CN103586479A - Large-scale preparation method for precisely regulating and controlling sizes of nanocrystalline nickel wires - Google Patents
Large-scale preparation method for precisely regulating and controlling sizes of nanocrystalline nickel wires Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 130
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 21
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- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims abstract description 11
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 11
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Abstract
The invention discloses a large-scale preparation method for precisely regulating and controlling the diameters and grains of nanocrystalline nickel wires. The large-scale preparation method includes that a simple and speedy microwave-assisted reduction technology is adopted, polyvinyl pyrrolidone (PVP) is used as a morphology control agent, hydrazine hydrate (N<2>H<4>) is used as a reducing agent, and the concentration of a precursor is changed, so that the sizes of the nanocrystalline nickel wires can be precisely regulated and controlled; when the concentration of Ni<2+> is increased, the concentration of the PVP and the concentration of the N<2>H<4> need to be assuredly proportionally increased; the prepared nanocrystalline nickel wires comprise the nanocrystalline grains with the uniform sizes, and the diameters of the wires can be controlled within the range from 70nm to 380nm; particularly, the diameters of the wires and the sizes of the grains are linearly and gradually changed along with change of the concentration of the precursor; magnetic coercive force is reduced along with increase of the diameters of the wires, and the intensity of saturation magnetization is correspondingly improved. The large-scale preparation method for precisely regulating and controlling the sizes of the nanocrystalline nickel wires has the advantages that the large-scale preparation method is efficient and economical, a preparation procedure only takes a few minutes without any hard templates or external magnetic fields, devices are simple, operation is easy, the controllability is high, and the nanocrystalline nickel wires can be easily manufactured on a large scale.
Description
Technical field
The present invention relates to the large-scale producing method of a kind of nano-crystal nickel linear diameter and crystal grain accuracy controlling, particularly, the diameter of nano wire 70-380nm on a large scale in adjustable, average grain size can be within the scope of 15-25nm accuracy controlling.
Background technology
Magnetic Nano material is widely used in fields such as medical imaging, magnetic induction switch, DNA separation and micro mechanical sensors because of its unique performance.In recent years, the magnetic transport property of character, the especially one-dimensional nano structure of low-dimensional (as a peacekeeping two dimension) magnetic Nano material has received people's very big concern.Compare with nano particle, these one dimension small-size materials often show magnetic coercive force and the saturation magnetization of enhancing.For example, the nano chain being formed by magnetic nano-particle assembling, its magnetic coercive force is than two orders of magnitude of this height of particle.Great many of experiments and theoretical research show, magnetic nanometer can be used as extremely sensitive magnetic resonance anisotropy functional unit; Due to the magnetic moment inductive effect at surface and interface place, along the uniaxial anisotropy enhancing of thin magnetic film surface normal.Therefore, the inducing action by surface and crystal grain boundary can cause magnetic anisotropy.When the inner crystal grain of material appearance Length Ratio is much larger, spatial induction anisotropy can surpass inherent magnetocrystalline anisotropy.For Fe, Co, Ni sill, magnetocrystalline anisotropy is relatively low, and pattern anisotropy occupies advantage in magnetic.Monocrystal nanowire is considered to the single domain magnet of the leading magnetic of pattern anisotropy; Multicrystal nano-wire is more complicated, and the factors such as the diameter of line, draw ratio, grain size, intergranular effect and surface roughness all can affect its magnetic.Therefore, simple, the effective preparation method of development, realizes nano-crystal nickel linear diameter and crystal grain accuracy controlling, to realizing the design of required performance and nanostructured, has very important significance.
Nickel is a kind of important ferromagnetic material, and its nanostructured has potential application at aspects such as magnetics, catalysis and microwave absorptions.At present, for the preparation method of one dimension Ni nano material, be mainly the magnetic induction self assembly of and nano particle auxiliary based on template.These methods are low, the pattern heterogeneity of productive rate often, and structural stability is poor.Without template, be still a challenge without the nanometer crystalline Ni line of preparing on a large scale pattern homogeneous under magnetic field condition.Heating using microwave becomes a kind of simple, effective preparation method just day by day, and some novel nanostructureds can only be auxiliary lower acquisition of microwave.Compare with traditional heating, its inner heating can produce higher efficiency, and Reaction time shorten, and reaction condition greatly can carry out program setting by microwave power, temperature and time etc.Because size (comprising diameter and crystal grain), degree of crystallinity and orientation etc. have impact to the Mechanical Reliability of magnetic, catalytic activity and nano wire etc., the micro-structural of nano wire and size Control have important impact to its performance regulation and control.Although many Ni nano materials are successfully made by microwave assisting method, the extensive preparation of the brilliant nickel wire of even and diameter thereof, crystallite dimension accuracy controlling not yet have report.
The present invention proposes the large-scale producing method of a kind of nano-crystal nickel linear diameter and crystal grain accuracy controlling.The method adopts simple and quick Microwave-assisted Reduction technology, realizes the accuracy controlling of size by changing the concentration of presoma.For avoiding the generation of other pattern product, work as Ni
2+when concentration increases, pattern controlling agent and reductant concentration will guarantee proportional increase.Gained nano wire is that the nanocrystal by size homogeneous is formed.Especially, the diameter of the nanocrystalline nickel wire of gained of the present invention and crystallite dimension are all linear change with the variation of precursor concentration.The preparation process that the present invention proposes only needs a few minutes, and without any die version and catalyst, device is simple, easily operation, controllability are good, easily accomplish scale production.
Summary of the invention
Object of the present invention: the large-scale producing method that cheap, the easy-operating nano-crystal nickel linear diameter of a kind of low one-tenth and crystal grain accuracy controlling are provided.The method has overcome that conventional method cost is high, the reaction time is long, energy loss is large, can not fine control nickel nanowire diameter and the technical barrier of inner crystallite dimension.Diameter and the crystallite dimension of the nanocrystalline nickel wire of gained of the present invention are all linear change with the variation of precursor concentration, to realizing performance regulation and control, have very important significance.The method also can be used for the controlled preparation of other magnetic one-dimensional nano material size.
Technical scheme of the present invention: the extensive preparation scheme of nano-crystal nickel linear diameter of the present invention and crystal grain accuracy controlling is: adopt simple and quick Microwave-assisted Reduction technology, with polyvinylpyrrolidone (PVP, K30, MW=30,000) be pattern controlling agent, N
2h
4for reducing agent, by changing the concentration of presoma, realize the accuracy controlling of size.For avoiding the generation of other pattern product, work as Ni
2+when concentration increases, PVP and N
2h
4concentration will guarantee proportional increase.By the NiCl of 0.02-0.1g
26H
2the PVP of O and 0.05-0.15g is dissolved in the ethylene glycol of 20mL, more than vigorous stirring 15min.Then, by the N of certain volume
2h
4(85wt%) join in the mixed liquor of stirring.Microwave reaction 2min under 400W power, then at 150W microwave reaction 4min, obtain black suspension.Container is cooled to room temperature, and collecting precipitation, with deionized water and alcohol cyclic washing, 40 ℃ of dry 8h under vacuum drying oven or air-flow protection.
Because reaction reagent solubility in ethylene glycol is low, stir into (magnetic force) strong stirring, more than time 15min.
Described reaction all can be carried out in programme controlled microwave reaction system in microwave power, reaction temperature and reaction time.
First adopt the heating using microwave of high-power 400W to make temperature be raised to fast 130-190 ℃, carry out microwave heating temperature again remain on 130-190 ℃ at small-power 150W, the time is respectively 2min and 4min.
In microwave reaction system, for preventing solution boiling, adopt top that the glass tube of 2 millimeters of diameters, 15 centimetres of length is attached to reaction bulb as condenser.
Ni
2+with N
2h
4mol ratio 1: 3-1: between 5, PVP and Ni
2+mol ratio be at least greater than 0.5.
The dry temperature of vacuum or air-flow protection is 40 ℃, and be more than 6 hours drying time.
For avoiding the generation of other pattern product, work as Ni
2+when concentration increases, pattern controlling agent and reductant concentration will guarantee proportional increase.
Feature of the present invention is exactly to adopt simple and quick Microwave-assisted Reduction technology, and reaction rate is fast, and products collection efficiency is high.By changing the concentration of presoma, realize the accuracy controlling of nanowire diameter and crystallite dimension.Preparation method is simple, and cost is lower, is easy to realize, and has certain prospects for commercial application.
Beneficial effect of the present invention:
(1) large-scale producing method of a kind of nano-crystal nickel linear diameter with low cost, easy-operating and crystal grain accuracy controlling has been proposed.Successfully prepare diameter at 70-380nm, crystal grain controlled polycrystalline nickel nano wire within the scope of 15-25nm.
(2) the method has overcome that conventional method cost is high, the reaction time is long, energy loss is large, can not fine control nickel nanowire diameter and the technical barrier of inner crystallite dimension.
(3) diameter of nanocrystalline nickel wire and crystallite dimension are all linear change with the variation of precursor concentration, and this has very important significance to realizing its performance regulation and control.
(3) microwave heating method is compared with existing technology of preparing, has following distinct advantages:
1. experimental provision, experiment condition and preparation process are very simple, easily operation, and material preparation efficiency is high;
2. productive rate is high.Product is the nanocrystalline nickel wire of size, pattern homogeneous, Ni
2+ conversion ratio approach 100%;
3. controllability is good, by regulating the apparent size internal structure of precursor concentration, heat treatment temperature and controlled product processed of time;
4. with low cost, easily realize, there is good industrial applications prospect.
Accompanying drawing explanation
Fig. 1 is that other reaction condition is constant, adopts different Ni
2+concentration (PVP and N
2h
4the corresponding equal proportion of concentration change) scanning electron microscopy (SEM) picture of prepared nickel nano wire.Ni
2+concentration is respectively: (a-b) 5mM, (c-d) 10mM, (e-f) 20mM and (g-h) 50mM.The SEM figure of illustration for amplifying.
The average diameter of the nanocrystalline nickel wire of Fig. 2 (black line) and average grain size (blue line) are with Ni
2+the variation of concentration.
Fig. 3 (a-b) is transmission electron microscopy (TEM) picture of representative nickel nano wire (seeing Fig. 1 c), (c) SEAD spectrum and (d) high-resolution transmission electron microscopy (HRTEM) figure.
Fig. 4 different Ni
2+concentration (PVP and N
2h
4the TEM figure of the nickel nano wire corresponding equal proportion variation of concentration) obtaining.Ni
2+concentration is respectively: (a-b) 5mM, (c) 20mM and (d) 40mM.Illustration is the SAED collection of illustrative plates that selected areas is corresponding.
Fig. 5 is without TEM and the SAED figure of the Ni particle obtaining under PVP condition.
The XRD collection of illustrative plates of nickel nano wire shown in Fig. 6 Fig. 1 a, 1c, 1e and 1g, illustration (111) characteristic diffraction peak for amplifying.
The hysteresis curve that the nanocrystalline nickel wire of Fig. 7 different-diameter, crystallite dimension records when 5K, the amplification in region centered by illustration.
M (T) curve of Fig. 8 different-diameter, crystallite dimension nickel nano wire, figure b is that extra show cooling curve is at the enlarged drawing of low-temperature space.
The specific embodiment
In the present invention, adopt the specific embodiment of the brilliant nickel wire of the extensive preparation size controllable nano of microwave assisting method as follows:
Embodiment 1
By the NiCl of 0.05g
26H
2the PVP of O and 0.1g is dissolved in the ethylene glycol of 20mL, violent magnetic agitation (the magnetic agitation of strong rotating speed, improves speed of agitator in industrial production) 20 minutes.Then, 0.2mL hydrazine hydrate (85wt%) is added drop-wise in the vigorous stirring mixed solution of (prime time of magnetic agitation).Initial transparent bright green solution is transformed into light blue at once, because formed stable complex compound [Ni (N
2h
4)
3] Cl
2, Ni now
2+concentration is 10mM, and PVP concentration is 150mM.Ni in solution
2+concentration increases, PVP and N
2h
4guarantee proportional increase.The conical flask that fills reaction mixture is put into microwave reactor, for preventing solution boiling, adopt top that the glass tube of 2 millimeters of diameters, 15 centimetres of length is attached to reaction bulb as condenser.Microwave reaction 2min under 400W power, then at 150W microwave reaction 4min, obtain black suspension.Container is cooled to room temperature, and collecting precipitation, with deionized water and alcohol cyclic washing, 40 ℃ of dry 8h under vacuum drying oven or air-flow protection.
Adopt different characterizing methods, comprise that SEM (SEM), transmission electron microscope (TEM), high resolution transmission electron microscope (HRTEM), SEAD (SAED), thermogravimetric analysis (TG) and X-ray diffraction (XRD) etc. have carried out detailed sign to product.Its magnetic (comprising hysteresis curve, coercivity, saturation magnetization) is measured.
Embodiment 2
Change Ni
2+concentration is 0.1mM, and PVP concentration is 7.5mM, and adding hydrazine hydrate (85wt%) volume is 0.01mL, and all the other are with embodiment 1;
Embodiment 3
Change Ni
2+concentration is 2.5mM, and PVP concentration is 37.5mM, and adding hydrazine hydrate volume is 0.05mL, and all the other are the same;
Change Ni
2+concentration is 5mM, and PVP concentration is 75mM, and adding hydrazine hydrate volume is 0.10mL, and all the other are the same;
Change Ni
2+concentration is 20mM, and PVP concentration is 300mM, and adding hydrazine hydrate volume is 0.40mL, and all the other are the same;
Embodiment 6
Change Ni
2+concentration is 30mM, and PVP concentration is 450mM, and adding hydrazine hydrate volume is 0.60mL, and all the other are the same;
Embodiment 7
Change Ni
2+concentration is 40mM, and PVP concentration is 600mM, and adding hydrazine hydrate volume is 0.80mL, and all the other are the same;
Change Ni
2+concentration is 50mM, and PVP concentration is 750mM, and interpolation hydrazine hydrate is 1mL, and all the other are the same;
Fig. 1 is that other reaction condition (microwave power, temperature and reaction time etc.) is constant, adopts different Ni
2+concentration (PVP and N
2h
4the corresponding equal proportion of concentration change) scanning electron microscopy (SEM) picture of prepared nickel nano wire.Work as Ni
2+during concentration lower (5mM, embodiment 4), product is a large amount of nano wires uniformly, and length can reach tens of microns, and diameter is about 70 ± 12nm (as shown in Figure 1a).From the SEM figure (Fig. 1 b) of further amplification, can see not having the product of other pattern to generate.These nanowire surface are coarse, and non-rectilinear, but crooked form arbitrarily distribution.Work as Ni
2+during concentration double (10mM, embodiment 1), the diameter of nano wire is increased to 100 ± 18nm (seeing Fig. 1 c and d).Now nanowire surface and pattern do not have significant change.Ni
2+concentration is further increased to 20mM (embodiment 5), and the diameter of nickel nano wire is increased to 180 ± 21nm (Fig. 1 e and f).Work as Ni
2+when concentration increases to 50mM, the diameter of nickel nano wire is increased to 380 ± 20nm.The average diameter of nano wire and mean-squared departure value are added up by 30 nano wires.When concentration reduces, the diameter of gained nano wire is corresponding to be reduced, but concentration is while being less than certain value (as 2.5mM), and product is the mixture of nano nickel particles and line.Can obtain, work as Ni
2+concentration (PVP and N
2h
4the corresponding equal proportion of concentration change) be respectively 0.1mM (embodiment 2), 2.5mM (embodiment 3), 5mM (embodiment 4), 10mM (embodiment 1), 20mM (embodiment 5), 30mM (embodiment 6), when 40mM (embodiment 7) and 50mM (embodiment 8), the diameter of gained nano wire is followed successively by 4 ± 2nm, 45 ± 6nm, 70 ± 12nm, 100 ± 18nm, 180 ± 21nm, 260 ± 23nm, 320 ± 19nm and 380 ± 20nm.In addition, from the SEM figure of illustration amplification, can see, during low concentration, line rough surface, along with Ni
2+concentration increases surface and is tending towards smooth (as Fig. 1 f illustration).
Fig. 2 is that the average diameter (black line) of nanocrystalline nickel wire and average grain size (blue line) are with Ni
2+the change curve of concentration.Can see, work as Ni
2+when concentration is less than 2.5mM, linear diameter increases progressively fast with the increase of concentration; Work as Ni
2+concentration is during higher than 2.5mM, and the diameter of line is with Ni
2+concentration is linear change (as shown in Figure 2).Because the performance of magnetic Nano material has strong size-dependent, thereby this has very important significance to realizing performance regulation and control.
Fig. 3 is the TEM picture that embodiment 1 makes nano wire.Can see, the diameter of nano wire is about 100nm, and this observes with SEM, and to obtain result (seeing Fig. 1 c) consistent.The TEM picture of high-amplification-factor (Fig. 3 b) shows, nano wire is that the nanocrystal by a large amount of size uniforms is formed, and crystallite dimension is 17 ± 3nm.SAED collection of illustrative plates (Fig. 3 c) has further confirmed its polycrystalline structure feature.In the HRTEM figure of nano wire (Fig. 3 d), lattice fringe clearly continuously, the arbitrary orientation of local location striped has confirmed that single nano-wire is comprised of much random distribution crystal grain.
Fig. 4 is different Ni
2+concentration (PVP and N
2h
4the TEM figure of the nickel nano wire corresponding equal proportion variation of concentration) obtaining.Ni
2+when concentration is 5mM (Fig. 4 a, embodiment 4), the diameter of nano wire is about 70nm, its rough surface, and the observed result of this SEM is consistent.The thick nanometer sheet clad of about 1nm is in the surrounding (Fig. 4 b) of nano wire.Work as Ni
2+concentration is higher than 10mM, and (as Fig. 4 c, embodiment 4) no longer appear in these nanometer sheet.Work as Ni
2+when concentration is 40mM (embodiment 7), the diameter of nano wire is about 320nm, as shown in Fig. 4 d.Corresponding SAED schemes (Fig. 4 a, 4c and 4d illustration) and shows, under variable concentrations, prepared nano wire is polycrystalline.Diffracted intensity is with Ni
2+concentration increases and strengthens, and shows that crystal grain increases gradually.
Embodiment 9
Change Ni
2+concentration is 50mM, and PVP concentration is 0mM, and interpolation hydrazine hydrate is 1mL, and all the other are the same;
Pattern controlling agent PVP is most important to the formation of nanocrystalline nickel wire.While not adding PVP (embodiment 9), product is the spherical particle of class, and its average diameter is about 580 ± 20nm, as shown in Figure 5 a.SAED result (Fig. 5 b) shows, these particles are still polycrystalline, much undersized crystal grain, are consisted of.
Fig. 6 is Fig. 1 a, 1c, the nickel nano wire shown in 1e and 1g and nickel particle (Fig. 5 XRD collection of illustrative plates a).Can see, in 2 θ=43.8, three diffraction maximums of 51.8 and 76.4 ° correspond respectively to (111) of face-centred cubic structure nickel, the characteristic peak of (200) and (220).(111) and the strength ratio at (200) peak from 2.32 (black curves), be increased to 3.13 (red curve), product pattern changes to line from particle, shows the preferred orientation of Ni crystal grain in nano wire.For nickel nano wire, along with Ni
2+the increase of concentration, strength ratio is respectively 2.98,3.08 and 3.46 (red to black curve).Can infer, there is preferred orientation in Ni crystal grain in nano wire.According to the halfwidth method of (111) diffraction maximum, calculate Ni
2+concentration makes nickel nano wire average grain size while being respectively 5mM (embodiment 4), 20mM (embodiment 5), 40mM (embodiment 7) and 50mM (embodiment 8) is followed successively by 15nm, 19nm, 24nm and 25nm.These values are consistent with TEM acquired results.
Fig. 7 is the hysteresis curve that different-diameter Ni nano wire records under 5K.Nanocrystalline nickel wire shows the typical ferromagnetic behavior of metallic nickel.Along with the diameter of nickel nano wire is increased to 260nm from 70nm, magnetic coercive force is reduced to 158Oe (green line) from 382Oe (blue line).The magnetic coercive force of these nano wires is up to 20 times of Ni nano particle (19.4Oe), and is significantly higher than the magnetic coercive force (0.70e) of nickel body material.Especially, the coercivity of the 70nm nickel nano wire that the present invention obtains when 5K is higher than the peak (305Oe) of same diameter nickel nano chain, even taller than the coercivity of the polycrystalline nickel nano wire of the auxiliary preparation in magnetic field.This shape anisotropy owing to nano wire and little crystallite dimension cause.
The M-T curve of the nanocrystalline nickel wire of different-diameter as shown in Figure 8.Can see, null field cooling (ZFC) cooling with extra show (FC) curve is completely separated, even also separate at 395K.This is mainly that pattern anisotropy by one-dimensional material causes.M
zFCalong with temperature increases and raises, M
fCalong with temperature increases and reduces.At low-temperature region, M
zFC(T) curve shows T in 16K left and right
fpeak value (Fig. 8 a illustration).The position at peak does not also rely on the diameter of nano wire, but the height at peak constantly reduces along with the increase of diameter.
Claims (8)
1. a large-scale producing method for nano-crystal nickel linear dimension accuracy controlling, is characterized in that, adopts simple and quick Microwave-assisted Reduction technology, take polyvinylpyrrolidone (PVP) as pattern controlling agent, hydrazine hydrate (N
2h
4) be reducing agent, by changing the concentration of presoma, realize the accuracy controlling of size.For avoiding the generation of other pattern product, work as Ni
2+when concentration increases, PVP and N
2h
4concentration will guarantee proportional increase.Concrete steps are as follows: by the NiCl of 0.02-0.1g
26H
2the PVP of O and 0.05-0.15g is dissolved in the ethylene glycol of 20mL, more than vigorous stirring 15min.Then, by the N of certain volume
2h
4(85wt%) join in the mixed liquor of stirring.Ni in solution
2+concentration increases, PVP and N
2h
4guarantee proportional increase.Microwave reaction 2min under 400W power, then at 150W microwave reaction 4min, obtain black suspension.Container is cooled to room temperature, collecting precipitation, with deionized water and alcohol cyclic washing, dry under vacuum drying oven or air-flow protection.
2. according to the large-scale producing method of the nano-crystal nickel linear dimension accuracy controlling described in claim 1, it is characterized in that, reaction all can be carried out in programme controlled microwave reaction system in microwave power, reaction temperature and reaction time.
3. according to the preparation method described in claim 1, it is characterized in that, first adopt the heating using microwave of high-power 400W to make temperature be raised to fast 130-190 ℃, at small-power 150W, carry out microwave heating temperature again and remain on 130-190 ℃, time is respectively 2min and 4min, is finally cooled to room temperature.
4. according to the preparation method described in claim 1, it is characterized in that, for guaranteeing the extensive preparation of high-purity nickel nano wire, Ni
2+with N
2h
4mol ratio 1: 3-1: between 5, PVP and Ni
2+mol ratio be at least greater than 0.5.
5. the dry temperature of vacuum or air-flow protection is 40 ℃, and be more than 6 hours drying time.
6. according to the preparation method described in claim 1, it is characterized in that, for avoiding the generation of other pattern product, work as Ni
2+when concentration increases, PVP and N
2h
4concentration will guarantee proportional increase.
7. according to the preparation method described in claim 1, it is characterized in that, PVP is pattern controlling agent, most important to the formation of the nanocrystalline nickel wire of homogeneous, N
2h
4for reducing agent, by changing the concentration of presoma, can realize the accuracy controlling of size.
8. the diameter of gained nano wire is controlled within the scope of 70-380nm, is that the nanocrystal by size homogeneous is formed.During low concentration, line rough surface, is tending towards smooth along with Ni2+ concentration increases surface.Especially, the diameter of the nanocrystalline nickel wire of gained of the present invention and crystallite dimension are all linear change with the variation of precursor concentration.
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