CN101620057B - Method for preparing quartz crystal microbalance humidity sensor based on sequential silica-based mesoporous materials SBA-15 - Google Patents
Method for preparing quartz crystal microbalance humidity sensor based on sequential silica-based mesoporous materials SBA-15 Download PDFInfo
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- CN101620057B CN101620057B CN2009100523785A CN200910052378A CN101620057B CN 101620057 B CN101620057 B CN 101620057B CN 2009100523785 A CN2009100523785 A CN 2009100523785A CN 200910052378 A CN200910052378 A CN 200910052378A CN 101620057 B CN101620057 B CN 101620057B
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Abstract
The invention relates to a method for preparing quartz crystal microbalance humidity sensor based on sequential silica-based mesoporous materials SBA-15, belonging to the technical field of humidity sensitive material and humidity sensor. The invention adopts the silica-based mesoporous materials SBA-15 with large specific surface areas, good absorption property, uniform bore diameters, adjustable dimensions in nanometer admeasurement and sequential structural height as the humidity sensitive materials of a quartz crystal microbalance (QCM) quality type sensor to prepare the humidity sensor. The humidity sensor has the advantages of large humidity measuring range (can be measured within a whole relative humidity range), little humidity hysteresis, fast response, high sensitivity, good repeatability, stable property, simple manufacturing technology, small material using amount, corrosion resistance, low cost, easy integrating, and the like, not only provides the very good humidity sensitive materials for the quartz crystal microbalance (QCM) quality type sensor, but also opens a new way for the application of the sequential silica-based mesoporous materials.
Description
Technical field
The present invention relates to a kind of preparation method of the quartz crystal microbalance humidity sensor based on sequential silicon-based mesoporous material SBA-15, belong to humidity-sensitive material and humidity sensor technical field.
Technical background
Humidity sensor is the important sensor of a class, has a wide range of applications at aspects such as storage, commercial production, process control, environmental monitoring, household electrical appliance, meteorologies.As: the storage of the mildew-resistant of grain, chamber planting, precision electronic element manufacturing, space missile, rocket, aerological sounding etc., therefore research is very active both at home and abroad.Humidity sensor is various in style, but with regard to its employed wet sensory material, mainly contains electrolyte and macromolecular compound material, semiconductor ceramic material and elemental semiconductor, porous metal oxide etc.The electrolyte humidity sensor has shortcomings such as measurement range is narrow, repeatability is poor, serviceable life is short; The macromolecular compound humidity sensor has advantages such as wet sensing performance is good, sensitivity height, but under high temperature and super-humid conditions degradation, poor stability, anticorrosive and anti-contamination ability; But the semiconductor ceramic material humidity sensor have wet sensing performance better, produce advantage such as simple, cost is low, short heated wash of response time but accuracy is lower, poor performance under the high temperature, be difficult to integrated.Sequential silicon-based mesoporous material has bigger specific surface area and pore volume, duct size homogeneous and adjustable continuously on nanoscale; Regular pore passage structure from the one dimension to the two dimension, controlled pattern, as film, sheet, ball etc.; The surface is rich in the silicon hydroxyl and is easy to functionalization; Silicon dioxide does not have series of advantages such as physiology toxicity, make they big molecule or heavy ion absorption with separate, the field such as synthetic of chemical sensor, biomedicine, chemical industry catalysis, environmental protection and nano material shows wide application prospect.It is the humidity-sensitive material of QCM (Quartz Crystal Microbalance) (QCM) mass type sensor that the present invention uses sequential silicon-based mesoporous material first, makes up humidity sensor.Not only overcome the shortcoming of the sensor, also for QCM has found a kind of well wet sensitive sensing material, more mesoporous material has been opened up a kind of new application simultaneously.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of the quartz crystal microbalance humidity sensor based on sequential silicon-based mesoporous material SBA-15.Another object of the present invention provides a kind of humidity sensor sensing element with superior wet quick performance.
The present invention is a kind of preparation method of the quartz crystal microbalance humidity sensor based on sequential silicon-based mesoporous material SBA-15, it is characterized in that being to have following technological process and step:
The preparation method of a.SBA-15 sequential silicon-based mesoporous material: earlier the poly-oxirene ether of 1.0-2.0 gram-poly-propylene oxide ether-poly-oxirene ether (P123) is dissolved in the acid solution that 75ml concentration is 1.0-2.0M, after stirring 1-3 hour under 40 ℃ of temperature, the more own ester of positive silicic acid (TEOS) about the 3-4 gram is joined in this solution.Directly under said temperature, continue to stir 24 hours after adding, transfer to then in the water heating kettle 100 ℃ of following crystallization 24 hours.After filtration, washing, the drying, the product that obtains in 550 ℃ of following roastings 6 hours, is promptly obtained the SBA-15 sequential silicon-based mesoporous material that the aperture is 2-50nm after being cooled to room temperature.
B. the preparation of quartz crystal microbalance humidity sensor parts: with ultrasonic dispersion 20-50 minute in certain medium of the above-mentioned aperture that the makes SBA-15 sequential silicon-based mesoporous material that is 2-50nm, coating liquid; Used medium is any of water, acetone or alcohol; Then coating liquid evenly is coated in electrode surface, and, promptly obtains described quartz crystal microbalance humidity sensor parts 80～120 ℃ of oven dry 3～8 hours through strict QCM (Quartz Crystal Microbalance) of cleaning.
The sequential silicon-based mesoporous material SBA-15 that the present invention adopts is as described below as the mechanism of humidity-sensitive material:
(1) chemisorption desorption: the inorganic wall of mesoporous silicon oxide is amorphous, contain abundant surface silanol group on the wall, and the silicon hydroxyl can combine with weak hydrogen bond action power with airborne moisture, and this reaction is with regard to reversible carrying out when airborne humidity changes.
(2) physisorption desorption: ordered mesoporous material has big specific surface area (generally at 500m
2/ g), so high porosity is the moisture in can absorbed air.
The advantage and the characteristics of the quartz crystal microbalance humidity sensor parts that the inventive method makes are as described below:
(1) the used sequential silicon-based mesoporous material SBA-15 of the present invention is as humidity-sensitive material, its aperture homogeneous and adjustable, specific surface area is big (generally at 500m
2More than/the g), the porosity height and since wall on contain abundant surface silanol group, can combine with weak hydrogen bond action power with airborne moisture, increased the sensitivity of humidity sensor greatly.Simultaneously SBA-15 (its principal ingredient is that silicon dioxide does not have physiology toxicity) as its consumption of humidity-sensitive material seldom, more economical compared with the high molecular polymer humidity-sensitive material of the marketization, more help environmental protection.
(2) the prepared humidity sensor of the inventive method, it is highly sensitive, response is fast, the linearity is good, stable performance, anticorrosive, device is simple, cost is low, it is integrated to be easy to: and quartz crystal microbalance sensor is easy to accept and transmit signal.
(3) the prepared humidity sensor of the inventive method has humidity range big (1-100%RH), humidity hysteresis is little, response is fast, highly sensitive, good reproducibility, stable performance, material usage seldom, corrosion resistivity is good and manufacture craft is simple.
Description of drawings:
The aperture that Fig. 1 is respectively used be 4-7nm ordered mesoporous material SBA-15 the TEM photo of transmission electron microscope;
Fig. 2 is by ordered mesoporous material SBA-15 nitrogen adsorption desorption curve and the desorption pore diameter distribution used among the embodiment 1,
Fig. 3 is by the scanned photograph of among the embodiment 2 mesoporous material being clapped to quartz crystal microbalance sensor (QCM) electrode surface;
Fig. 4 is cyclic curve figure under 73% condition for the SBA-15 humidity-sensitive material that is about 5nm by following embodiment 1 described aperture in relative humidity;
Fig. 5 is respectively sample 1 and sample 2 and the frequency one relative humidity response curve of uncoated silicon base ordered mesopore material quartz crystal microbalance sensor (QCM) in the humidity uphill process of 16nm and 28nm for the sequential silicon-based mesoporous material coating thickness that applies by sensor among the embodiment 1,2.
Embodiment
Now specific embodiments of the invention are narrated some.
Embodiment one:
The preparation method of order mesoporous silica-base material aperture SBA-15 quartz crystal microbalance sensor (QCM), its process and step are as follows:
(1) preparation method of the order mesoporous silica-base material of SBA-15: earlier 1.5 gram P123 are dissolved in the hydrochloric acid solution that 75ml concentration is 1.0-2.0M, after stirring 3 hours under 40 ℃ of temperature, again the 4.3 gram own esters of positive silicic acid (TEOS) are joined in this solution.Directly under this temperature, continue to stir 24 hours after adding, transfer to then in the water heating kettle 100 ℃ of following crystallization 24 hours.After filtration, washing, the drying, the product that obtains in 550 ℃ of following roastings 6 hours, is promptly obtained required sample after being cooled to room temperature.Its aperture is about 7nm.
With the aperture of gained is ultrasonic dispersion 20-50 minute in certain medium of mesoporous material about 5nm, coating liquid; It is uniformly coated on QCM (Quartz Crystal Microbalance) (QCM) sensor electrode 80-120 ℃ of oven dry.Finally make the quick performance test of wetting of humidity sensor device.
The thickness that above-mentioned material is coated in QCM (Quartz Crystal Microbalance) (QCM) sensor electrode is respectively 16nm and 28nm, obtains sample and is labeled as S1 and S2 respectively.
Every detection and test
The detection of gained sample in the foregoing description and result of experiment referring to the Fig. 1 in the accompanying drawing and Fig. 5, are also had and the corresponding table 1 of Fig. 5.
Referring to Fig. 1, Fig. 1 can find out clearly that for transmission electron microscope (TEM) photo of the used ordered mesoporous material SBA-15 of the present invention this ordered mesoporous material SBA-15 has the duct of orderly homogeneous.
Referring to accompanying drawing 2,, as can be seen from the figure the SBA-15 of synthetic gained has IV type adsorption curve, proves that this material has typical linear pattern pore structure, pore diameter distribution is very narrow as can be seen from graph of pore diameter distribution; The duct that the used ordered mesoporous material SBA-15 of the two illustrated together has uniform and ordered.
Referring to accompanying drawing 3 as can be seen from the figure ordered mesoporous material SBA-15 be coated to electrode surface, and consumption is seldom.
Referring to accompanying drawing 4, as can be seen from the figure this sensor, frequency change very sensitive to the response of humidity reaches 2200Hz, and respond highly stable fast, good reproducibility.
Referring to accompanying drawing 5 and table 1: straight line is the line of response by the match of Origin software.Table 1 has provided the equation and the related coefficient of sample matched curve, and wherein Y represents frequency change value (Hz), and x represents rh value (RH%).Can see that the frequency response of the QCM (Quartz Crystal Microbalance) that uncoated mesoporous material is film modified changes with the variation of humidity hardly, sample 1 is respectively the device that applies the different thickness in same aperture with sample 2.Thickness through calculation sample 1 and 2 is respectively 16nm and 28nm.The sensitivity that can see sample 1 is 46.41Hz/%RH, and the sensitivity of sample 2 more reaches 68.40Hz/%RH.Can see that under identical relative humidity situation along with the increase of coating thickness, the frequency change value is also along with increase, this just shows the increase with sensitive material thickness, and the sensitivity of sensor is risen.But be not to mean that thickness can infinitely increase, when surpassing certain value, the little balance of quartz crystal oscillator is difficult to starting of oscillation.
Can confirm from the frequency change relation research of sensor with humidity: ordered mesoporous material SBA-15 has high sensitivity, is the desirable alternative materials of humidity sensor.Even in experiment, can also see quartz crystal microbalance sensor based on ordered mesoporous material under the very high situation of humidity (＞90%RH) still can starting of oscillation, than applying the sensor that other material can not starting of oscillation under high humility, be good improvement, have remarkable advantages.
Table 1
[0035]?
| Sample | The match linear equation | Related coefficient | Standard deviation |
| Uncoated | y＝0.0543x+1.8293? | 0.3242? | 5.7930? |
| S-1? | y＝-46.41x+1307.1? | 0.9890? | 252.23? |
| S-2? | y＝-68.40x+2002.9? | 0.9551? | 779.42? |
Claims (1)
1. preparation method based on the quartz crystal microbalance humidity sensor of sequential silicon-based mesoporous material SBA-15 is characterized in that having following technological process and step:
The preparation method of a.SBA-15 sequential silicon-based mesoporous material: earlier the poly-oxirene ether of 1.0-2.0 gram-poly-propylene oxide ether-poly-oxirene ether (P123) is dissolved in the acid solution that 75ml concentration is 1.0-2.0M, after stirring 1-3 hour under 40～48 ℃ of temperature, the more own ester of positive silicic acid (TEOS) about 34 grams is joined in this solution; Directly under said temperature, continue to stir 24 hours after adding, transfer to then in the water heating kettle 80～130 ℃ of following crystallization 24 hours; After filtration, washing, the drying, the product that obtains in 550 ℃ of following roastings 6 hours, is promptly obtained the SBA-15 sequential silicon-based mesoporous material that the aperture is 2-50nm after being cooled to room temperature;
B. the preparation of quartz crystal microbalance humidity sensor parts: with ultrasonic dispersion 20-50 minute in certain medium of the above-mentioned aperture that the makes SBA-15 sequential silicon-based mesoporous material that is 2-50nm, coating liquid; Used medium is any of water, acetone or alcohol; Then coating liquid evenly is coated in electrode surface, and, promptly obtains described quartz crystal microbalance humidity sensor parts 80～120 ℃ of oven dry 3～8 hours through strict QCM (Quartz Crystal Microbalance) of cleaning.
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| CN102033028B (en) * | 2010-09-21 | 2012-08-29 | 上海大学 | Preparation method of mass type formaldehyde sensor based on functionalized SBA-15 |
| CN102175764A (en) * | 2011-02-24 | 2011-09-07 | 中国科学院上海微系统与信息技术研究所 | Quality chemical sensor using functionalized mesoporous material as sensitive material and method |
| BRPI1102638B1 (en) * | 2011-06-16 | 2020-10-20 | Universidade Federal Do Rio Grande Do Sul | zeolite and mesoporous materials organized as filler for the formulation of rubber compounds, thermoplastic rubber, plastic and product manufacturing |
| CN102778408B (en) * | 2012-06-15 | 2014-11-26 | 天津大学 | Device of quartz crystal monitor (QCM) chip with surface modified by zinc oxide nanometer chain and preparation method of QCM chip |
| CN104198321B (en) * | 2014-09-03 | 2017-01-25 | 电子科技大学 | QCM (quartz crystal microbalance) formaldehyde sensor with chemical and physical adsorption effects and preparation method thereof |
| DE102017127341B4 (en) * | 2017-11-20 | 2019-08-14 | Trafag Ag | Humidity sensor element, method for producing a humidity sensor element, humidity or dew point sensor and moisture measurement method |
| CN108982277B (en) * | 2018-06-20 | 2020-05-19 | 华中科技大学 | Preparation method of quartz crystal microbalance humidity sensor and product |
| CN114397361B (en) * | 2021-02-23 | 2024-05-24 | 北京理工大学 | Preparation method of green polymer material for humidity sensor |
| CN113390748A (en) * | 2021-06-16 | 2021-09-14 | 电子科技大学 | Humidity sensor based on quartz crystal microbalance and preparation method |
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| JP特开2008-32413A 2008.02.14 |
| 石新军.石英晶振微天平湿度传感器响应特性研究.《桂林航天工业高等专科学校学报》.2006,(第2期), * |
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