CN103424329B - A kind of preparation method detecting the gas sensor array of strong fragrant aromatic white spirit - Google Patents
A kind of preparation method detecting the gas sensor array of strong fragrant aromatic white spirit Download PDFInfo
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- CN103424329B CN103424329B CN201310364390.6A CN201310364390A CN103424329B CN 103424329 B CN103424329 B CN 103424329B CN 201310364390 A CN201310364390 A CN 201310364390A CN 103424329 B CN103424329 B CN 103424329B
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- evaporation
- gas sensor
- sensor array
- white spirit
- aromatic white
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Abstract
The invention provides a kind of preparation method detecting the gas sensor array of strong fragrant aromatic white spirit, comprise step: (1) with vacuum coating equipment respectively by sodium polyacrylate, poly-trimethyl silicane-1-propine, polystyrene, alkyd resin, polypropylene evaporation on different quartz substrates; (2) by quartz substrate good for evaporation welding on circuit boards; Apply gas sensor array size prepared by method of the present invention little, cost is low, reproducible, can long-term stable operation, and the impact that co-existing gases produces is little, high to the resolution performance of mixed gas.And with the electric nasus system that it is made in conjunction with piezoelectric system, the pretreatment process not needing sample loaded down with trivial details when detecting the strong fragrant aromatic white spirit true and false, can directly carry out, and fast response time, accuracy is high.
Description
Technical field
The invention belongs to gas sensor technology field, especially relate to a kind of preparation method detecting the gas sensor array of strong fragrant aromatic white spirit.
Background technology
At present, food security has been global problems, especially in the liquor industry of relation broad masses of the people life, there is the problems such as lower, the quick detectability deficiency of quality and safety control level, correlation technique and equipment fall behind, how to differentiate that white wine quality becomes the Focal point and difficult point of food products market management.The nineties in 20th century, occur that a kind of mode combined by gas sensor and mode identification technology simulates Biologic Olfaction system, thus realize the new equipment-Electronic Nose (also known as smell scanner) of volatile matter being carried out to detection and Identification function, its core component is gas sensor, has objective, quick, repeated advantage.
In the development of Electronic Nose, the choice and application of gas sensor array is key factor, and suitable sensor array is most important to the performance improving whole system.Gas sensor mainly conductance control sensor (having body conductance control type and surface conductance control type two kinds) of current application, if publication number is the gas sensor of CN114655A, its structure mainly comprises layer of metal oxide gas sensory (as ZnO, SnO
2deng) and a well heater.This kind of gas sensor needs to be heated to carrying out smoothly of about 300 DEG C of guarantee redox reactions, therefore there is following drawback in it: one, need heating and temperature controlling device, add the volume of sensor, power consumption and complexity, inconvenience makes of existing microelectronic technique; Two, integrated level is not high; Three, not high to the organic gas sensitivity that most of oxidation-reduction quality is more weak.Therefore, development a kind ofly can be detected fast, liquor determination device that resolution is high, the effective development of China's food service industry is significant.
Summary of the invention
The object of the invention is to provide a kind of preparation method detecting the gas sensor array of strong fragrant aromatic white spirit, and size of the present invention is little, and cost is low, reproducible, and energy long-term stable operation, the impact that co-existing gases produces is little, high to the resolution performance of mixed gas.
Realize a kind of preparation method detecting the gas sensor array of strong fragrant aromatic white spirit of the object of the invention, comprise step:
(1) with vacuum coating equipment respectively by sodium polyacrylate, poly-trimethyl silicane-1-propine, polystyrene, alkyd resin, polypropylene evaporation on different quartz substrates;
(2) by quartz substrate good for evaporation welding on circuit boards.
In described step (1), the vacuum tightness of vacuum coating equipment is 1 × 10
-6-1 × 10
-5mbar.
In described step (1), four kinds of thin polymer film evaporation thickness are 30 μm-50 μm.
In described step (1), evaporation temperature is 80-120 DEG C.
The beneficial effect of the gas sensor array that application the method is made:
Size of the present invention is little, and cost is low, reproducible, and energy long-term stable operation, the impact that co-existing gases produces is little, high to the resolution performance of mixed gas.The electric nasus system that this gas sensor array is made in conjunction with piezoelectric system, the pretreatment process not needing sample loaded down with trivial details when detecting strong fragrant aromatic white spirit, can directly carry out, and fast response time, accuracy is high.
Embodiment
For better the present invention being described, below the technical scheme in the embodiment of the present invention is clearly and completely described.
Be water, ethanol, ethyl acetate, ethyl hexanoate, acetal by the GC-MS characteristic volatile ingredient analyzed in strong fragrant aromatic white spirit (for Jiu Gui Jiu) in the lab.Have carboxyl according in the structural formula of sodium polyacrylate, easily and between hydrone form stronger hydrogen bond action, so sodium polyacrylate is soluble in water, namely it has good compatibility to water; Form stronger hydrogen bond action according to the oxygen atom of the hydrogen atom on silicon methyl in poly-trimethyl silicane-1-propine structure easily and in ethanol molecule, judge that it is soluble in ethanol, namely it has good compatibility to ethanol; Solubility parameters (δ=9.1) according to the solubility parameters (δ=8.9) of polystyrene and ethyl acetate is very close, and the degree of their polarity and formation hydrogen bond is roughly equal, so polystyrene is soluble in ethyl acetate, namely ethyl acetate p-poly-phenyl ethene has good compatibility; Electrophilic group (-COOH) is contained, containing electron donating group (-OCOCH in ethyl hexanoate according in Structure Detemination of Alkyd Resins
3), alkyd resin and the intermolecular hydrogen bond action in addition of ethyl hexanoate in addition, judge that alkyd resin is soluble in ethyl hexanoate, namely alkyd resin has good compatibility to ethyl hexanoate; Can judge that polypropylene is soluble in acetal according to rule of similarity, and it is close according to the solubility parameters (δ=16.5) of polyacrylic solubility parameters (δ=17) and acetal, also can judge that polypropylene is soluble in acetal, namely polypropylene has good compatibility to acetal.Following table is the fluoropolymer resin structural formula of characteristic compounds in Jiu Gui Jiu and compatibility sensitivity thereof:
Therefore five kinds of polymkeric substance in the present invention are corresponding respectively has good compatibility with principal ingredient water, ethanol, ethyl acetate, ethyl hexanoate, acetal etc. in strong fragrant aromatic white spirit.When detecting the mixed gas in sample white wine by this gas sensor array, polymer film can to there being higher responsiveness, the electric signal collection of illustrative plates of comprehensive response is obtained by piezoelectric system, namely the characteristic spectrum storehouse reflecting this sample is obtained, by contrasting with the standard diagram of strong fragrant aromatic white spirit, to reach the qualitative analysis to detecting sample white wine.
Embodiment 1:
1, testing sodium polyacrylate used buys in Aladdin reagent company limited, and molecular weight is 4,000,000; Water is secondary deionized water; Poly-trimethyl silicane-1-propine is bought in Aladdin reagent company limited, and molecular weight is 500,000; Ethanol is bought in Aladdin reagent company limited, is AR level pure reagent; Polystyrene is bought in lark prestige reagent company limited, and molecular weight is 15000; Ethyl acetate is bought in lark prestige reagent company limited, and purity is 99.8%; Alkyd resin is bought in Aladdin reagent company limited, and molecular weight is 2,000,000; Ethyl hexanoate is bought in Aladdin reagent company limited, and purity is 99%; Polypropylene is bought in lark prestige reagent company limited; Acetal, purity is 99%.
2, on UNIVEX-300 type vacuum coating equipment respectively by sodium polyacrylate, poly-trimethyl silicane-1-propine, polystyrene, alkyd resin, polypropylene evaporation on the circular quartz substrate of diameter to be 8mm thickness be 1mm, its concrete steps are as follows:
(1) select suitable substrate frame, place quartz substrate and polystyrene;
(2) check recirculated cooling water, pressurized air and high pure nitrogen state, check the oil level of mechanical pump and outlet oil mist filter;
(3) primary power knob is threaded to vertical position, after instrument self checking is normal, bell jar is buckled, note the connecting rod position in left side;
(4) F is passed through
1and F
5display screen is switched to interface of bleeding, starts to bleed, after starting to bleed, forbid power-off;
(5) on thickness setting instrument, setting evaporation thickness is 30 μm; Control mode is changed into auto in the baffle controls interface of main screen;
(6) when vacuum tightness reaches 1 × 10
-6during mbar, start evaporation;
(7) hot evaporated segment: the hot evaporation power-supply controller of electric opening bottom, changes control model into internal, give tacit consent to No. 1 (inner side) heated by electrodes.Regulate electric current to rise to 80 DEG C to vacuum the temperature inside the box, observe heating boat situation by view window.Baffle plate opened by the open button pressing film-thickness monitoring, starts evaporation.When thickness reaches 30 μm, the automatic closing baffle plate of film-thickness monitoring, by the control mode switch of hot evaporation power-supply controller of electric to external, cuts off electric current.This layer material evaporation completes;
(8) evaporation continues after completing to vacuumize about 10 minutes, stops bleeding after waiting plating material to cool completely again;
(9) be switched to interface of bleeding when closing vacuum pump, after pressing switch, first molecular pump starts stall, now molecular pump power source controller shows the load of molecular pump.After load pilot lamp extinguishes, main screen is switched to inflation interface, presses inflation button and start inflation.Now need the reduction valve opening High Purity Nitrogen, back pressure is forbidden more than an atmospheric pressure.Open bell jar after having exitted, take out sample and plating material, evaporation process completes, orderly close-down High Purity Nitrogen, primary power, recirculated cooling water and pressurized air;
(10) in like manner, by sodium polyacrylate, poly-trimethyl silicane-1-propine, alkyd resin, polypropylene respectively evaporation on the circular quartz substrate of diameter to be 8mm thickness be 1mm.
3, the model bought in Beijing Orient De Fei Instrument Ltd. be OCA20 contact angle instrument on measure the contact angle of often kind of reagent and its correspondence, the contact angle of measurement result display water and sodium polyacrylate film is 17.5 °, much smaller than 90 °, show that the compatibility of water and sodium polyacrylate is fine; The contact angle of ethanol and poly-trimethyl silicane-1-propine film is 20.6 °, shows that the compatibility of ethanol and poly-trimethyl silicane-1-propine is fine; The contact angle of ethyl acetate and plasticon is 25.5 °, shows that the compatibility of ethyl acetate and polystyrene is better; The contact angle of ethyl hexanoate and alkyd resin film is 23 °, shows that the compatibility of ethyl hexanoate and alkyd resin is better; The contact angle of acetal and polypropylene film is 20 °, shows that the compatibility of acetal and acrylic resin is better.
4, five kinds of polymer film piezoids of preparation in step 2 are welded on circuit board respectively, make gas sensor, be finally arranged in a row in the plastics box being fixed on long × wide × height=50 × 1.5 × 15mm, made gas sensor array.
Embodiment 2:
1, agents useful for same and polymkeric substance in the same manner as in Example 1.
2, be 10mm by sodium polyacrylate, poly-trimethyl silicane-1-propine, polystyrene, alkyd resin, polypropylene evaporation at diameter respectively on UNIVEX-300 type vacuum coating equipment, thickness is that on the circular quartz substrate of 0.8mm, its concrete steps are as follows:
(1) select suitable substrate frame, place quartz substrate and alkyd resin;
(2) check recirculated cooling water, pressurized air and high pure nitrogen state, check the oil level of mechanical pump and outlet oil mist filter;
(3) primary power knob is threaded to vertical position, after instrument self checking is normal, bell jar is buckled, note the connecting rod position in left side;
(4) F is passed through
1and F
5display screen is switched to interface of bleeding, starts to bleed, after starting to bleed, forbid power-off;
(5) on thickness setting instrument, setting evaporation thickness is 40 μm; In the baffle controls interface of main screen
Change control mode into auto;
(6) when vacuum tightness reaches 0.5 × 10
-5during mbar, start evaporation;
(7) hot evaporated segment: the hot evaporation power-supply controller of electric opening bottom, changes control model into internal, give tacit consent to No. 1 (inner side) heated by electrodes.Regulate electric current to rise to 100 DEG C to vacuum the temperature inside the box, observe heating boat situation by view window.Baffle plate opened by the open button pressing film-thickness monitoring, starts evaporation.When thickness reaches 40 μm, the automatic closing baffle plate of film-thickness monitoring, by the control mode switch of hot evaporation power-supply controller of electric to external, cuts off electric current.This layer material evaporation completes;
(8) evaporation continues after completing to vacuumize about 10 minutes, stops bleeding after waiting plating material to cool completely again;
(9) be switched to interface of bleeding when closing vacuum pump, after pressing switch, first molecular pump starts stall, now molecular pump power source controller shows the load of molecular pump.After load pilot lamp extinguishes, main screen is switched to inflation interface, presses inflation button and start inflation.Now need the reduction valve opening High Purity Nitrogen, back pressure is forbidden more than an atmospheric pressure.Open bell jar after having exitted, take out sample and plating material, evaporation process completes, orderly close-down High Purity Nitrogen, primary power, recirculated cooling water and pressurized air;
(10) in like manner, by sodium polyacrylate, poly-trimethyl silicane-1-propine, polystyrene, polypropylene etc. respectively evaporation be 10mm at diameter, thickness is on the circular quartz substrate of 0.8mm.
3, the model bought in Beijing Orient De Fei Instrument Ltd. be OCA20 contact angle instrument on measure the contact angle of the thin polymer film of often kind of reagent and its correspondence, measurement result is identical with in embodiment 1.
4, five kinds of polymer film piezoids of preparation in step 2 are welded on circuit board respectively, make gas sensor, be finally arranged in a row in the plastics box being fixed on long × wide × height=60 × 1.5 × 15mm, just made gas sensor array.
Embodiment 3:
1, agents useful for same and polymkeric substance in the same manner as in Example 1.
2, on UNIVEX-300 type vacuum coating equipment, respectively sodium polyacrylate, poly-trimethyl silicane-1-propine, polystyrene, alkyd resin, polypropylene evaporation are being grown × wide=10 × 10mm, thickness is that on the square quartz substrate of 1mm, its concrete steps are as follows:
(1) select suitable substrate frame, place quartz substrate and alkyd resin;
(2) check recirculated cooling water, pressurized air and high pure nitrogen state, check the oil level of mechanical pump and outlet oil mist filter;
(3) primary power knob is threaded to vertical position, after instrument self checking is normal, bell jar is buckled, note the connecting rod position in left side;
(4) F is passed through
1and F
5display screen is switched to interface of bleeding, starts to bleed, after starting to bleed, forbid power-off;
(5) on thickness setting instrument, setting evaporation thickness is 50 μm; In the baffle controls interface of main screen
Change control mode into auto;
(6) when vacuum tightness reaches 1 × 10
-5during mbar, start evaporation;
(7) hot evaporated segment: the hot evaporation power-supply controller of electric opening bottom, changes control model into internal, give tacit consent to No. 1 (inner side) heated by electrodes.Regulate electric current to rise to 120 DEG C to vacuum the temperature inside the box, observe heating boat situation by view window.Baffle plate opened by the open button pressing film-thickness monitoring, starts evaporation.When thickness reaches 50 μm, the automatic closing baffle plate of film-thickness monitoring, by the control mode switch of hot evaporation power-supply controller of electric to external, cuts off electric current.This layer material evaporation completes;
(8) evaporation continues after completing to vacuumize about 10 minutes, stops bleeding after waiting plating material to cool completely again;
(9) be switched to interface of bleeding when closing vacuum pump, after pressing switch, first molecular pump starts stall, now molecular pump power source controller shows the load of molecular pump.After load pilot lamp extinguishes, main screen is switched to inflation interface, presses inflation button and start inflation.Now need the reduction valve opening High Purity Nitrogen, back pressure is forbidden more than an atmospheric pressure.Open bell jar after having exitted, take out sample and plating material, evaporation process completes, orderly close-down High Purity Nitrogen, primary power, recirculated cooling water and pressurized air;
(10) in like manner, by sodium polyacrylate, poly-trimethyl silicane-1-propine, polystyrene, polypropylene etc. respectively evaporation growing × wide=10 × 10mm, thickness is on the square quartz substrate of 1mm.
3, the model bought in Beijing Orient De Fei Instrument Ltd. be OCA20 contact angle instrument on measure the contact angle of the thin polymer film of often kind of reagent and its correspondence, measurement result is identical with in embodiment 1.
4, five kinds of polymer film piezoids of preparation in step 2 are welded on circuit board respectively, make gas sensor, be finally arranged in a row in the plastics box being fixed on long × wide × height=60 × 1.5 × 12mm, just made gas sensor array.
With the gas sensor array that the method is made, electric nasus system is can be made in conjunction with piezoelectric system, when detecting sample, gas sensor array is placed in the bottleneck of sample white wine, bottleneck is opened, smells of wine are through the injection port of gas sensor box, polymer film on gas sensor array is by the feature volatile ingredient of this wine of absorption, its quality is increased, this phenomenon obtains the electric signal spectrogram of comprehensive response by piezoelectric system, namely the feature spectrogram that can reflect sample white wine is obtained, this spectrogram contrasts with the standard spectrogram as the strong fragrant aromatic white spirit of identification, to reach the qualitative analysis to detected sample white wine.
The present invention is by analyzing the physicochemical property of the feature volatile matter of strong fragrant aromatic white spirit, study and screen the polymer thin film coating materials of suitable compatibility sensitivity, to study and the feature intelligent gathering strong fragrant aromatic white spirit smells news collection of illustrative plates, by collection of illustrative plates comparison, whether the true and false and the quality that detect sample white wine reach a standard.
The gas sensor array that application the present invention makes, size is little, and cost is low, reproducible, and energy long-term stable operation, the impact that co-existing gases produces it is little, high to the resolution performance of mixed gas.And its electric nasus system made in conjunction with piezoelectric system, the pretreatment process not needing sample loaded down with trivial details when detecting strong fragrant aromatic white spirit, can directly carry out, fast response time, accuracy is high.
The above; be only the present invention's preferably embodiment, but protection scope of the present invention is not limited thereto, is anyly familiar with those skilled in the art in the technical scope that the present invention discloses; the change that can expect easily or replacement, all should be encompassed within protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the protection domain of claims.
Claims (1)
1. detect a preparation method for the gas sensor array of strong fragrant aromatic white spirit, it is characterized in that, comprise step:
(1) with vacuum coating equipment respectively by sodium polyacrylate, poly-trimethyl silicane-1-propine, polystyrene, alkyd resin, polypropylene evaporation on different quartz substrates;
(2) by quartz substrate good for evaporation welding on circuit boards;
In described step (1), the vacuum tightness of vacuum coating equipment is 1 × 10
-6-1 × 10
-5mbar; In described step (1), the evaporation thickness of five kinds of thin polymer films is 30 μm-50 μm; In described step (1), evaporation temperature is 80-120 DEG C;
Described sodium polyacrylate molecular weight is 4,000,000; Described poly-trimethyl silicane-1-propine molecular weight is 500,000; Described polystyrene molecular weight is 15000; Described alkyd resin molecular weight is 2,000,000; Described polypropylene is bought in lark prestige reagent company limited.
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| CN103424329B true CN103424329B (en) | 2016-02-03 |
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Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| RU2598551C1 (en) * | 2015-09-03 | 2016-09-27 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Воронежский государственный университет инженерных технологий" (ФГБОУ ВО "ВГУИТ"). | Mobile device for rapid assessment of liquid and solid and amorphous samples |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6321588B1 (en) * | 1998-09-11 | 2001-11-27 | Femtometrics, Inc. | Chemical sensor array |
| CN103063705A (en) * | 2012-12-25 | 2013-04-24 | 华中农业大学 | Trimethylamine gas sensor and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1215342C (en) * | 2003-05-08 | 2005-08-17 | 中国科学院上海技术物理研究所 | Film gas sensor |
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2013
- 2013-08-20 CN CN201310364390.6A patent/CN103424329B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6321588B1 (en) * | 1998-09-11 | 2001-11-27 | Femtometrics, Inc. | Chemical sensor array |
| CN103063705A (en) * | 2012-12-25 | 2013-04-24 | 华中农业大学 | Trimethylamine gas sensor and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| "基于气体传感器阵列的白酒分类与识别";王立川;《中国优秀硕士学位论文全文数据库 工程科技I辑》;20110915(第9期);第B024-101页第2-4章 * |
| "酒鬼酒馥郁香型风格的研究";刘建新 等;《酿酒科技》;20051231(第10期);第98-104页第3节 * |
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