n≤1, M is at least a in the oxide compound of calcium, copper, manganese, barium, yttrium, strontium, titanium, zirconium, lanthanum, magnesium, aluminium, silicon, iron, cobalt, nickel, silver, tin, antimony and tungsten or the composite oxides, n represents the molar fraction of M component.
Preparation method of the present invention is a batching after according to the non-stoichiometric general formula raw materials by weight being weighed, and confected materials is that medium carries out batch mixing in the mode of ball milling or vibration with the dehydrated alcohol, and the time is 1-8 hour, and oven dry obtains dry powder; With the dry powder roasting, maturing temperature 500-900 ℃, be incubated 1-10 hour, carry out the synthetic of niobate; With the compression moulding in the mould of φ 5-30mm of packing into of pre-burning synthetic powder, put sintering in the sintering oven then into, under 600-1200 ℃ of temperature in the atmosphere, heat preservation sintering 1-5 hour; Potassium-sodium niobate series piezoelectric ceramic disk is coated with roasting silver electrode, polarizes in silicone oil, the polarization temperature is 80-200 ℃, and the time is 10-60min, and voltage is 1-10kV/mm, carries out every electrical performance testing after polarization is finished.
Non-stoichiometric general formula of the present invention is: (Na aK bLi c) (Nb xTa ySb z) O 3Expression, wherein a, b, c represent that A position composition element, x, y, z represent the molar fraction of B position composition element, the range of choice of numerical value is: 0≤a≤1.5,0≤b≤1.5,0＜c≤1.5,1＜a+b+c≤3,0＜x≤1.5,0≤y≤1.5,0≤z≤1.5,1＜(a+b+c)/(x+y+z)≤3 or 0.2＜(a+b+c)/(x+y+z)＜1; Perhaps, (Na aK bLi c) (Nb xTa ySb z) O 3-nM represents, 0≤a≤1.5,0≤b≤1.5,0＜c≤1.5 wherein, 1＜a+b+c≤3,0＜x≤1.5,0≤y≤1.5,0≤z≤1.5,1＜(a+b+c)/(x+y+z)≤3 or 0.2＜(a+b+c)/(x+y+z)＜1,0＜n≤1, M is at least a in the oxide compound of calcium, copper, manganese, barium, yttrium, strontium, titanium, zirconium, lanthanum, magnesium, aluminium, silicon, iron, cobalt, nickel, silver, tin, antimony and tungsten or the composite oxides, n represents the molar fraction of M component.
The polynary system piezoelectric ceramics that the present invention proposes has following advantage:
(1) good piezoelectric property, its piezoelectric constant d 33Be not less than 150pC/N;
(2) good ferroelectric performance is shown in the ferroelectric hysteresis loop figure of Fig. 1 piezoelectric ceramics sample;
(3) electromechanical coupling factor Kp reaches 10-50%; Having reached can the actual performance index of using.
Description of drawings
Fig. 1 is ferroelectric hysteresis loop figure.
Embodiment:
Piezoelectric ceramics sample of the present invention utilizes the solid-phase sintering process preparation, and its process comprises grinding batch mixing, roasting synthetic in advance niobate, fine grinding, adds technical process such as caking agent, moulding, solid state sintering, grind away, quilt silver, polarization.Be specially: according to general formula (Na aK bLi c) (Nb xTa ySb z) O 3Batching after-nM weighs raw materials by weight, confected materials is that medium carries out batch mixing in the mode of ball milling or vibration with the dehydrated alcohol, the time dries and obtains dry powder after being 1-8 hour; With the dry powder roasting, maturing temperature 500-900 ℃, be incubated 1-10 hour, carry out the synthetic of niobate; With the compression moulding in the mould of φ 5-30mm of packing into of pre-burning synthetic powder, put sintering in the sintering oven then into, under 600-1200 ℃ of temperature in the atmosphere, heat preservation sintering 1-5 hour; Potassium-sodium niobate series piezoelectric ceramic disk is coated with roasting silver electrode, polarizes in silicone oil, the polarization temperature is 80-200 ℃, and the time is 10-60min, and voltage is 1-10kV/mm.After finishing, polarization carries out every electrical performance testing.
Exemplifying following embodiment is specified the present invention.
Provide 2-3 specific examples below.
Example 1: at first raw material is pressed equation (Na 0.569Kb 0.485Li 0.40) (Nb 0.850Ta 1..5) O 3Carry out weighing, the quality of each material is: 0.7912g yellow soda ash, 0.9255g salt of wormwood, 0.1255g Quilonum Retard 3.5581g Niobium Pentxoxide, 6.5713g tantalum pentoxide.Raw material and put into ball grinder, adding the 30ml dehydrated alcohol is medium, and ball milling is 1 hour under 160 rev/mins rotating speed, shift the material oar and 80 ℃ dry 8 hours down.Powder after will drying then was 500 ℃ of roasting temperatures 10 hours.The compression moulding in the mould of φ 20mm of packing into of pre-burning synthetic powder.Put the powder after the moulding in sintering oven sintering then, under 600 ℃ of temperature in the atmosphere, heat preservation sintering 5 hours.Potassium-sodium niobate series piezoelectric ceramic disk is coated with roasting silver electrode, polarizes in silicone oil, temperature progressively is raised to 100 ℃ by room temperature during polarization, is 10 minutes in the 1kV/mm time then.
Example two: at first raw material is pressed equation (Na 0.716K B 0.630Li 0.823) (Nb 0.220Ta 0.213Sb 0.421) O 3Carry out weighing, the concrete quality of each material is: 0.2395g yellow soda ash, 0.3722g salt of wormwood, 1.2197g Niobium Pentxoxide, 2.4293g tantalum pentoxide, 0.1520g Quilonum Retard, 2.45126 antimonous oxides.Raw material and put into ball grinder, adding the 30ml dehydrated alcohol is medium, and ball milling is 1 hour under 160 rev/mins rotating speed, shift the material oar and 80 ℃ dry 8 hours down.Powder after will drying then was 900 ℃ of roasting temperatures 1 hour.The compression moulding in the mould of φ 5mm of packing into of pre-burning synthetic powder.Put the powder after the moulding in sintering oven sintering then, under 1200 ℃ of temperature in the atmosphere, heat preservation sintering 5 hours.Potassium-sodium niobate series piezoelectric ceramic disk is coated with roasting silver electrode, polarizes in silicone oil, temperature progressively is raised to 80 ℃ by room temperature during polarization, is 10 minutes in the 2kV/mm time then.
Example three: at first raw material is pressed equation (Na 0.456K B 0.630Li 0.412) (Nb 0.360Ta 0.213Sb 0.421) O 3-0.045-CaO carries out weighing, and the concrete quality of each material is: 0.4295g yellow soda ash, 0.6522g salt of wormwood, 3.1197g Niobium Pentxoxide, 4.7164g tantalum pentoxide, 0.3521g Quilonum Retard, 6.3124 antimonous oxides, 0.1211g calcium oxide.Raw material and put into ball grinder, adding the 30ml dehydrated alcohol is medium, and ball milling is 8 hours under 160 rev/mins rotating speed, shift the material oar and 80 ℃ dry 8 hours down.Powder after will drying then was 700 ℃ of roasting temperatures 3 hours.The compression moulding in the mould of φ 16mm of packing into of pre-burning synthetic powder.Put the powder after the moulding in sintering oven sintering then, under 1020 ℃ of temperature in the atmosphere, heat preservation sintering 5 hours.Potassium-sodium niobate series piezoelectric ceramic disk is coated with roasting silver electrode, polarizes in silicone oil, temperature progressively is raised to 200 ℃ by room temperature during polarization, is 60 minutes in the 1kV/mm time then.
Example four: at first raw material is pressed equation (Na 0.463K B0.620Li 0.420) (Nb 0.126Ta 0.713Sb 0.421) O 3-0.036-SrO carries out weighing, and the concrete quality of each material is: 0.2395g yellow soda ash, 0.3722g salt of wormwood, 1.2197g Niobium Pentxoxide, 11.3164g tantalum pentoxide, 0.2525g Quilonum Retard, 6.0671 antimonous oxides, 0.3311g strontium oxide.Raw material and put into ball grinder, adding the 30ml dehydrated alcohol is medium, and ball milling is 6 hours under 160 rev/mins rotating speed, shift the material oar and 80 ℃ dry 8 hours down.Powder after will drying then was 750 ℃ of roasting temperatures 4 hours.The compression moulding in the mould of φ 30mm of packing into of pre-burning synthetic powder.Put the powder after the moulding in sintering oven sintering then, under 1040 ℃ of temperature in the atmosphere, heat preservation sintering 3 hours.Potassium-sodium niobate series piezoelectric ceramic disk is coated with roasting silver electrode, polarizes in silicone oil, temperature progressively is raised to 100 ℃ by room temperature during polarization, is 20 minutes in the 10kV/mm time then.
Provided several preferred embodiments of the present invention in the following table.D wherein 33, Kp, ε, tan δ represent piezoelectric constant, electromechanical coupling factor, specific inductivity and dielectric loss respectively.
Embodiment:
Sample Sintering temperature (℃) a b c x y z n Element d 33(pC/N)
1 1050 0.000 1.500 0.010 1.000 0.000 0.000 0.000 Do not have 165
2 1060 0.525 0.485 0.010 0.100 0.000 0.820 0.000 Do not have 191
3 1040 0.569 0.485 0.040 0.850 1.500 0.000 0.000 Do not have 230
4 1070 0.530 0.490 0.055 1.500 0.000 0.000 0.000 Do not have 243
5 1060 0.540 0.490 0.070 0.100 0.000 1.500 0.000 Do not have 187
6 1130 0.550 1.500 0.080 0.140 0.040 1.205 0.000 Do not have 247
7 1040 0.612 0.560 0.021 0.160 0.600 0.600 0.000 Do not have 160
8 970 0.740 0.570 0.640 0.149 0.400 0.101 0.000 Do not have 304
9 1090 0.760 0.580 0.650 0.180 0.210 0.360 0.000 Do not have 210
10 1050 0.800 0.620 0.760 0.200 0.680 0.631 0.000 Do not have 185
11 1130 0.716 0.630 0.823 0.220 0.213 0.421 0.000 Do not have 176
12 900 0.100 0.710 0.954 0.260 0.362 0.325 1.000 Mg 190
13 980 1.100 0.630 1.000 0.360 0.412 0.541 0.450 Ca 178
14 1160 1.200 0.600 1.200 0.950 0.060 0.214 0.692 Sr 216
15 1120 1.500 0.000 1.500 0.160 0.860 0.258 0.250 Ba 203
16 940 0.542 0.531 0.042 0.213 0.080 0.165 0.564 Cu 195
17 1160 1.300 0.501 0.006 0.546 0.094 0.370 0.587 Mn 234
18 1130 1.500 0.000 1.400 0.800 0.758 0.140 0.366 Y 212
19 1040 0.055 0.251 0.354 0.945 1.450 0.885 0.450 Ti 248
20 1080 0.015 0.250 0.956 0.150 0.250 1.230 1.000 Zr 173
21 1180 1.500 0.000 1.430 0.160 0.763 0.140 0.680 La 201
22 1000 0.325 0.982 1.215 0.544 0.250 1.032 0.460 Al 186
23 1170 0.256 0.248 1.341 0.135 0.065 0.968 0.853 Si 215
24 980 0.464 0.780 0.896 0.160 0.386 0.352 0.574 Fe 224
25 1130 0.768 0.512 1.500 0.165 0.452 0.481 0.056 Co 258
26 1040 0.257 1.156 1.356 0.089 0.847 0.150 0.745 Ni 196
27 1000 0.348 0.257 1.224 0.202 0.460 0.147 0.032 Ag 185
28 1050 1.266 0.000 1.047 0.308 0.068 0.572 0.227 Sn 168
29 1090 0.209 0.636 0.350 0.453 0.758 0.142 0.792 Sb 210
30 1180 0.503 0.967 0.706 0.569 0.066 0.459 0.358 W 225

Claims (4)

1, a kind of potassium-sodium niobate lithium radical leadless piezo-electric ceramic with high tension performance is characterized in that, with non-stoichiometric general formula (Na aK bLi c) (Nb xTa ySb z) O 3Expression, wherein a, b, c represent that A position composition element, x, y, z represent the molar fraction of B position composition element, the range of choice of numerical value is: 0≤a≤1.5,0≤b≤1.5,0＜c≤1.5,1＜a+b+c≤3,0＜x≤1.5,0≤y≤1.5,0≤z≤1.5,1＜(a+b+c)/(x+y+z)≤3 or 0.2＜(a+b+c)/(x+y+z)＜1.
2, according to claim 1 leadless piezoelectric ceramics, it is characterized in that, add one or more hotchpotchs and formed piezoelectric ceramics, with non-stoichiometric general formula (Na aK bLi c) (Nb xTa ySb z) O 3-nM represents, 0≤a≤1.5,0≤b≤1.5,0＜c≤1.5 wherein, 1＜a+b+c≤3,0＜x≤1.5,0≤y≤1.5,0≤z≤1.5,1＜(a+b+c)/(x+y+z)≤3 or 0.2＜(a+b+c)/(x+y+z)＜1,0＜n≤1, n represents the molar fraction of M component, M is at least a in the oxide compound of calcium, copper, manganese, barium, yttrium, strontium, titanium, zirconium, lanthanum, magnesium, aluminium, silicon, iron, cobalt, nickel, silver, tin, antimony and tungsten or the composite oxides.
3. method for preparing claim 1 or 2 described leadless piezoelectric ceramicss, it is characterized in that, according to the non-stoichiometric general formula with weigh back batching of raw materials by weight, confected materials is that medium carries out batch mixing in the mode of ball milling or vibration with the dehydrated alcohol, time is 1-8 hour, and oven dry obtains dry powder; With the dry powder roasting, maturing temperature 500-900 ℃, be incubated 1-10 hour, carry out the synthetic of niobate; With the compression moulding in the mould of φ 5-30mm of packing into of pre-burning synthetic powder, put sintering in the sintering oven then into, under 600-1200 ℃ of temperature in the atmosphere, heat preservation sintering 1-5 hour; Potassium-sodium niobate series piezoelectric ceramic disk is coated with roasting silver electrode, polarizes in silicone oil, the polarization temperature is 80-200 ℃, and the time is 10-60min, and voltage is 1-10kV/mm, carries out every electrical performance testing after polarization is finished.
4, in accordance with the method for claim 3, it is characterized in that described non-stoichiometric general formula is: (Na aK bLi c) (Nb xTa ySb z) O 3Expression, wherein a, b, c represent that A position composition element, x, y, z represent the molar fraction of B position composition element, the range of choice of numerical value is: 0≤a≤1.5,0≤b≤1.5,0＜c≤1.5,1＜a+b+c≤3,0＜x≤1.5,0≤y≤1.5,0≤z≤1.5,1＜(a+b+c)/(x+y+z)≤3 or 0.2＜(a+b+c)/(x+y+z)＜1; Perhaps, (NaK bLic) (Nb xTa ySb z) O 3-nM represents, 0≤a≤1.5,0≤b≤1.5,0＜c≤1.5 wherein, 1＜a+b+c≤3,0＜x≤1.5,0≤y≤1.5,0≤z≤1.5,1＜(a+b+c)/(x+y+z)≤3 or 0.2＜(a+b+c)/(x+y+z)＜1,0＜n≤1, M is at least a in the oxide compound of calcium, copper, manganese, barium, yttrium, strontium, titanium, zirconium, lanthanum, magnesium, aluminium, silicon, iron, cobalt, nickel, silver, tin, antimony and tungsten or the composite oxides, n represents the molar fraction of M component.
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