CN104439247A - Molybdenum alloy target preparation method - Google Patents
Molybdenum alloy target preparation method Download PDFInfo
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Abstract
The invention belongs to the technical field of material processing, and particularly relates to a molybdenum alloy target preparation method. Alloy powder is formed by molybdenum powder and other metal powder in a mechanical alloying mode, the alloy powder is processed, and a molybdenum alloy target is obtained. The mechanical alloying process is adopted, so that distribution uniformity and alloying performance of the powder raw materials are better; hot isostatic pressing is conducted after cold isostatic pressing, so that the compactness of the molybdenum alloy target is better; through the multi-stage degassing process, the oxygen content of the molybdenum alloy target is lower, and the degassing performance is better.
Description
Technical field
The invention belongs to materials processing technology field, be specifically related to a kind of preparation method of molybdenum alloy target.
Background technology
Molybdenum is a kind of transition metal of grey, belongs to refractory metal, is positioned at VI A subgroup in the periodic table of elements, and ordinal number is 42, atomic weight 95.94.Mo and Mo alloys has excellent electrical conductance and heat endurance.Electrode, wiring material or barrier material in manufacturing using molybdenum alloy as TFT have application prospect.The specific luminance of device, contrast, color and life-span is improved by the advantage of molybdenum alloy sputtering target.The more important thing is, use molybdenum titanium sputtering target than using chromium sputtering target material and more meet environmental protection.Therefore, Mo and Mo alloys instead of the manufacture that chromium is applied to the flat panel display devices such as liquid crystal display at present.
Magnetron sputtering molybdenum alloy target is generally divided into plane formula (being wherein divided into again rectangular slat formula and disc type) target and the rotary target of pipe two kinds with geometry.Due to the comprehensive function in its electric field, magnetic field, planar target is extremely uneven at the sputter rate of whole sputtering plane, and so-called " runway district " can be formed etch deep trench, once this " runway district " etches deep trench run through target, then target cancels, and therefore the stock utilization of planar target is generally about 25% ~ 30%; For avoiding this shortcoming, can adopt circular pipe type rotary target material, due to the basically identical property of the sputter rate along target axial direction material, its stock utilization generally can reach about 70%.
Mo and Mo alloys target is the raw material making Mo metal film electrode in TFT-LCD array processes, and its quality directly affects final tft array properties of product.Be mainly manifested in aspects such as the strict overall uniformities of the chemical purity of target material and maximum segregation value, packing, microscopic structure (grain size, grain size) and its microstructure and various performance to the quality requirement of Mo and Mo alloys target, to TFT High-Purity Molybdenum target, its purity is not less than 99.95% (3N5); Packing is not less than 99.8%; Grain size size is not more than 100 μm; Surface roughness is not less than 0.8 μm; Thickness deviation ± 0.10mm; Target plane degree or cylindricity 0.10mm.
In order to there be good spatter film forming performance, require that the size of molybdenum and target crystalline grains degree thereof and the uniformity of grain size in overall target will be got well.Mo and Mo alloys target generally with the delivery of stress relief annealing state, does not allow, in microscopic structure, recrystallization phenomenon occurs.
The production technology of molybdenum alloy target divides nothing more than two kinds with the reparation technology of target blank, and a kind of is vacuum melting casting, and one is powder metallurgic method.Melting and casting method refers to the alloy raw material melting of certain ingredients proportioning, then is cast in mould by alloy solution, forms ingot casting, makes target finally by machining.For ensureing that in ingot casting, impurity content is low as far as possible, melting and casting method carries out melting and casting in a vacuum.But in casting process, there is certain porosity in material structure inside, these porositys can cause the particulate in sputter procedure to splash, thus affect the quality of sputtered film unavoidably.For this reason, subsequent thermal processing and Technology for Heating Processing is needed to reduce its porosity.The alloy phase ratio prepared with powder method, the impurity content (particularly gaseous impurity) of molten alloy target is low, and can densification, maximization.Conventional method of smelting has vacuum induction melting, vacuum arc melting and vacuum electronic bombardment melting etc.But for the alloy material of fusing point and all very large two or more metal composition of density, the alloy target material adopting common smelting process to be generally difficult to obtain chemical analysis and phase composition to be evenly distributed.
Powder sintering mainly for the making problem of refractory metal sputtering targets material, have easily obtain even aplitic texture, save material, production efficiency advantages of higher.Utilize the method to select high-purity, superfines as raw material, select the shaping sintering technology that can realize quick densifying, to ensure the low porosity of target, and control grain size, and the strict introducing controlling impurity element in preparation process.It is even that powder sintering obtains target material composition, but there is the problems such as density is low, impurity content is high.
The production of current TFT High-Purity Molybdenum target generally all adopts the method for powder metallurgy.Through selecting powder, mixed powder, cold isostatic compaction, sintering, hot shaping processing, destressing heat treatment, manufacturing defect Non-Destructive Testing, machined, manual grinding, carry on the back the operations such as target soldering, brazing quality Non-Destructive Testing, vacuum packaging delivery with copper and complete the whole production process of molybdenum target material.And the method for high temperature insostatic pressing (HIP) is generally adopted for the molybdenum alloy target of touch screen every trade industry, by selecting powder, mixed powder, cold isostatic compaction, hip moulding, manufacturing defect Non-Destructive Testing, machined, manual grinding, carry on the back the operations such as target soldering, brazing quality Non-Destructive Testing, vacuum packaging delivery with copper and complete the whole production process of molybdenum alloy target.
For obtaining the good target of performance, it is generally acknowledged use molybdenum powder should chemical purity high, powder particle granularity is moderate and reunion degree (especially hard aggregation) light, grain shape subglobular as much as possible between its narrowly distributing, powder particle.
The shaping general employing isostatic cool pressing mode of biscuit.Isostatic cool pressing dwell pressure about 200MPa, 15 ~ 20 minutes dwell times.
Conventional powder metallurgical sintering process comprises that hydrogen atmosphere is normal pressure-sintered, vacuum or hydrogen atmosphere hot pressing and high temperature insostatic pressing (HIP) etc.Wherein high temperature insostatic pressing (HIP) method is because sintering temperature is low, sintered body packing is high, sintered body grain size is tiny and be subject to increasing favor.
Chinese invention patent 201210291768.X provides a kind of preparation method of molybdenum target material, and the method is by molybdenum ingot through adding hot extrusion, smooths after heats forged and heating rolling, then obtains molybdenum target material according to finished size blanking, milling and surface treatment.Can obtain by preparation method of the present invention the molybdenum target material that crystallite dimension, relative density and product size all meet plated film industry requirement, experiment display, prepare molybdenum target material crystallite dimension between 120-160 μm by the present invention, relative density is greater than 99%.
Chinese invention patent 201310578124.3 provides a kind of preparation method of molybdenum niobium 10 target, first by molybdenum powder and be divided into three aliquot niobium powder, then the niobium powder of the molybdenum powder of three aliquots and three aliquots is mixed to get three parts of molybdenum niobium mixed powders respectively between two, then three parts of molybdenum niobium mixed powders is put into respectively Vacuum mixer and carry out 48 hours batch mixings and obtain three parts of mixed powders; Just three parts of mixed powders are mixed into one again, again carry out 48 hours batch mixings and the molybdenum niobium mixed powder that sieves to obtain in Vacuum mixer; Be ingot blank by molybdenum niobium mixed powder by cold isostatic compaction, put into heat after shaping again and wait press to suppress, pressure 230MPa, temperature 1400 DEG C, is incubated 4 hours, makes alloy ingot blank; Finally alloy ingot blank is machined to target finished product.Adopt the present invention to produce molybdenum niobium alloy ingot blank, the process-cycle is short, yield rate is high and cost is low, and the alloy ingot blank compactness produced is good, has very high practical value.
Chinese invention patent 201310010396.3 provides a kind of production technology of molybdenum niobium alloy target; it is characterized in that: high-purity molybdenum powder and niobium powder are mixed in batch mixer; niobium powder and molybdenum powder are placed in batch mixer according to the weight ratio of 1:8-9; molybdenum niobium alloy is sintered in 1400 ~ 1900 DEG C of high-temperature vacuum calcining furnaces; agglomerate hydraulic press is broken into after fritter in agate ball grinding machine, grinding under helium protection.Abrading-ball proportioning is 1/3, with revolve round the sun 600 micro mist, compressing in vacuum pressed sintering equipment, pressure 12 ~ 25 MPa, 1450 ~ 2020 DEG C pressure 30 ~ 90 minutes, obtain target base.On grinding machine, finishing obtains finished product target.Method technological process of the present invention is simple, is easy to realize suitability for industrialized production.Pollution-free, preparation process can not produce the pollutants such as any waste material, spent acid.
The preparation method of Chinese invention patent 201310102230.4 1 kinds of molybdenum alloy target.Be characterized in, comprise the steps: first molybdenum powder and niobium powder to be loaded in mould to mix, wherein Mo powder by weight: Nb powder=5 ~ 15:85 ~ 95, then mould is put into sintering furnace and be warming up to 900 ~ 1100 DEG C, be incubated 60 ~ 180 minutes, then 1900 ~ 2200 DEG C are warming up to, be incubated 60 ~ 180 minutes, hydrogen protection is passed in temperature-rise period, pressurization is started while intensification, pressure is 1 ~ 3 ton, when temperature arrives 1850 ~ 2000 DEG C, boost to 4 ~ 7 tons, pressurize 4 ~ 7 tons 2000 ~ 2200 DEG C time, until insulation terminates, insulation terminates rear decrease temperature and pressure, then namely the demoulding of coming out of the stove obtains molybdenum niobium alloy target.The invention provides a kind of with low cost, but the new method of making molybdenum-niobium alloy target that each side such as quality can meet the demands, be mainly used in the fields such as flat-panel monitor.
Chinese invention patent 201110334975.4 provides a kind of preparation method of Mo-Nb alloy board for sputtering target material, and the method is: one, by niobium powder and Fei Shi particle mean size be 3 μm ~ 8 μm molybdenum powder according to 1: 9 mass ratio be placed in batch mixer and be mixed to get compound; Two, vibration compacting is carried out to compound, obtain molybdenum niobium alloy powder pressed compact; Three, molybdenum niobium alloy powder pressed compact is placed in vacuum sintering furnace sinters, obtained molybdenum niobium alloy slab; Four, machine cuts is carried out to molybdenum niobium alloy slab, obtain the Mo-Nb alloy board for sputtering target material of required size.Method technological process of the present invention is simple, and be easy to realize suitability for industrialized production, yield rate is high, and preparation process can not produce the pollutants such as any waste material, spent acid.The density of the molybdenum niobium alloy plate adopting method of the present invention to prepare is not less than 9.85g/cm
3, meet the requirement of sputtering target material.
Chinese invention patent 201310102061.4 provides a kind of preparation method of molybdenum-niobium alloy plate for target material.Be characterized in; comprise the steps: first molybdenum powder and niobium powder to be mixed to get mixed powder according to the mass ratio of 5 ~ 15:85 ~ 95; this mixed powder is pressed into alloy preform; then sinter; hydrogen protection is passed in sintering process; when sintering temperature was to 1000 DEG C of insulations 2 ~ 3 hours; be warmed up to 1700 DEG C of insulations 2 ~ 3 hours again; then 1950 DEG C of insulations 8 ~ 10 hours are warmed up to; finally sinter alloy billet into, then through 1200 ~ 1400 DEG C of high temperature forge make after at 1500 ~ 1600 DEG C, be rolled into sheet material.The invention provides a kind of with low cost, the new method of the molybdenum-niobium alloy plate for target material that each side such as quality can meet the demands, product is mainly used in the fields such as flat-panel monitor.
Chinese invention patent 201310247053.9 provides the preparation method of a kind of high-purity, high-compactness, large-size molybdenum alloy target, belongs to coloured preparation of target materials technical field.Its step comprises: mixed powder, briquetting, pre-burning reduction, application of vacuum, integer, the processing of high temperature insostatic pressing (HIP) jacket, jacket charging, the degassed soldering and sealing of jacket, hip treatment, processed finished products.Molybdenum alloy target planar dimension prepared by the present invention can reach 1300mm × 850mm, and bending strength reaches more than 800MPa, and density reaches more than 99.0%, and purity reaches more than 99.9%.Compared with the technology announced, technique of the present invention has the characteristics and advantages that cost is low, efficiency is high, purity is high, performance is high.
Summary of the invention
The object of this invention is to provide a kind of preparation method of molybdenum alloy target, the target of production has the feature of high-purity, high densification, distributed components.
The preparation method of molybdenum alloy target of the present invention uses metal molybdenum powder and other metal powder to obtain alloy powder by the mode of mechanical alloying, and alloy powder post processing, to obtain final product.
Other described metal powder is one or more in niobium, tantalum, tungsten, vanadium, neodymium, titanium, zirconium, vanadium or chromium, and the content of other metal powder is 0.1-40at%.
The preparation method of molybdenum alloy target of the present invention, step is as follows:
(1) select molybdenum powder and other metal powder as powder material, powder material is tentatively mixed by V-type batch mixer, and then mixed powder is placed in high energy ball mill ball milling;
(2) isostatic cool pressing process is carried out by material powder good for ball milling loading rubber sleeve;
(3) loaded in steel capsule by the powder suppressed, steel capsule reserves pore;
(4) steel capsule is carried out one-phase is degassed, two-stage hydrogen reduction and the degassed process of three stages, then all pores are shut;
(5) jacket manufactured is placed in hot isostatic press carries out HIP sintering;
(6) jacket is removed, alloy pig is cut into and specifies target shape;
(7) density of target, purity, oxygen content, metallographic, crystallite dimension magnetron sputtering becomes film to carry out moisture-proof test is measured.
The maximum particle diameter of the raw material described in step (1) is 1-20 micron, and purity is 99.9-99.999%, and oxygen content is 1-2000ppm.
Incorporation time described in step (1) is 10-30 minute.
The ball selected in mechanical milling process described in step (1) is high compact zirconia ball, and ensure that environmental pressure is 1-50atm, Ball-milling Time is 1-24 hour, protective atmosphere to be purity be 99.999% argon gas.
Isostatic cool pressing processing pressure described in step (2) is 20-200MPa, and the press time is 10-60 minute.
The number of the pore described in step (3) is 1-50.
One-phase degassing temperature described in step (4) is 100-300 DEG C, and degassing time is 2-12 hour, and the pressure in jacket is 1.0 × 10
-2-5.0 × 10
-2pa; Two-stage hydrogen reduction temperature is 500-1000 DEG C, and the hydrogen reduction time is 4-48 hour, and the Hydrogen Vapor Pressure in jacket is 1.0 × 10
4-1.0 × 10
5pa; Three stage degassing temperature are 600-1000 DEG C, and degassing time is 4-48 hour, and the pressure in jacket is 1.0 × 10
-2-5.0 × 10
-2pa.
HIP sintering temperature described in step (5) is 1000-1400 DEG C, and sintering time is 1-12 hour, and sintering pressure is 100-170Mpa.
The relative density of the target described in step (7) is 99-100%, and purity is 99.9-99.999%, and oxygen content is 1-2000ppm, and average grain diameter is 1-100 micron.
Described density measuring method is drainage solid density measuring instrument.
Described purity determination method is ICP-MS.
Described oxygen content measuring/method is nitrogen oxygen analyzer.
Described metallographic and the measuring method of crystallite dimension are metallographic microscope.
Described moisture-proof measuring method for film is placed in temperature is 60 degree, in the sodium chloride brine of 10% 120 hours.
More concentrated between the screening area that the main improvement of the present invention is raw material, and carry out mechanical alloying process by the mode of high-energy ball milling.And powder has also been carried out to the degassed process of hydrogen reduction, heat and other static pressuring processes has also carried out process of refinement.
The present invention compared with prior art, has following beneficial effect:
(1) have employed mechanical alloying treatment process, distributing homogeneity and the alloying performance of powder material are better;
(2) carry out hip treatment again after adopting isostatic cool pressing process, the compactness of product is better;
(3) through multistage vacuum degasing pretreatment, the oxygen content of product is lower, and degassing performance is better.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described further.
Embodiment 1
(1) select raw material, tentatively mixed by V-type batch mixer with niobium, tantalum molybdenum powder, atomic ratio is Mo:Nb:Ta=92:4:4, and then mixed powder is placed in high energy ball mill ball milling;
(2) carry out isostatic cool pressing process by material powder good for ball milling loading rubber sleeve, isostatic cool pressing processing pressure is 120MPa, and the press time is 20 minutes;
(3) loaded in steel capsule by the powder suppressed, steel capsule reserves 24 pores;
(4) steel capsule is carried out one-phase degassed, degassing temperature is 250 degree, and degassing time 12 hours, two-stage hydrogen reduction temperature are 680 DEG C, and 8 hours recovery times and three stage degassed treatment temperatures are 720 DEG C, degassing time 18 hours, then shuts all pores;
(5) be placed in hot isostatic press by the jacket manufactured and carry out HIP sintering HIP sintering parameter and be, temperature 1250 DEG C, sintering pressure is 150MPa, and the equalizing temperature time is 1 hour, and sintering time is 4 hours;
(6) jacket is removed, alloy pig is cut into and specifies target shape;
(7) density of target, purity, oxygen content, metallographic, crystallite dimension magnetron sputtering becomes film to carry out moisture-proof test is measured.Testing result is in table 1.
Embodiment 2
(1) select raw material, tentatively mixed by V-type batch mixer with niobium, tungsten, vanadium, zirconium, chromium molybdenum powder, atomic ratio is Mo:Nb:W:V:Zr:Cr=90:5:1:2:1:1, and then mixed powder is placed in high energy ball mill ball milling;
(2) carry out isostatic cool pressing process by material powder good for ball milling loading rubber sleeve, isostatic cool pressing processing pressure is 100MPa, and the press time is 30 minutes;
(3) loaded in steel capsule by the powder suppressed, steel capsule reserves 26 pores;
(4) steel capsule is carried out one-phase degassed, degassing temperature is 230 degree, and degassing time 8 hours, two-stage hydrogen reduction temperature are 650 DEG C, and 12 hours recovery times and three stage degassed treatment temperatures are 700 DEG C, degassing time 11 hours, then shuts all pores;
(5) be placed in hot isostatic press by the jacket manufactured and carry out HIP sintering HIP sintering parameter and be, temperature 1250 DEG C, sintering pressure is 160MPa, and the equalizing temperature time is 2 hours, and sintering time is 3 hours;
(6) jacket is removed, alloy pig is cut into and specifies target shape;
(7) density of target, purity, oxygen content, metallographic, crystallite dimension magnetron sputtering becomes film to carry out moisture-proof test is measured.Testing result is in table 1.
Embodiment 3
(1) select raw material, tentatively mixed by V-type batch mixer with niobium, neodymium, titanium molybdenum powder, atomic ratio is Mo:Nb:Nd:Ti=90:6:1:3, and then mixed powder is placed in high energy ball mill ball milling;
(2) carry out isostatic cool pressing process by material powder good for ball milling loading rubber sleeve, isostatic cool pressing processing pressure is 150MPa, and the press time is 30 minutes;
(3) loaded in steel capsule by the powder suppressed, steel capsule reserves 20 pores;
(4) steel capsule is carried out one-phase degassed, degassing temperature is 240 degree, and degassing time 10 hours, two-stage hydrogen reduction temperature are 680 DEG C, and 18 hours recovery times and three stage degassed treatment temperatures are 720 DEG C, degassing time 12 hours, then shuts all pores;
(5) be placed in hot isostatic press by the jacket manufactured and carry out HIP sintering HIP sintering parameter and be, temperature 1000 DEG C, sintering pressure is 140MPa, and the equalizing temperature time is 1 hour, and sintering time is 3 hours;
(6) jacket is removed, alloy pig is cut into and specifies target shape;
(7) density of target, purity, oxygen content, metallographic, crystallite dimension magnetron sputtering becomes film to carry out moisture-proof test is measured.Testing result is in table 1.
Embodiment 4
(1) select raw material, tentatively mixed by V-type batch mixer with niobium molybdenum powder, atomic ratio is Mo:Nb=90:10, and then mixed powder is placed in high energy ball mill ball milling;
(2) carry out isostatic cool pressing process by material powder good for ball milling loading rubber sleeve, isostatic cool pressing processing pressure is 100MPa, and the press time is 20 minutes;
(3) loaded in steel capsule by the powder suppressed, steel capsule reserves 25 pores;
(4) steel capsule is carried out one-phase degassed, degassing temperature is 240 degree, and degassing time 12 hours, two-stage hydrogen reduction temperature are 650 DEG C, and 12 hours recovery times and three stage degassed treatment temperatures are 790 DEG C, degassing time 8 hours, then shuts all pores;
(5) be placed in hot isostatic press by the jacket manufactured and carry out HIP sintering HIP sintering parameter and be, temperature 1200 DEG C, sintering pressure is 170MPa, and the equalizing temperature time is 1 hour, and sintering time is 4 hours;
(6) jacket is removed, alloy pig is cut into and specifies target shape;
(7) density of target, purity, oxygen content, metallographic, crystallite dimension magnetron sputtering becomes film to carry out moisture-proof test is measured.Testing result is in table 1.
Table 1 embodiment 1-4 testing result
| Embodiment | Purity | Relative density | Oxygen content | Average grain diameter | Moisture-proof |
| Embodiment 1 | 99.99％ | 99.8％ | 239ppm | 14 microns | Very well |
| Embodiment 2 | 99.98％ | 99.8％ | 427ppm | 12 microns | Better |
| Embodiment 3 | 99.97％ | 99.7％ | 322ppm | 13 microns | Better |
| Embodiment 4 | 99.98％ | 99.9％ | 388ppm | 17 microns | Poor |
Claims (10)
1. a preparation method for molybdenum alloy target, it is characterized in that using metal molybdenum powder and other metal powder to obtain alloy powder by the mode of mechanical alloying, alloy powder post processing, to obtain final product.
2. the preparation method of molybdenum alloy target according to claim 1, it is characterized in that other described metal powder is one or more in niobium, tantalum, tungsten, vanadium, neodymium, titanium, zirconium, vanadium or chromium, the content of other metal powder is 0.1-40at%.
3. the preparation method of molybdenum alloy target according to claim 1 and 2, is characterized in that step is as follows:
(1) select molybdenum powder and other metal powder as powder material, powder material is tentatively mixed by V-type batch mixer, and then mixed powder is placed in high energy ball mill ball milling;
(2) isostatic cool pressing process is carried out by material powder good for ball milling loading rubber sleeve;
(3) loaded in steel capsule by the powder suppressed, steel capsule reserves pore;
(4) steel capsule is carried out one-phase is degassed, two-stage hydrogen reduction and the degassed process of three stages, then all pores are shut;
(5) jacket manufactured is placed in hot isostatic press carries out HIP sintering;
(6) jacket is removed, alloy pig is cut into and specifies target shape;
(7) density of target, purity, oxygen content, metallographic, crystallite dimension magnetron sputtering becomes film to carry out moisture-proof test is measured.
4. the preparation method of molybdenum alloy target according to claim 3, it is characterized in that the maximum particle diameter of the raw material described in step (1) is 1-20 micron, purity is 99.9-99.999%, and oxygen content is 1-2000ppm.
5. the preparation method of molybdenum alloy target according to claim 3, is characterized in that the incorporation time described in step (1) is 10-30 minute; The ball selected in mechanical milling process is high compact zirconia ball, and ensure that environmental pressure is 1-50atm, Ball-milling Time is 1-24 hour, protective atmosphere to be purity be 99.999% argon gas.
6. the preparation method of molybdenum alloy target according to claim 3, it is characterized in that the isostatic cool pressing processing pressure described in step (2) is 20-200MPa, the press time is 10-60 minute.
7. the preparation method of molybdenum alloy target according to claim 3, is characterized in that the number of the pore described in step (3) is 1-50.
8. the preparation method of molybdenum alloy target according to claim 3, it is characterized in that the one-phase degassing temperature described in step (4) is 100-300 DEG C, degassing time is 2-12 hour, and the pressure in jacket is 1.0 × 10
-2-5.0 × 10
-2pa; Two-stage hydrogen reduction temperature is 500-1000 DEG C, and the hydrogen reduction time is 4-48 hour, and the Hydrogen Vapor Pressure in jacket is 1.0 × 10
4-1.0 × 10
5pa; Three stage degassing temperature are 600-1000 DEG C, and degassing time is 4-48 hour, and the pressure in jacket is 1.0 × 10
-2-5.0 × 10
-2pa.
9. the preparation method of molybdenum alloy target according to claim 3, it is characterized in that the HIP sintering temperature described in step (5) is 1000-1400 DEG C, sintering time is 1-12 hour, and sintering pressure is 100-170Mpa.
10. the production method of high dense conductive niobium oxide target according to claim 3, it is characterized in that the relative density of the target described in step (7) is 99-100%, purity is 99.9-99.999%, and oxygen content is 1-2000ppm, and average grain diameter is 1-100 micron.
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