CN104067114A - Zinc oxide sulfur sensors and methods of manufacture thereof - Google Patents
Zinc oxide sulfur sensors and methods of manufacture thereof Download PDFInfo
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- CN104067114A CN104067114A CN201380005853.8A CN201380005853A CN104067114A CN 104067114 A CN104067114 A CN 104067114A CN 201380005853 A CN201380005853 A CN 201380005853A CN 104067114 A CN104067114 A CN 104067114A
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/26—Oils; viscous liquids; paints; inks
- G01N33/28—Oils, i.e. hydrocarbon liquids
- G01N33/2835—Oils, i.e. hydrocarbon liquids specific substances contained in the oil or fuel
- G01N33/287—Sulfur content
Abstract
A sensor is disclosed for determining a sulfur concentration in a liquid, such as a liquid fuel. The sensor includes a substrate (30) that is at least partially coated with zinc oxide and, more specifically, zinc oxide microstructures. The zinc oxide microstructures have a crystal lattice structure that is oriented in the (002) plane, are oxygen-deficient and have a rod-like microstructure. If the substrate (30) is conductive, it may be connected directly to a working electrode (32) which is connected to a potentiometer (36) which, in turn, is connected to a reference electrode (35). If the substrate (30) is non- conductive, the conductive layer can be deposited on the substrate (30) prior to deposition of the zinc oxide to form a working electrode (32). An application of a constant current (or voltage) to either electrode will result in a voltage across (or current flow between) the working and reference electrodes (32).
Description
Technical field
Disclosure relate generally to is for detection of the sensor of the sulphur concentration in liquid.More specifically, the disclosure relates to for measuring the method for improved zinc paste sulfer sensor and the improved zinc paste sulfer sensor of the spendable manufacture of this area operator of liquid sulphur concentration.
Background technology
The concentration of can be accurately and measuring reliably the sulphur in liquid is important, because can occur to discharge harmful sulphur compound in atmosphere or to the various chemical reactions in sulfur-containing liquid physical arrangement around.For example, the burning of diesel fuel generates sulfur oxide (SO conventionally
2, SO
3) and sulfuric acid (H
2sO
4), it is for the composition of acid rain and be limited by Environment Regulation.Further, these sulphur compounds are associated with the catalyst poisoning in diesel particulate thing filtrator (DPF), and the corrodible engine components such as refrigeratory and piston ring liner component of sulfuric acid.When use high-sulfur (>350ppm) and low-sulfur (15-350ppm) fuel the two time, these phenomenons can occur.
Due to these reasons, comprise the sensitivity to the after-treatment components of sulphur compound, present many modern diesel engines are being designed to use ultra-low-sulphur diesel (ULSD) fuel (<15ppm S).The result changing as these designs, for the optimum performance of many modern diesel engines, the low sulphur concentration in diesel fuel is necessary now.Although can realize in laboratory or other proving installation lower than sulphur in the liquid of 15ppm level, detect, can not realize in the art at present by accurate, portable, reliably, fast and cheap sensor carry out such detection.The example of the known means at ultra low levels detection sulphur comprises flame photometric detection (FPD) and inductively coupled plasma (ICP) device, but due to the duration of size and the test loop of equipment, the two be all in lab setup, use more appropriate.
Correspondingly, need cheap, be easy to use and can the equipment operator fast detecting liquid in this area in the sulphur pick-up unit of sulphur concentration.
Summary of the invention
The sensor of the sulphur concentration in a kind of definite liquid is disclosed in an example.Disclosed sensor can comprise the substrate that is coated with at least in part zinc paste.Further, described zinc paste can have the crystalline network along (002) planar orientation.
In another example, a kind of sulphur concentration detection system is disclosed.Described disclosed detection system comprises the sensor that comprises working electrode, and described working electrode comprises the substrate that is coated with zinc paste.Described zinc paste comprises the microstructure having with the crystalline network of (002) planar orientation.Described sensor also can comprise contrast electrode.Described detection system also can comprise current source and voltage-level detector, wherein, described current source can be connected to described working electrode and described voltage-level detector is connected to described reference and working electrode.
A kind of method of the sulphur concentration for definite liquid is disclosed in a further example.Described disclosed method comprises described liquid exposure to sulfer sensor.Described sensor can comprise there is substrate, conductive material and from the working electrode of the outstanding zinc oxide microstructure of described substrate.At least some in described zinc oxide microstructure can have along the crystalline network of described (002) planar orientation.Described sulfer sensor also can comprise contrast electrode.Described method further comprise apply steady current to described substrate, monitor the voltage between described work and contrast electrode and described voltage be associated with to the sulphur concentration in liquid.
Accompanying drawing explanation
Fig. 1 is the schematic cross-section of the zinc oxide microstructure on substrate disclosed herein.
Fig. 2 is the schematic diagram of a kind of method of open circuit potential measurement, wherein disclosed sensor is immersed at least in part in liquid to be measured and is connected to working electrode, this working electrode is connected to pot, this pot and then be connected to the contrast electrode in liquid at least in part.
Fig. 3 shows disclosed zinc paste sensor and absorbs sulphur until sulphur concentration reaches the ability of particular value, and this has indicated concentration and the liquid of sulphur.
Fig. 4 shows for using the X-ray diffraction spectrum of seven different Zinc oxide coatings (A-G) of different presomas and/or the generation of differential responses condition.
Fig. 5 is scanning electron microscope (SEM) photo of microstructure that shows the sample A of Fig. 4, and Fig. 6 shows and lacks sulphur compound to the absorption in the microstructure shown in the photo of Fig. 5.
Fig. 7 is the SEM photo of microstructure of the sample B of Fig. 4, and Fig. 8 illustrates when the concentration of sulphur in about 350ppm, and the microstructure of sample B absorbs sulphur compound to the ability in the microstructure of sample B.
Fig. 9 is the SEM photo of microstructure of the sample G of Fig. 4, and Figure 10 illustrates at least when the concentration of sulphur in about 350ppm, and the microstructure of sample G absorbs the ability of sulphur compound.
Figure 11 illustrates the ability that is arranged on the sulphur compound in the concentration from 1ppm to 350ppm in the Zinc oxide coating absorption liquid in copper substrate as shown in the photo of Figure 12.
Figure 13 illustrates the ability of the sulphur compound in the concentration from 15ppm to 3600ppm in the absorption liquid of disclosed Zinc oxide coating at the bottom of stainless steel lining as shown in figure 14.
Figure 15 illustrates two SEM photos of the different amplification of the Zinc oxide coating that comprises the bar-shaped or banded microstructure from substrate to upper process.
Figure 16 and Figure 17 are the preparation that is illustrated in two Zinc oxide coatings under different collector temperatures, wherein, the collector temperature that is used for the coating of Figure 16 is 200 ℃, and it is 300 ℃ for the collector temperature of the coating of Figure 17, thereby set up: the collector temperature of the increase of Figure 17 produces bar-shaped or banded to the microstructure of upper process and wherein, the lower collector temperature of Figure 16 produces shorter and round microstructure.
Figure 18 and 19 illustrates the impact of reaction time on the microstructure of Zinc oxide coating, wherein, the club shaped structure of Figure 18 has and is about the average thickness of 0.7 micron and through the reaction time preparation of two hours, and the thicker microstructure of Figure 19 has and is about the average thickness of 1 micron and through the reaction time preparation of 3.5 hours.
Figure 20 shows the coating shown in Figure 18 and in approximately 100 seconds, absorbs and detect the ability of the sulphur of the concentration in 5ppm, the ability of the sulphur of the concentration in about 386ppm with absorption in approximately 80 seconds and detection, and Figure 20 also illustrates the sensitivity that the sensor of being made by the coating of Figure 18 is shown.
It is 10ppm to the ability of the sulphur in the liquid of 155ppm that Figure 21 illustrates a disclosed zinc paste sensor detectable concentration scope, and further illustrates, and such sensor is limited for the effect of 183ppm or higher sulphur concentration.
Figure 22 shows the high-crystallinity of four Zinc oxide coatings in (002) face, and particularly, the label that is the manufacture of use same process parameter is 65,67,130 and 134 sample.
Figure 23 also illustrates and illustrates with label is 23 to compare with 106 sample, the high-crystallinity structure of the sample that label is 67 in (002) face.
Figure 24 illustrates sample 67 and detects sulphur in low concentration (10.7ppm is to 48ppm) and the ability of liquid, and the sample 67 of high-crystallinity with (002) face is with respect to the sample 23 of low-crystallinity and the sensitivity of 106 increase with having as shown in Figure 22-23 (002) face.
Embodiment
Fig. 1 shows the cross section of the substrate 30 that is coated with at least in part a plurality of zinc oxide microstructures 31.Under given conditions and use specific substrate 30 or electrode, microstructure 31 can be outwards outstanding from substrate 30.The processing of substrate 30 (or electrode) also can affect the form of microstructure 31.When using term " microstructure " when describing the character of size of zinc oxide microstructure herein, the physical size that it will be appreciated by those skilled in the art that zinc paste projection 31 can approach or enter nanoscale or alternatively, is greater than microscale.
Substrate 30 can be conduction or non-conductive.Non-conductive substrate 30 can be any in pottery or any apparent various non-conductive substrate to those skilled in the art.Conductive substrates also can greatly change, and can eliminate the demand of working electrode 32 (seeing Fig. 2) or working electrode 32 is wherein attached or is coupled to the demand of the independent manufacturing step of substrate 30 and zinc paste projection 31.
Based on organosulfur compound, to the Physical Absorption on zinc paste, design disclosed sulfer sensor.Inventor be surprised to find that organosulfur compound to the speed of the Physical Absorption on zinc paste can be zinc paste crystallinity and, more specifically, along (002) face or the substrate from Fig. 1 30 face of projection or the surface 33 from the substrate 30 as shown in Figure 2 function of the orientation of the crystallinity of the zinc paste of the face of projection to the right flatly vertically upward.As described below, be also surprised to find that, the speed of Physical Absorption also depends on the bar-shaped or banded form of Zinc oxide coating and the oxygen lack of Zinc oxide coating.
Organosulfur compound causes the change of the outer field resistivity of zinc oxide microstructure to the Physical Absorption in zinc paste projection.The amount of the change of zinc oxide microstructure directly with in liquid can with zinc oxide microstructure 31 in the amount of the sulphur that reacts of zinc corresponding.Can apply under the condition of current known across sulfer sensor and fluid to be measured, by measuring voltage, change the change of measuring this resistivity.Certainly, vice versa; Once Zinc oxide coating become saturated with sulphur compound or with liquid 34 in sulphur concentration in balance, across work and contrast electrode 32,35 apply constant voltage will cause steady current stream between electrode 32,35.Further, as follows, can work as while applying steady current by measurement, the amount of voltage stabilization required time, or work as while applying constant voltage by measurement, the amount of current stabilization required time, determines sulphur concentration.
With reference to figure 2, in one aspect, the substrate 30 with oxide layer coating (not shown) on its surface 33 is dipped in liquid 34 at least in part.Contrast electrode 35 is also dipped in liquid 34 at least in part.Work and contrast electrode 32,35 are coupled to pot 36.By working electrode 32, current known is applied to substrate 30 and the Zinc oxide coating on surface 33.As shown in Figure 3, because proceed to the absorption on surface 33, by the concentration equilibrium establishment of the sulphur based in fluid to be measured.Particularly, in Fig. 3, X-axis is the concentration of the sulphur in fluid to be measured, and Y-axis is sulphur to the equilibrium constant of the absorption on zinc paste.As can be seen from Figure 3,, once reach certain concentration, for higher concentration, it is constant that absorption equilibrium constant keeps.Therefore, as explained, depend on crystallinity, the form of zinc oxide microstructure and the oxygen lack of Zinc oxide coating in (002) face below, can be provided in effective various sensor coatings under various sulphur concentrations.
Forward Fig. 4 to, show the X-ray diffraction spectrum of seven different sample A-G.By the crystallinity in 34 places or the indication of peak around (002) face along X-axis (2 θ scale).Therefore, sample A and C illustrate along (002) face without crystallinity or minimum degree of crystallinity, and sample B and D-G have shown along the crystallinity of (002) face, sample G has shown along the highest level of the crystallinity of (002) face.
Fig. 5-10 are relatively the ability of the sulphur of 15ppm and 350ppm from sample A, B and the G detectable concentration of Fig. 4.Fig. 5-10 also show the physical characteristics that variation in technological parameter can affect Zinc oxide coating.
Particularly, use metal organic chemical compound vapor deposition (MOCVD) equipment to prepare disclosed Zinc oxide coating.Use zinc acetylacetonate presoma to be about 500 ℃, pressure at cavity temperature and be about 2.5 holders, oxygen flow and be about under the condition that temperature that 50ml/min, argon flow amount be about 50ml/min and zinc acetylacetonate presoma is about 145 ℃, prepare sample A and B.As shown in Figure 6, the coating of sample A is not effective for the sulphur concentration of measuring in 15ppm or the arbitrary concentration of 350ppm.Forward Fig. 7-8 to, use zinc acetylacetonate presoma, be about the cavity temperature of 550 ℃, oxygen and the argon flow amount that is about the pressure of 10 holders and is about 50ml/min prepared sample B.As shown in Figure 8, sample B can not detect and be low to moderate 15ppm sulphur level, but can detect 350ppm sulphur level completely.
Forward Fig. 9-10 to, the SEM photo of the coating of sample G shown in Figure 9, is used diethyl zinc presoma, is about the cavity temperature of 500 ℃, the pressure that is about 2.5 holders, the oxygen that is about 50ml/min and argon flow amount and is only about the presoma temperature of 30 ℃ and prepare this sample G.As shown in figure 10, the sulphur concentration that sample G can fast detecting 350ppm, but sensitive not to detecting the sulphur concentration of 15ppm.
Comparison diagram 4-10, obviously can be absorbed with organic sulfur compound such as the Zinc oxide coating with high crystalline that sample B and D-G present.Further, it should be noted that the sulphur many Zinc oxide coating faster than sample B that produces the concentration that detects 350ppm for the diethyl zinc presoma of sample G, wherein use zinc acetylacetonate presoma to form this sample B.Fig. 5-6 have been set up: do not have under the condition of the crystallinity of (002) face, at least, under 15ppm and 350ppm concentration, the quick absorption of setting up organosulfur compound is impossible.Therefore, Fig. 4-10 illustrate the factor that crystallinity in (002) face can be the absorption that strengthens the sulphur compound on Zinc oxide coating in surprise.
Forward Figure 11-14 to, the comparison of different substrates and different coating density is provided.The copper substrate that is coated with zinc paste is shown and can detects the sulphur concentration of 1,15 and 350ppm as shown in figure 11 in Figure 12.When with Figure 14 relatively time, the Zinc oxide coating of Figure 12 owes fine and close than the Zinc oxide coating of Figure 14, on the Zinc oxide coating of Figure 14 is applied at the bottom of stainless steel lining, and as shown in figure 13, can detect 15,350 and the sulphur concentration of 3600ppm.As shown in figure 11, the sulphur of owing dense coating detection 1ppm and the low concentration of 15ppm and the higher concentration of 350ppm of Figure 12.By the coating of Figure 11-12, the higher concentration that detects 350ppm is faster than the concentration that detects 15ppm and 1ppm.On the contrary, the dense coating of Figure 14 cannot detect the sulphur of the low concentration of about 1ppm, but can detect the sulphur of the higher concentration of about 15ppm, 350ppm and 3600ppm.Therefore, from Figure 11-14, can reach a conclusion, finer and close Zinc oxide coating is more useful for the higher concentration of the sulphur in liquid, and it is more useful for the lower sulphur concentration in tracer liquid to owe fine and close Zinc oxide coating.
Forward Figure 15 to, shown two SEM photos of the different amplification of identical coating.Use the collector temperature of the increase of the furnace temperature of 500 ℃ and 300 ℃ to prepare the sample of Figure 15.Utilize zinc acetylacetonate presoma, and be under 10 holders, to carry out the coating processes of two hours at pressure.Argon gas and oxygen flow are 50ml/min.This operation produces the weary Zinc oxide coating of anoxic as shown in figure 15, and it has excellent club shaped structure from substrate (not shown) to upper process that can be from and thereby has a high-crystallinity at (002) face.By measurement, set up oxygen lack, this measurement shows that the coating of Figure 15 comprises the carbon of 3.31wt%, the oxygen of 17.9wt%, 1.04% chromium, 4.53% iron and 73.22% zinc.For complete saturated zinc paste (ZnO) coating, the wt% ratio of zinc and oxygen is 3.75, or with the molecular weight (30) of zinc the molecular weight (8) divided by oxygen.Therefore, 4.09 of the coating of Figure 15 ratio (73.22/17.9) has been indicated oxygen lack Zinc oxide coating.
Forward Figure 16-17 to, except collector temperature in Figure 16 is set to 200 ℃, and be set to outside 300 ℃ for the collector temperature of the coating of Figure 17, used identical parameter.Therefore, comparison diagram 16-17, the collector temperature of increase produces better bar-shaped microstructure.Forward Figure 18-19 to, measure the impact of the variation in the reaction time.In Figure 18, carry out the depositing operation of two hours, this depositing operation produces the club shaped structure with the average thickness of approximately 0.7 micron shown in Figure 18.Yet, as shown in figure 19, increase the reaction time by approximately 3.5 hours, produce the club shaped structure of the average thickness with approximately 1 micron.Therefore, preferably Figure 18 owe dense coating for measuring low sulphur concentration, and more preferably the more dense coating of Figure 19 for measuring the higher concentration of sulphur compound.
Figure 20 illustrate the coating that is coated with Figure 18 sensor to thering is the response of liquid of the amount (5ppm and 386ppm particularly) of different sulphur.Voltage table for the measurement shown in Figure 20 can not be greater than the detection of 15 volts, and thus, for the sensor of Figure 20 and the combination of voltage table can not fully detect as shown in figure 20 be the concentration of 4940ppm.The club shaped structure of 0.7 micron thickness that Figure 20 also illustrates the coating of Figure 18 provides and is suitable for low-sulfur simultaneously and detects the sensor that (5ppm) and relative high-sulfur detect (386ppm).Further, as shown in figure 20, the response time of the coating of Figure 18, for 5ppm sulphur concentration liquid, be substantially reduced to approximately 100 seconds, and for 386ppm sulphur concentration liquid, be substantially reduced to approximately 80 seconds.
Figure 21 illustrates the response to the sulphur concentration changing liquid of the zinc paste sensor made from sample 106, this sample 106 is stainless steel, this liquid is in particular diesel fuel, although the disclosure is intended to the detection of the organosulfur compound in any liquid and any liquid fuel.Sensor shown in Figure 21 10,20 and the low concentration of 48ppm under less sensitivity is provided, but for 135 and the concentration of 155ppm, provide large sensitivity.Sensor shown in Figure 21 to such as 183 and the higher concentration of 297ppm be not useful, this is because sensor occurs saturated under these concentration.
The bar chart that the x x ray diffraction (XRD) of the crystal structure that Figure 22-23 are the Zinc oxide coating made with different parameters is analyzed.Particularly, cycling time, vacuum pressure, bubbler (bubbler) temperature, collector temperature set point and cavity temperature are all different.With reference to Figure 22, the sample for label 65,67,130 and 134, is used identical parameter.In order to the parameter of the sensor coatings of the perparation of specimen 65,67,130 and 134 be listed in the table below 1 first or left column.Be used for the parameter of other sample shown in Figure 22 and 23 also shown in table 1.
Table 1
| Sample # | 67 | 25 | 49 | 57 | 74 | 90 |
| Cycling time (hrs) | 7 | 8 | 8 | 5 | 4 | 4 |
| Vacuum pressure (holder) | 15 | 2.5 | 2.5 | 10 | 2.5 | 2.5 |
| Ar flow (sccm) | 50 | 50 | 50 | 50 | 50 | 50 |
| O 2Flow (sccm) | 50 | 50 | 50 | 50 | 50 | 50 |
| Bubbler temperature (℃) | 125 | 125 | 125 | 125 | 110 | 125 |
| O 2Inlet temperature (℃) | 200 | 250 | 250 | 200 | 200 | 200 |
| Collector temperature (℃) | 225 | 265 | 250 | 225 | 225 | 225 |
| Chamber flange temperature (℃) | 522-527 | 477-487 | 495-499 | 525-532 | 527-529 | 527-529 |
| (002) of proofreading and correct | 43119 | 6446 | 7640 | 4777 | 17734 | 3380 |
| (101) of proofreading and correct | 6634 | 6939 | 7082 | 7671 | 6536 | 7411 |
| (002)/(001) | 6.5 | 0.93 | 1.08 | 0.62 | 2.71 | 0.46 |
As can be seen from Table 1, many factors impacts (002) crystal lattice orientation.These factors comprise cycling time, vacuum pressure, bubbler temperature, collector temperature and cavity temperature.Seem that vacuum pressure and cycling time are primary factor, and collector temperature, fan diffuser temperature and cavity temperature are secondary cause.The height ratio of offering sample (002) orientation that the label that uses the parameter manufacture identical with sample 65,130 and 134 is 67 to (001) orientation, obviously keep vacuum pressure slightly high in 15 holders and cycling time at approximately 7 hours, keep simultaneously collector temperature at approximately 225 ℃, bubbler temperature at approximately 125 ℃ and, inferior strategic point, cavity temperature, at approximately 500 ℃, will provide the zinc oxide microstructure with strong (002) orientation.Certainly, these parameters can change greatly and can select parameter to be used for the application-specific to high-sulfur combustor such as super-low sulfur fuel.
Finally, with reference to Figure 24, obviously sample 67 provides the optimum sensitivity between the concentration of 10.7ppm and48ppm.It shall yet further be noted that all samples become saturated or equilibrium establishment in relatively short time durations.Particularly, although be slightly slower than sample 23 and 106, sample 67 is when the higher concentration of 48ppm, with approximately 30 seconds equilibrium establishments, and when lower concentration, with approximately 50 seconds equilibrium establishments.
Industrial applicibility
Sensor disclosed herein is useful in the field application of sulfur content of determining fuel with permission operator before fuel is introduced to machine especially, and this machine can be designed to by having the operating fuel of specific sulphur concentration.Sensor disclosed herein can be modified to airborne sensor disposable, reusable or conduct sulfur content of the fuel in definite tanks neck before entering the fuel of appreciable amount.
Figure 21 demonstration is exposed to the multiple resulting result of liquid with various sulphur concentrations by the exemplary ZnO sulfer sensor forming according to the disclosure.Particularly, use MOCVD in copper substrate, to form ZnO microstructure.Figure 21 the results are shown under steady current, and when exposing sensor to having 10,20,48,135,155,183 and during the liquid of the sulphur of 297ppm, the voltage applying across sensor and liquid is temporal evolution how.The sensor of Figure 21 shows the excellent sensitivity for lower sulphur concentration (10-155ppm), and for the poor sensitivity of higher sulphur concentration (183-297ppm).As shown in figure 20, the sensor shown in Figure 18 is presented under low (5ppm) and higher (386ppm) concentration excellent sensitivity.For 5ppm liquid, the sensor of Figure 20 reached saturation point in approximately 100 seconds, and for whole concentration, the sensor of Figure 21 reaches saturation point in less than one minute.Therefore, disclosed sensor is enough fast and with minimum inconvenience concerning using in field.
As alternative, as indicated in the stabilization across the voltage of sensor when keeping constant when electric current, operator can monitor for the ZnO sulfer sensor amount of saturated required time.Operator can come associated stabilization voltage to sulfur content with look-up table, or uses this association of known automaticization technology robotization such as the computing machine of a series of look-up tables of access, and definitely sulphur reading can be distributed to operator.
For form ZnO microstructure on substrate, can use any suitable deposition known in the art and/or growing method.For example, as mentioned above, can use MOCVD to form ZnO sediment in conduction or ceramic substrate.Figure 22 and table 1 show vacuum pressure and cycling time or the impact of sedimentation time on (002) crystallinity, and secondary cause is collector temperature and bubbler temperature simultaneously.The about ZnO microstructure of two hours that Figure 18 shows growth, and Figure 19 shows the ZnO microstructure of growing under the same conditions approximately 3.5 hours.The thickness of the ZnO microstructure shown in Figure 18 is about 0.7 micron and its density and is suitable for allowing ZnO microstructure to leave substrate growth with the direction of height random.By comparing, the thickness of the ZnO microstructure shown in Figure 19 is about 1.0 microns.Although thickness itself is acceptable, because high density suppresses the interaction between microstructure and liquid, the density of the lip-deep ZnO of conductive substrates is for the low concentration of sulphur and Yan Taigao.Such high density forces ZnO microstructure with highly compact, mode is left substrate growth in an orderly manner.Therefore, can adopt two or more sensor for the fuel of different sulphur concentrations.
Although the disclosure has mentioned that ZnO microstructure is as microstructure, those skilled in the art should understand microstructure can have subsidiary a considerable amount of, may during deposition and growth technique, come from other element of substrate.For example, when conductive substrates is stainless steel, microstructure can have the C between about 1.0-5.0wt%, the O between about 14.0-24.0wt%, and the Cr between about 0.5-1.5wt%, and the Fe between about 2.5-7.0wt%, counterbalance is Zn.In an example, the ZnO microstructure that analysis is presented at stainless steel Grown has following composition, according to percentage by weight: C--3.31; O--17.90; Cr--1.04; Fe--4.53; And Zn--73.22.
For the required time of the sulfur content in accurate tracer liquid, except other factors, as shown in Fig. 6,8,10,11,13,20-21 and 24, this conductivity, ZnO microstructure that highly depends on substrate is exposed to total surface area in liquid and the sulphur concentration of liquid.From data, can find out, when using the sulphur level of the ZnO sulfer sensor test fuel forming according to the disclosure, due to the sulphur level increase of liquid, the response time reduces and the voltage of stabilization increases.
Claims (10)
1. for determining a sensor for the sulphur concentration of liquid (34), described sensor comprises:
Substrate (30);
Described substrate (30) is coated with zinc paste at least in part; And
Wherein, described zinc paste has the crystalline network along (002) planar orientation.
2. according to the sensor of claim 1, wherein, described zinc paste is polycrystalline.
3. according to the sensor of claim 1 or 2, wherein, described substrate (30) conducts electricity.
4. according to any sensor in claims 1 to 3, wherein, described substrate (30) is connected to working electrode (32) for pottery and described substrate (30) and zinc paste.
5. according to the sensor of claim 4, also comprise contrast electrode (35).
6. according to any sensor in claim 1 to 5, wherein, described Zinc oxide coating is oxygen lack.
7. according to any sensor in claim 1 to 6, wherein, described zinc paste comprises the microstructure (31) of bar-shaped or belt-like form.
8. according to the sensor of claim 7, wherein, the width of described microstructure (31) is at least about 0.1 micron.
9. according to the sensor of claim 7, wherein, the width of described microstructure (31) is between approximately 0.1 micron and approximately 3 microns.
10. for determining a method for the sulphur concentration of liquid (34), described method comprises:
Described liquid (34) is exposed to sulfer sensor, described sensor comprises working electrode (32), described working electrode (32) comprises substrate (30), conductive material and from the outstanding zinc oxide microstructure (31) of described substrate (30), at least some in described zinc oxide microstructure (31) have the crystalline network along (002) planar orientation, and described sulfer sensor also has contrast electrode (35);
Steady current is applied to described substrate (30);
The voltage of monitoring between described work and contrast electrode (32); And
Described voltage is associated with to the sulphur concentration in described liquid (34).
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US13/354,766 | 2012-01-20 | ||
| US13/354,766 US8653839B2 (en) | 2009-07-17 | 2012-01-20 | Zinc oxide sulfur sensors and method of using said sensors |
| PCT/US2013/021676 WO2013109588A1 (en) | 2012-01-20 | 2013-01-16 | Zinc oxide sulfur sensors and methods of manufacture thereof |
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| Publication Number | Publication Date |
|---|---|
| CN104067114A true CN104067114A (en) | 2014-09-24 |
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| CN201380005853.8A Pending CN104067114A (en) | 2012-01-20 | 2013-01-16 | Zinc oxide sulfur sensors and methods of manufacture thereof |
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| JP (1) | JP2015504172A (en) |
| CN (1) | CN104067114A (en) |
| DE (1) | DE112013000635T5 (en) |
| WO (1) | WO2013109588A1 (en) |
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| CN114994140B (en) * | 2022-05-24 | 2023-06-16 | 哈尔滨工业大学 | Zinc oxide-titanium dioxide sensor for detecting sulfur content and preparation method and application thereof |
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- 2013-01-16 JP JP2014553358A patent/JP2015504172A/en active Pending
- 2013-01-16 DE DE112013000635.9T patent/DE112013000635T5/en not_active Withdrawn
- 2013-01-16 WO PCT/US2013/021676 patent/WO2013109588A1/en active Application Filing
- 2013-01-16 CN CN201380005853.8A patent/CN104067114A/en active Pending
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| CN1445821A (en) * | 2002-03-15 | 2003-10-01 | 三洋电机株式会社 | Forming method of ZnO film and ZnO semiconductor layer, semiconductor element and manufacturing method thereof |
| US20040234823A1 (en) * | 2003-05-20 | 2004-11-25 | Burgener Robert H. | Zinc oxide crystal growth substrate |
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| DE112013000635T5 (en) | 2014-10-09 |
| WO2013109588A1 (en) | 2013-07-25 |
| JP2015504172A (en) | 2015-02-05 |
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