CN109001273A - A kind of minisize pH sensor and preparation method thereof - Google Patents
A kind of minisize pH sensor and preparation method thereof Download PDFInfo
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- CN109001273A CN109001273A CN201810652079.4A CN201810652079A CN109001273A CN 109001273 A CN109001273 A CN 109001273A CN 201810652079 A CN201810652079 A CN 201810652079A CN 109001273 A CN109001273 A CN 109001273A
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/302—Electrodes, e.g. test electrodes; Half-cells pH sensitive, e.g. quinhydron, antimony or hydrogen electrodes
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Abstract
The invention discloses a kind of minisize pH sensors and preparation method thereof.The pH sensor for using the method for the invention to prepare is sheet type, all solid state minisize pH sensor, have the advantages that small in size, structural stability is good, high reliablity, good airproof performance, any test position of instrument and equipment can be placed in, it is influenced by extraneous factor small, is particularly suitable for the direct real-time monitoring of aircraft corrosion condition under the micro- liquid film environment of high humidity with high salt.And the hydrogen ion sensitive sense electrode that the present invention uses compensates in the prior art, and the pH sensor defect poor in alkaline environment stability inferior further increases potential stability of the pH sensor under high humidity environment with high salt.Only the micro- liquid of a drop need to be pipetted using liquid-transfering gun between two electrodes, it can make to form access between reference electrode and working electrode, according to the potential difference between two electrodes, to monitor hydrionic concentration, the stability that aircraft corrosion condition monitors under complex environment is improved, while improving the service life of sensor.
Description
Technical field
The present invention relates to pH sensor technical fields, more particularly to a kind of minisize pH sensor and preparation method thereof.
Background technique
Corrosion is one of the principal mode of Flight Vehicle Structure damage, accounts for the 20% of entire infrastructure damage.Flight Vehicle Structure is rotten
Erosion is the accumulation chemical loss and break that component is occurred under the micro- liquid film environment of atmospheric corrosion by chemistry or electrochemical action
It is bad.In corrosion early period of origination, corrosion location is difficult to detect, will more than other lesion developments if not being controlled after its germinating
Fastly, more serious.The corrosion damage of aircraft directly affects the rate of attendance of aircraft, more drastically influences the life peace of pilot
Entirely.Therefore, it is necessary to take positive safeguard procedures, aircraft extent of corrosion is estimated ahead of time, to reduce aircraft maintenance cost and keep away
Exempt from the generation of tragedy.
Deposits in Eastern Coastal China area is either civilian or military aircraft, due to for a long time high salt fog, high humility etc. it is severe,
Aerial mission is executed under complex environment, aircraft surface even cockpit is not suffering from various corruption all the time
Erosion.These corrosion are in early period of origination human eye overview less than until discovery, aircraft surface has been had been subjected to seriously
Corrosion, this will reduce the service life of aircraft, and the life safety that will seriously threaten pilot significantly.
Currently, China to the corrosion protection of aircraft also only to seal water proof and based on body inspects periodically, tradition inspection
Survey mode efficiency is lower, high expensive, assesses the corruption of aircraft etc. although also having been reported that through technologies such as ultrasound, infrared imagings
Erosion situation, but these methods are all just to have detected corrosion location, low efficiency in the case where aircraft has been corroded and has compared serious conditions
Lower and higher cost.The instrument of existing common monitoring hydrogen ion concentration is glass pH meter, but glass pH electrode exists easily
It broken, the disadvantages of internal resistance is larger, stability is poor and easily-deformable in soda acid acid-base solution, can not be used for the micro- liquid of high humidity with high salt
The direct real-time monitoring of aircraft corrosion condition under membrane environment.
Summary of the invention
The object of the present invention is to provide a kind of minisize pH sensors and preparation method thereof, high, clever to prepare a kind of stability
Quick property is good, can suitable for the micro- liquid film environment of high humidity with high salt pH value real-time monitoring minisize pH sensor.
To achieve the above object, the present invention provides following schemes:
A kind of minisize pH sensor, the minisize pH sensor include: polyimide substrate, conductive silver glue screen printing
Brush layer, Ag/AgCl reference electrode, hydrogen ion sensitive sense electrode, polyurethane interlayer and AB glue coating；
The conductive silver glue screen-printed layers are printed on above the polyimide substrate；The Ag/AgCl reference
Electrode and the hydrogen ion sensitive sense electrode are arranged in the conductive silver glue screen-printed layers and are not in contact with each other；The polyurethane every
Layer is coated on the polyimide substrate；The AB glue coating is coated in the Ag/AgCl reference electrode and the hydrogen
Ion-sensitive electrode surrounding.
Optionally, the conductive silver glue screen-printed layers are by electrode bonding printing layer, conducting wire printing layer and solder joint printing layer
Composition；The electrode bonding printing layer specifically includes first electrode bonding printing layer and second electrode bonding printing layer；The Ag/
AgCl reference electrode is adhered in the first electrode bonding printing layer；The hydrogen ion sensitive sense electrode is adhered to second electricity
It is very viscous to connect in printing layer；The first electrode bonding printing layer and second electrode bonding printing layer do not contact；The conducting wire
Printing layer includes the first conducting wire printing layer and the second conducting wire printing layer, and the first conducting wire printing layer and second conducting wire print
Layer does not contact；The solder joint printing layer includes the first solder joint printing layer and the second solder joint printing layer, the first solder joint printing layer
It is not contacted with the second solder joint printing layer；One end of the first conducting wire printing layer connects the first solder joint printing layer, separately
One end connects the first electrode and is bonded printing layer；One end of the second conducting wire printing layer connects the second solder joint printing
Layer, the other end connect the second electrode and are bonded printing layer；The polyurethane interlayer is coated in the polyimide substrate
The polyurethane interlayer coating zone on surface, the polyurethane interlayer coating zone are in the polyimide upper surface of base plate
Region in addition to the electrode is bonded printing layer and the solder joint printing layer.
Optionally, the Ag/AgCl reference electrode includes reference electrode matrix and is deposited on the reference electrode matrix table
The AgCl layer in face；The hydrogen ion sensitive electrification extremely RuO2-IrO2Base H+Working electrode or RuO2Base H+Working electrode；
The RuO2-IrO2Base H+Working electrode includes the first matrix and the first hydrogen coated in first matrix surface
Ion-sensitive substance；First matrix is titanium sheet；The first hydrogen ion sensitive materials are RuO2And IrO2Composition；
The RuO2Base H+Working electrode includes the second matrix and the second hydrogen ion sensitive coated in second matrix surface
Feel substance；Second matrix is silicon chip；The second hydrogen ion sensitive materials are RuO2。
The present invention also provides a kind of minisize pH transducer production method, the preparation method is used to prepare the minisize pH
Sensor, the preparation method include:
Prepare polyimide substrate；
Conductive silver glue screen-printed layers are printed in the polyimide upper surface of base plate；
Ag/AgCl reference electrode and hydrogen ion sensitive sense electrode are bonded in the conductive silver glue screen-printed layers；The Ag/
AgCl reference electrode is not in contact with each other with the hydrogen ion sensitive sense electrode；
Polyurethane is coated on the polyimide substrate, forms polyurethane interlayer；
AB glue is coated in the Ag/AgCl reference electrode and the hydrogen ion sensitive sense electrode surrounding, forms AB glue coating.
Optionally, described to print conductive silver glue screen-printed layers in the polyimide upper surface of base plate, it is specific to wrap
It includes:
One layer of conductive silver glue screen-printed layers are printed in the polyimide upper surface of base plate using silk screen print method；
The conductive silver glue screen-printed layers are made of electrode bonding printing layer, conducting wire printing layer and solder joint printing layer；The electrode is viscous
It connects printing layer and specifically includes first electrode bonding printing layer and second electrode bonding printing layer；The first electrode is bonded printing layer
It is not contacted with second electrode bonding printing layer；The conducting wire printing layer includes that the first conducting wire printing layer and the second conducting wire print
Layer, the first conducting wire printing layer and the second conducting wire printing layer do not contact；The solder joint printing layer is printed including the first solder joint
Brush layer and the second solder joint printing layer, the first solder joint printing layer are not contacted with the second solder joint printing layer；Described first leads
One end of line printing layer connects the first solder joint printing layer, and the other end connects the first electrode and is bonded printing layer；Described
One end of two conducting wire printing layers connects the second solder joint printing layer, and the other end connects the second electrode and is bonded printing layer.
Optionally, described that Ag/AgCl reference electrode and hydrogen ion sensitivity are bonded in the conductive silver glue screen-printed layers
Electrode specifically includes:
The Ag/AgCl reference electrode is bonded in first electrode bonding printing layer；The Ag/AgCl reference electrode
Including reference electrode matrix and the AgCl layer for being deposited on the reference electrode matrix surface；
The hydrogen ion sensitive sense electrode is bonded in second electrode bonding printing layer.
Optionally, before the step of being bonded the Ag/AgCl reference electrode in first electrode bonding printing layer, also
Include:
The Ag/AgCl reference electrode is prepared using electrochemical workstation chronoptentiometry.
Optionally, before the step of being bonded the hydrogen ion sensitive sense electrode in second electrode bonding printing layer, also
Include:
Prepare titanium sheet；
The titanium sheet is pre-processed, the first matrix is formed；
First hydrogen ion sensitive materials are prepared using Via Polymeric Precursor Method；The first hydrogen ion sensitive materials are RuO2
And IrO2Composition；
The first hydrogen ion sensitive materials are coated on first matrix, form the hydrogen ion sensitive sense electrode.
Optionally, before the step of being bonded the hydrogen ion sensitive sense electrode in second electrode bonding printing layer, also
Include:
Prepare silicon chip；
The silicon chip is cleaned, second matrix is formed；
Second hydrogen ion sensitive materials are prepared using Via Polymeric Precursor Method；The second hydrogen ion sensitive materials are
RuO2；
The second hydrogen ion sensitive materials are deposited in second matrix surface using magnetron sputtering technique, described in formation
Hydrogen ion sensitive sense electrode.
Optionally, described that polyurethane is coated on the polyimide substrate, polyurethane interlayer is formed, it is specific to wrap
It includes:
The polyurethane is coated in the polyurethane interlayer coating zone of the polyimide substrate surface, described in formation
Polyurethane interlayer；The polyurethane interlayer coating zone is in the polyimide upper surface of base plate except the electrode is bonded
Region other than printing layer and the solder joint printing layer.
The specific embodiment provided according to the present invention, the invention discloses following technical effects:
The present invention provides a kind of minisize pH sensor and preparation method thereof.It is passed using the pH of method provided by the invention preparation
Sensor is sheet type, all solid state minisize pH sensor, with small in size, structural stability is good, high reliablity, good airproof performance
Advantage can be placed in any test position of instrument and equipment, be influenced by extraneous factor small, be particularly suitable for micro- in high humidity with high salt
The direct real-time monitoring of aircraft corrosion condition under liquid film environment.And the RuO that the present invention uses2-IrO2Base H+Working electrode energy
It enough makes up in working before this, the pH sensor defect poor in alkaline environment stability inferior further increases pH sensor in height
Potential stability under salt high humidity environment.Only the micro- liquid of a drop need to be pipetted using liquid-transfering gun between two electrodes, that is, may make that reference is electric
Access is formed between pole and working electrode, according to the potential difference between two electrodes, to monitor hydrionic concentration, is improved multiple
The stability that aircraft corrosion condition monitors under miscellaneous environment, while also can be improved the service life of sensor.
Detailed description of the invention
It in order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, below will be to institute in embodiment
Attached drawing to be used is needed to be briefly described, it should be apparent that, the accompanying drawings in the following description is only some implementations of the invention
Example, for those of ordinary skill in the art, without any creative labor, can also be according to these attached drawings
Obtain other attached drawings.
Fig. 1 is the overall structure diagram of minisize pH sensor provided by the invention；
Fig. 2 is the structural schematic diagram of conductive silver glue screen-printed layers provided by the invention；
Fig. 3 is the setting position view of Ag/AgCl reference electrode provided by the invention and hydrogen ion sensitive sense electrode；
Fig. 4 is the setting position view of polyurethane interlayer provided by the invention and AB glue coating；
Fig. 5 is the method flow diagram of minisize pH transducer production method provided by the invention；
Fig. 6 is the schematic diagram provided by the invention for sputtering ruthenic oxide system on a silicon substrate；
Fig. 7 is the potential value and the graph of relation of time of minisize pH of embodiment of the present invention sensor；
Fig. 8 is potential value and the sensitivity relation curve graph of different pH value of minisize pH of embodiment of the present invention sensor；
Fig. 9 is the time response variation that different pH solution are successively added dropwise in minisize pH of embodiment of the present invention sensor from acid to alkali
Curve graph；
Figure 10 is the time response change that different pH solution are successively added dropwise from alkali to acid for minisize pH of embodiment of the present invention sensor
Change curve graph；
Figure 11 is minisize pH of embodiment of the present invention sensor by drying regime to acid time response change curve；
Figure 12 is that different pH solution are successively added dropwise to acid by alkali again from acid to alkali in minisize pH of embodiment of the present invention sensor
Time response change curve；
Figure 13 is Li of the embodiment of the present invention+、Na+、K+、Ca2+、Mg2+、SO2 4 -To the influence curve figure of minisize pH sensor.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other
Embodiment shall fall within the protection scope of the present invention.
The object of the present invention is to provide a kind of minisize pH sensors and preparation method thereof, to solve current atmospheric monitoring to pass
Unite based on monitoring station, website is few, area coverage is few, data update real-time it is poor, can not actual response go out people and connect at one's side
The problem of real air quality information of touching.
In order to make the foregoing objectives, features and advantages of the present invention clearer and more comprehensible, with reference to the accompanying drawing and specific real
Applying mode, the present invention is described in further detail.
Fig. 1 is the overall structure diagram of minisize pH sensor provided by the invention.Referring to Fig. 1, provided by the invention one
Kind minisize pH sensor includes: polyimide substrate 101, conductive silver glue screen-printed layers 102, Ag/AgCl reference electrode
103, hydrogen ion sensitive sense electrode 104, polyurethane interlayer 105, AB glue coating 106 and contact conductor 107.
The conductive silver glue screen-printed layers 102 are printed on 101 top of polyimide substrate；The Ag/
AgCl reference electrode 103 and the hydrogen ion sensitive sense electrode 104 are not arranged in the conductive silver glue screen-printed layers 102 and mutually not
Contact；The polyurethane interlayer 105 is coated on the polyimide substrate 101；The AB glue coating 106 is coated in institute
State Ag/AgCl reference electrode 103 and 104 surrounding of hydrogen ion sensitive sense electrode.
Wherein, the polyimide substrate 101 is 23mm long, wide 18mm, thickness 1mm.The polyimide base
101 material therefor of plate is polyimides (Polyimide, PI), and polyimides (PI) has high temperature resistant (up to 400 DEG C), excellent
The advantages that mechanical performance, high radiation-resistant property, good soda acid chemical stability and flexibility.Use polyimides as
PH sensor base plate material can be improved sensor use temperature range, and reducing extraneous corrosive environment influences pH sensor, mention
Stability and reliability of the high sensor under complex environment.Furthermore polyimides is flexible material, can widen pH sensor
Application field and application range.
The material of the conductive silver glue screen-printed layers 102 is conductive silver glue.Fig. 2 is conductive silver collodion silk provided by the invention
The structural schematic diagram of wire mark brush layer.Referring to fig. 2, the conductive silver glue screen-printed layers 102 are printed by electrode bonding printing layer, conducting wire
Brush layer and solder joint printing layer composition.The electrode bonding printing layer specifically includes first electrode bonding printing 201 and second electrode
It is bonded printing layer 202.The first electrode bonding printing layer 201 is square printing layer, and the side length of square printing layer is
5mm.The second electrode bonding printing layer 202 is identical as 201 shapes of first electrode bonding printing.The first electrode bonding print
Brush layer 201 and second electrode bonding printing layer 202 do not contact.
Fig. 3 is the setting position view of Ag/AgCl reference electrode provided by the invention and hydrogen ion sensitive sense electrode.Referring to
Fig. 3, the Ag/AgCl reference electrode 103 are adhered in the first electrode bonding printing layer 201.The Ag/AgCl reference electricity
Pole 103 is long and width is 5mm, with a thickness of 1mm.The Ag/AgCl reference electrode 103 includes reference electrode matrix and is deposited on institute
State the AgCl layer of reference electrode matrix surface.The reference electrode matrix is that long and width is 5mm, with a thickness of the silver strip of 1mm.Using
The silver or silver chloride electrode of laminated structure can provide stable current potential output valve as reference electrode for sensor, can be effective
Increase reference electrode and corrode the contact area of micro- liquid film environment, the sensitivity of sensor and stability is made to get a promotion.
The hydrogen ion sensitive sense electrode 104 is adhered in the second electrode bonding printing layer 202.The Ag/AgCl ginseng
It is 2mm than the spacing between electrode 202 and the hydrogen ion sensitive sense electrode 104.
The hydrogen ion sensitive sense electrode 104 is RuO2-IrO2Base H+Working electrode or RuO2Base H+Working electrode.It is described
RuO2-IrO2Base H+Working electrode includes the first matrix and the first hydrogen ion sensitive materials coated in first matrix surface.
First matrix is pretreated titanium sheet, and the titanium sheet is the laminated structure of long 5mm, width 5mm, thickness 1mm.First hydrogen
Ion-sensitive substance is RuO2And IrO2Composition.
The RuO2Base H+Working electrode includes the second matrix and the second hydrogen ion sensitive coated in second matrix surface
Feel substance.Second matrix is silicon chip；The second hydrogen ion sensitive materials are RuO2.
The conducting wire printing layer includes the first conducting wire printing layer 203 and the second conducting wire printing layer 204, the first conducting wire print
Brush layer 203 and the second conducting wire printing layer 204 do not contact.The first conducting wire printing layer 203 and second conducting wire printing
The distance between layer 204 is 5mm.The first conducting wire printing layer 203 is long 13mm, width 0.3mm rectangle printing layer.Described
Two conducting wire printing layers 204 are identical as the shape of the first conducting wire printing layer 203.
The solder joint printing layer includes the first solder joint printing layer 205 and the second solder joint printing layer 206, the first solder joint print
Brush layer 205 is not contacted with the second solder joint printing layer 206.The first solder joint printing layer 205 be long and width be 2mm just
Rectangular printing layer, the second solder joint printing layer 206 are identical as the shape of the first solder joint printing layer 205.
One end of the first conducting wire printing layer 203 connects the first solder joint printing layer 205, other end connection described the
One electrode is bonded printing layer 201；One end of the second conducting wire printing layer 204 connects the second solder joint printing layer 206, another
End connects the second electrode and is bonded printing layer 202.From the first solder joint printing layer 205 and the second solder joint printing layer
A lead is drawn on 206 respectively as the contact conductor 107.Spacing is 5mm between two contact conductors.
Fig. 4 is the setting position view of polyurethane interlayer provided by the invention and AB glue coating.Referring to fig. 4, described poly-
Urethane interlayer 105 be coated in 101 surface of polyimide substrate polyurethane interlayer coating zone, the polyurethane every
Layer coating zone is in 101 upper surface of polyimide substrate except the electrode is bonded printing layer and solder joint printing
Region other than layer.It is described to brush in polyurethane interlayer 105 a length of 18mm, the width 13mm in addition to solder joint and two electrodes, it is thick
Degree is about 2mm.In two electrode print layer top tiling, one strata urethane interlayer, in order to seal water proof, prevent extraneous corruption
Erosion environment impacts printed conductive layer.
The AB glue coating 106 is coated uniformly on two electrode surroundings, to be completely fixed two electrode positions.AB glue coating layer thickness
It is 2mm with the consistency of thickness of the polyurethane interlayer 105.
Aircraft corrosion condition under the micro- liquid film environment of high humidity with high salt is carried out using the pH sensor provided by the invention
When monitoring, be using sensor RuO2-IrO2H+ working electrode in Nernst equation and Ag/AgCl reference electrode current potential with it is molten
The linear relationship that existing slope is negative between liquid pH value, by measuring the interelectrode potential value size of sensor two, thus
The pH value of obtained unknown solution, the final real time on-line monitoring for realizing pH value, concrete principle are as follows:
The square titanium sheet of precursor sol coated with ruthenium source and iridium source can react in furnace at 360 DEG C with oxygen,
Titanium plate surface generates hydrogen ion sensitive materials ruthenic oxide (Ruthenium oxide, RuO2) and iridium dioxide (iridium
Oxide, IrO2), RuO2And IrO2Be that hydrionic sensitive materials are identified in working electrode, the two the difference lies in that RuO2
There is more low resistance in alkaline solution, stability is poor, and IrO2Both activity is more stable in alkaline solution, thus combine
The compound preparation of the two in acid-base solution, is formed in the good RuO of stability in acid-base solution by advantage and disadvantage, selection2-IrO2
Hydrogen ion sensitive sense electrode.Reactional equation is as follows:
It is deposited on pH sensor RuO2-IrO2Micro- liquid film between hydrogen ion working electrode and Ag/AgCl reference electrode can and
RuO2And IrO2Redox occurs and passes reaction, electrode reaction equation such as following formula:
There are some linear, basic principles for the logarithm of hydrogen ion concentration in the electrode potential of sensor and micro- liquid film
It can be illustrated with following Nernst equation:
Wherein, formula (1), (2) are the precursor sol annealing reaction equation containing ruthenium source and iridium source, formula (3), (4) point
Wei not anneal obtained RuO2And IrO2The redox reaction occurred with hydrogen ion in micro- liquid, formula (5) are pH value and electrode potential
Between energy this special relation equation.In formula (5), E indicates the actual measurement electrode potential of minisize pH sensor, E0For the mark of pH sensor
Collimator electrode potential, R are gas constant 8.314J/ (mol*K), and T is temperature, and F is Faraday constant 96487C/mol；RT/F is 25
Value at DEG C is 25.688.When reference electrode is Ag/AgCl reference electrode, E0=577mV.
Using liquid-transfering gun thin slice will be added drop-wise to by the standard buffer solution of the calibrated different pH value of commercial glass pH meter
Between formula all-solid-state pH working sensor and reference electrode, make Ag/AgCl reference electrode and RuO2-IrO2Base H+Working electrode it
Between form micro- liquid film access, by measuring the electrode potential that is formed between electrodes of the unknown micro- liquid film of corrosive environment, Ji Keyi
According to the anti-pH value for releasing micro- liquid film of above formula (5) Nernst equation, to carry out real time on-line monitoring to corrosive environment.
The present invention also provides a kind of minisize pH transducer production method, the preparation method is used to prepare the minisize pH
Sensor.The preparation method on the polyimide substrate pre-processed, is printed first by screen printing template
Two full symmetric patterns as shown in Figure 2 out, by the square silver strip pre-processed bonding side printed patterns (the wherein
One electrode is bonded printing layer) at, polyurethane water-proof interlayer is evenly laid out on 102 top of conductive silver glue-line, can make pH sensor
Circuit board, which is not corroded micro- pendular ring border by the external world, to be influenced, using electrochemical workstation chronoptentiometry at one layer of silver strip electroplating surface
AgCl layers, titanium-based RuO is prepared using sol-gal process2-IrO2Base H+Working electrode, and be bonded in and Ag/AgCl reference electricity
At extremely opposite other side conductive silver glue printing (second electrode bonding printing layer), using AB glue by reference electrode and working electrode
Surrounding is fixed, and first electrode lead passes through Ag/AgCl reference electrode tail portion solder joint (the first solder joint printing layer and second weldering
Point printing layer) it draws, second electrode lead passes through RuO2-IrO2Base H+Working electrode tail portion solder joint is drawn.
Fig. 5 is the method flow diagram of minisize pH transducer production method provided by the invention, referring to Fig. 5, the preparation side
Method includes:
Step 501: preparing polyimide substrate.
Polyimide is individually placed to ultrasound cleaning 30min in 0.2mol/LNaOH solution, in order to remove
Then substrate surface greasy dirt is individually placed to clean 30min in dehydrated alcohol and deionized water again, is then placed on 80 DEG C of baking ovens
In dry completely, obtain the polyimide substrate.The polyimide substrate size are as follows: a length of 23mm, width are
18mm, with a thickness of 1mm.
Step 502: printing conductive silver glue screen-printed layers in the polyimide upper surface of base plate.Specifically:
Processed polyimide substrate is placed in below designed screen printing template in advance, takes and leads on a small quantity
Electric elargol is placed at printing stencil pattern, is then struck off conductive silver glue with scraper plate, is occurred until on polyimide substrate
Designed pattern stops blade coating, forms the conductive silver glue screen-printed layers.Leading on the polyimide substrate
Electric elargol layer pattern is printed by designed screen printing template, is printed on the polyimide substrate
The full symmetric distribution of conductive silver glue layer pattern.
Specifically, the conductive silver glue screen-printed layers are by electrode bonding printing layer, conducting wire printing layer and solder joint printing layer
Composition；The electrode bonding printing layer specifically includes first electrode bonding printing layer and second electrode bonding printing layer；Described
One electrode bonding printing layer and second electrode bonding printing layer do not contact；The conducting wire printing layer is printed including the first conducting wire
Layer and the second conducting wire printing layer, the first conducting wire printing layer and the second conducting wire printing layer do not contact；The solder joint printing
Layer includes the first solder joint printing layer and the second solder joint printing layer, and the first solder joint printing layer and the second solder joint printing layer are not
Contact；One end of the first conducting wire printing layer connects the first solder joint printing layer, and it is viscous that the other end connects the first electrode
Connect printing layer；One end of the second conducting wire printing layer connects the second solder joint printing layer, other end connection second electricity
It is very viscous to connect printing layer.
Step 503: Ag/AgCl reference electrode and hydrogen ion sensitive electrification are bonded in the conductive silver glue screen-printed layers
Pole.It specifically includes:
Step 5031: being bonded the Ag/AgCl reference electrode in first electrode bonding printing layer.The Ag/
AgCl reference electrode includes reference electrode matrix and the AgCl layer for being deposited on the reference electrode matrix surface.The reference electrode
Matrix is that long and width is 5mm, with a thickness of the silver strip of 1mm.The silver strip passes through polishing machine polishing treatment first, then puts into respectively
Ultrasound cleaning 30min, it is stand-by to take out drying in dehydrated alcohol and deionized water.Then processed silver strip is sticked to described first
Electrode be bonded printing layer on, be then placed in 65 DEG C of baking ovens and toast, make silver strip printing layer (elargol) Nian Jie with first electrode,
It is clung completely between first electrode bonding printing layer and polyimide substrate.Then electrochemical workstation time-measuring electric potential is used
Method deposits AgCl on silver strip surface.The preparation process of the Ag/AgCl reference electrode are as follows: it with diameter is 0.5mm, a length of 6cm's
Platinum wire is cathode, and pretreated 5mm × 5mm × 1mm silver strip is anode, and saturation KCl solution is electrolyte, passes through electrochemistry
Work station chronoptentiometry is electroplated, and constant current is set as 6mV when plating, and electroplating time is set as 1800s, when two electricity of yin-yang
When potential difference between pole gradually tends towards stability, shows that silver strip surface forms one layer of stable AgCl layer, furthermore pass through silver strip
Surface color observation, which becomes black gray expandable also from silvery white, can determine whether out to form stable AgCl layer on silver strip surface, that is, complete
The preparation of Ag/AgCl reference electrode.The AgCl thickness degree of the Ag/AgCl reference electrode plating is about 79.6 μm.The present invention exists
Silver strip surface is electroplated one layer AgCl layers using electrochemical deposition method, it is therefore an objective to play the role of stable pH sensor current potential.
Step 5032: being bonded the hydrogen ion sensitive sense electrode in second electrode bonding printing layer.
Before the step 5032 is bonded the hydrogen ion sensitive sense electrode, the hydrogen ion sensitive sense electrode is also carried out
Preparation.The hydrogen ion sensitive sense electrode can be RuO2-IrO2Base H+Working electrode or RuO2Base H+One of working electrode.
As a kind of specific embodiment of the hydrogen ion sensitive sense electrode, the RuO2-IrO2Base H+Working electrode includes
First matrix and the first hydrogen ion sensitive materials coated in first matrix surface；First matrix is titanium sheet；It is described
First hydrogen ion sensitive materials are RuO2And IrO2Composition.The RuO2-IrO2Base H+Working electrode the preparation method comprises the following steps:
Prepare titanium sheet, the titanium sheet is pre-processed, forms the first matrix.The pre-treatment step of the titanium sheet is as follows:
Titanium sheet is polished with fine sandpaper first, coarse processing then is carried out to it using coarse sandpaper, titanium sheet is then respectively put into 60 DEG C
20~30min is impregnated in hot 0.2mol/L~1mol/L HCl solution and hot 5%~10% oxalic acid solution, is finally drawn off anti-
It is stand-by that multiplexing deionized water rinses drying well.The purpose using hydrochloric acid and oxalic acid alternating corrosion pickling titanium-based piece be in order to
Increase titanium surface roughness, and then increase the adhesiveness of matrix and colloidal sol, while pickling is increasing the same of titanium plate surface roughness
When, it can also increase pH sensor response site, increase pH transducer sensitivity.It is finally drawn off being rinsed with deionized water and dry
It is dry stand-by.
First hydrogen ion sensitive materials are prepared using Via Polymeric Precursor Method；The first hydrogen ion sensitive materials are dioxy
Change ruthenium-iridium dioxide sensitive layer (i.e. RuO2And IrO2Composition).The first hydrogen ion sensitive materials the preparation method is as follows:
RuO is prepared using sol-gal process2-IrO2Base H+Sensitive materials use hydrate ruthenium trichloride and to be hydrated four chlorinations
Iridium respectively as hydrogen ion sensitive materials ruthenium source and iridium source, first by citric acid (CA) and ethylene glycol (EG) with 1:4.25 moles
Than being stirred in 65 DEG C of magnetic stirring apparatus；Then by a certain amount of hydrate ruthenium trichloride (RuCl3) and to be hydrated tetrachloro
Change iridium (IrCl4) be added in above-mentioned solution and stir, and guarantee that CA: EG: Ru: Ti molal weight ratio is 1: 4.25:
0.16: 0.16, then the precursor sol prepared is evenly coated in pretreated titanium sheet, and place it in 130 in furnace
DEG C~150 DEG C of 20~30min of annealing, in order to the polymerization reaction for promoting presoma, 230 DEG C~250 DEG C anneal 20~
30min, in order to increase Titanium base and colloidal sol adhesion property, finally anneal at 340~380 DEG C 10~20min, purpose
It is to form hydrogen ion sensitive materials RuO2 and IrO2.
Then the first hydrogen ion sensitive materials are coated on first matrix, i.e. completion RuO2-IrO2H+ work
The preparation of electrode forms the hydrogen ion sensitive sense electrode.
RuO is prepared using Via Polymeric Precursor Method2-IrO2Base H+Sensitive materials, have preparation process is simple, cost is relatively low,
The advantages that electrode stability prepared is good.
As another specific embodiment of the hydrogen ion sensitive sense electrode, can also be prepared using magnetron sputtering technique
RuO2Basic matrix column pH sensor, the RuO used2Base H+Working electrode is including the second matrix and is coated in second matrix
The second hydrogen ion sensitive materials on surface；Second matrix is silicon chip；The second hydrogen ion sensitive materials are RuO2。
The RuO2Base H+Working electrode the preparation method comprises the following steps:
Prepare silicon chip, the silicon chip is cleaned, forms second matrix.It is quick using silicon wafer as ruthenic oxide
Feel the substrate of film deposition, needs to clean silicon chip using acetone and methanol before deposition.Silicon base is the orientation of p-type 100, electricity
Resistance rate is 15~25 Ω cm, and 99.99% ruthenium is as metal targets.Silicon chip is carried out using acetone and methanol first alternately super
Sound cleans 15min, then clean and drying is stand-by with deionized water repeated flushing.
Second hydrogen ion sensitive materials are prepared using Via Polymeric Precursor Method；The second hydrogen ion sensitive materials are
RuO2。
The second hydrogen ion sensitive materials are deposited in second matrix surface using magnetron sputtering technique, described in formation
Hydrogen ion sensitive sense electrode.The control of magnetron sputtering operating pressure is 10,000,000 supports in argon gas and oxygen mix atmosphere, and is continued
1h is sintered in the argon gas and oxygen mix atmosphere furnace.The gas flow ratio of argon gas and oxygen is set as 4:1, then cuts silicon chip
It is cut into the square dice that long and width is 0.5cm size, and with epoxy resin that the silicon chip of certain size is packaged, as
The RuO2Base H+Working electrode.
In the case where Japan produces SKN-05P type magnetic control sputtering device 13.56MHz frequency, radio-frequency power is set as 100W.Fig. 6 is this
The schematic diagram for sputtering ruthenic oxide system on a silicon substrate that invention provides, RuO2Base ISE pH sensor is divided into two parts:
One is ruthenic oxide hydrogen ion sensitive thin film, and two be MOSFET (Metal Oxide Semiconductor Field Effect Transistor) structure.Dioxy
Change ruthenium as pH sensor sensing camera lens, and with epoxy resin that its appearance is packaged, the separate region 2 × 2cm is as sensing
Device sensitivity window, i.e. completion RuO2The preparation of base hydrogen ion sensitive sense electrode.
Step 504: coating polyurethane on the polyimide substrate, form polyurethane interlayer.
Polyurethane interlayer coating zone using hairbrush in the polyimide substrate surface coats the polyurethane,
And place it in 65 DEG C of baking ovens and be fully cured, form the polyurethane interlayer.The polyurethane interlayer coating zone is described
Region in polyimide upper surface of base plate in addition to the electrode is bonded printing layer and the solder joint printing layer.In conduction
Tile one layer of water barrier on elargol printing layer top, in order to prevent extraneous corrosion moist environment from generating to pH sensor circuit
Interference.
Step 505: coating AB glue in the Ag/AgCl reference electrode and the hydrogen ion sensitive sense electrode surrounding, form AB
Gel coating.
The surrounding of Ag/AgCl reference electrode and hydrogen ion sensitive sense electrode is completely fixed using AB glue, and in Ag/AgCl
Two conducting wires are drawn at reference electrode and hydrogen ion sensitive sense electrode both ends, that is, are finally completed the preparation of the minisize pH sensor.
Use the minisize pH sensor of preparation method preparation provided by the invention to be all solid state and small in size, electrode is steady
It sets, there is sealing water isolating well, can be used in the direct of aircraft corrosion condition under the micro- liquid film environment of high humidity with high salt
Monitoring, and can be also used for water environment pollution situation on-line monitoring, the scope of application is wider.
In practical applications, the stability and sensitivity of pH sensor provided by the invention are studied.It will preparation
The composition test macro such as good described pH sensor and CHI660E type electrochemical workstation, testing jig, conducting wire, passes the PH
Micro- liquid film that sensor deposits under atmospheric corrosion environment carries out simulation test.Using liquid-transfering gun will by 0.3mol/LNaOH solution and
The pH value that 0.3mol/L HCl solution is adjusted is respectively that 2,4,6,8,10 5%NaCl solution successively pipettes RuO2-IrO2Base H+
Between working electrode and Ag/AgCl reference electrode, about 2 μ L of the amount of pipetting every time is controlled, the V-T curve of every kind of pH value solution is drawn,
Setting acquisition time is 600s, and acquisition interval is that 0.1s acquires a point, is carried out continuously same signal acquisition three times.Fig. 7 and
Fig. 8 is the potential value graph of relation with time, pH value respectively of minisize pH of embodiment of the present invention sensor.Fig. 7 is the present invention
The potential value and the graph of relation of time of embodiment minisize pH sensor, abscissa is the time in Fig. 7, and unit is the second, indulges and sits
It is designated as current potential, unit is volt.As shown in Figure 7, pH sensor has good identification, and pH sensor to different pH value
It is with good stability within the 600s time, current potential-time of pH sensor is studied every ten days, pH sensor exists
There is the good service life in long period.Fig. 8 is the sensitive of potential value and the different pH value of minisize pH of embodiment of the present invention sensor
Graph of relation is spent, abscissa is pH in Fig. 8, and ordinate is current potential, and unit is millivolt.As shown in Figure 8, pH sensor is carried out
Sensitivity test three times carried out the sensitivity of primary test pH sensor every ten days, and sensitivity is respectively as follows: 50.6mV/pH,
50.2mV/pH, 49.9mV/pH, showing pH sensor in the long period has good sensitivity.
In practical applications, also the response time of pH sensor provided by the invention is studied.Fig. 9-11 for institute
State the time response change curve that different PH solution are successively added dropwise in pH sensor by alkali to acid again from acid to alkali, cross in Fig. 9-11
Coordinate is the time, and unit is the second, and ordinate is current potential, and unit is volt.The testing time is in acid and alkaline solution
300s is not needed to be removed Liquid Residue between electrode using deionized water, is repeated to survey three times altogether in transformation solution every time
Examination.Fig. 9 is the time response change curve that different pH solution are successively added dropwise in minisize pH of embodiment of the present invention sensor from acid to alkali
Figure, is repeated three times, each response time is close to 1.9s.Figure 10 be minisize pH of embodiment of the present invention sensor from alkali to
The time response change curve of different pH solution is successively added dropwise in acid, and equally in triplicate, each response time is close to 1.5s.
Figure 11 is minisize pH of embodiment of the present invention sensor by drying regime to acid time response change curve.It can by Figure 11
Know, pH sensor of the present invention is about 2.0s by drying regime to acid response time, show the minisize pH sensor have compared with
Short response time.
In practical applications, the present invention also grinds the repeatability of the miniature PH sensor in the present embodiment
Study carefully.Different pH value V-T follow-on tests have been carried out to pH sensor, have been 2,4,6,8,11,2 solution sequence by pH value, by different pH
The 5%NaCl solution of value is successively added drop-wise between two electrodes, research by acidity to alkalinity, then by it is alkaline to acidic circulation to sensing
Device performance influences, every kind of pH value solution testing 300s, carries out 1800s test altogether, in triplicate.Figure 12 is the embodiment of the present invention
The time response change curve of different pH solution, cross in Figure 12 is successively added dropwise in minisize pH sensor by alkali to acid again from acid to alkali
Coordinate is the time, and unit is the second, and ordinate is current potential, and unit is volt.The minisize pH provided by the invention passes as shown in Figure 12
Sensor has good repeatability, and hysteresis is negligible.
In practical applications, since working electrode uses RuO2-IrO2Compound hydrogen ion sensitive sense electrode, high combination electrode
Belong to transition group metallic oxide, certain cations present in atmospheric environment can generate interference, such as Li to it+、Na+、K+、Ca2 +、Mg2+、SO2 4 -.Therefore, the anti-interference of the minisize pH sensor in the present embodiment is studied.Figure 13 is that the present invention is real
Apply a Li+、Na+、K+、Ca2+、Mg2+、SO2 4 -To the influence curve figure of minisize pH sensor.Abscissa is pH, ordinate in Figure 13
For current potential, unit is millivolt.Referring to Figure 13, Li will be contained+、Na+、K+、Ca2+、Mg2+、SO2 4 -The different pH value of plasma
It is added drop-wise between two electrode of minisize pH sensor, minisize pH sensor has good point to the pH value solution containing different ions
Boundary, and it is close to the solution containing above-mentioned ion and the solution sensitivity without above-mentioned ion, it follows that Li+、Na+、K+、
Ca2+、Mg2+、SO2 4 -For plasma to the interference very little of sensor, the anti-interference of minisize pH sensor provided by the invention is extremely strong.
As it can be seen that the minisize pH sensor provided by the invention has sheet type, all solid state, small in size, high reliablity, steady
The advantages of solidity is high and high sensitivity can be suitable for the direct of under the micro- liquid film environment of high humidity with high salt aircraft corrosion condition
Real-time monitoring.And when being monitored using the minisize pH sensor, need to only it use liquid-transfering gun that different pH value is added dropwise
Between Ag/AgCl reference electrode and hydrogen ion sensitive sense electrode, that is, may make minisize pH sensor formed access, according to two electrodes it
Between the potential difference that generates, to monitor hydrionic concentration, for structure mini pH sensor compares band groove type pH sensor,
Stability, reliability and safety of the sensor under complex environment are even more improved, while also can be improved sensor
Service life.
Each embodiment in this specification is described in a progressive manner, the highlights of each of the examples are with other
The difference of embodiment, the same or similar parts in each embodiment may refer to each other.For method disclosed in embodiment
For, since it is corresponding with system disclosed in embodiment, so being described relatively simple, related place is defended oneself referring to Account Dept
It is bright.
Used herein a specific example illustrates the principle and implementation of the invention, and above embodiments are said
It is bright to be merely used to help understand method and its core concept of the invention；At the same time, for those skilled in the art, foundation
Thought of the invention, there will be changes in the specific implementation manner and application range.In conclusion the content of the present specification is not
It is interpreted as limitation of the present invention.
Claims (10)
1. a kind of minisize pH sensor, which is characterized in that the minisize pH sensor includes: polyimide substrate, conduction
Elargol screen-printed layers, Ag/AgCl reference electrode, hydrogen ion sensitive sense electrode, polyurethane interlayer and AB glue coating；
The conductive silver glue screen-printed layers are printed on above the polyimide substrate；The Ag/AgCl reference electrode
It is arranged in the conductive silver glue screen-printed layers and is not in contact with each other with the hydrogen ion sensitive sense electrode；The polyurethane interlayer applies
It overlays on the polyimide substrate；The AB glue coating is coated in the Ag/AgCl reference electrode and the hydrogen ion
Sensitive electrode surrounding.
2. minisize pH sensor according to claim 1, which is characterized in that the conductive silver glue screen-printed layers are by electrode
It is bonded printing layer, conducting wire printing layer and solder joint printing layer composition；The electrode bonding printing layer specifically includes first electrode bonding
Printing layer and second electrode are bonded printing layer；The Ag/AgCl reference electrode is adhered in the first electrode bonding printing layer；
The hydrogen ion sensitive sense electrode is adhered in the second electrode bonding printing layer；First electrode bonding printing layer and described
Second electrode bonding printing layer does not contact；The conducting wire printing layer includes the first conducting wire printing layer and the second conducting wire printing layer, institute
It states the first conducting wire printing layer and the second conducting wire printing layer does not contact；The solder joint printing layer include the first solder joint printing layer and
Second solder joint printing layer, the first solder joint printing layer are not contacted with the second solder joint printing layer；The first conducting wire printing
One end of layer connects the first solder joint printing layer, and the other end connects the first electrode and is bonded printing layer；Second conducting wire
One end of printing layer connects the second solder joint printing layer, and the other end connects the second electrode and is bonded printing layer；The poly- ammonia
Ester interlayer is coated in the polyurethane interlayer coating zone of the polyimide substrate surface, polyurethane interlayer coating area
Domain is the area in the polyimide upper surface of base plate in addition to the electrode is bonded printing layer and the solder joint printing layer
Domain.
3. minisize pH sensor according to claim 2, which is characterized in that the Ag/AgCl reference electrode includes reference
Electrode matrix and the AgCl layer for being deposited on the reference electrode matrix surface；The hydrogen ion sensitive electrification extremely RuO2-IrO2Base H+
Working electrode or RuO2Base H+Working electrode；
The RuO2-IrO2Base H+Working electrode includes the first matrix and the first hydrogen ion coated in first matrix surface
Sensitive materials；First matrix is titanium sheet；The first hydrogen ion sensitive materials are RuO2And IrO2Composition；
The RuO2Base H+Working electrode includes the second matrix and the second hydrogen ion sensitivity object coated in second matrix surface
Matter；Second matrix is silicon chip；The second hydrogen ion sensitive materials are RuO2。
4. a kind of minisize pH transducer production method, which is characterized in that the preparation method is used to prepare described in claim 1
Minisize pH sensor, the preparation method include:
Prepare polyimide substrate；
Conductive silver glue screen-printed layers are printed in the polyimide upper surface of base plate；
Ag/AgCl reference electrode and hydrogen ion sensitive sense electrode are bonded in the conductive silver glue screen-printed layers；The Ag/AgCl
Reference electrode is not in contact with each other with the hydrogen ion sensitive sense electrode；
Polyurethane is coated on the polyimide substrate, forms polyurethane interlayer；
AB glue is coated in the Ag/AgCl reference electrode and the hydrogen ion sensitive sense electrode surrounding, forms AB glue coating.
5. minisize pH transducer production method according to claim 4, which is characterized in that described thin in the polyimides
Conductive silver glue screen-printed layers are printed in plate base upper surface, specifically include:
One layer of conductive silver glue screen-printed layers are printed in the polyimide upper surface of base plate using silk screen print method；It is described
Conductive silver glue screen-printed layers are made of electrode bonding printing layer, conducting wire printing layer and solder joint printing layer；The electrode bonding print
Brush layer specifically includes first electrode bonding printing layer and second electrode bonding printing layer；The first electrode bonding printing layer and institute
Second electrode bonding printing layer is stated not contact；The conducting wire printing layer includes the first conducting wire printing layer and the second conducting wire printing layer,
The first conducting wire printing layer and the second conducting wire printing layer do not contact；The solder joint printing layer includes the first solder joint printing layer
With the second solder joint printing layer, the first solder joint printing layer is not contacted with the second solder joint printing layer；The first conducting wire print
One end of brush layer connects the first solder joint printing layer, and the other end connects the first electrode and is bonded printing layer；Described second leads
One end of line printing layer connects the second solder joint printing layer, and the other end connects the second electrode and is bonded printing layer.
6. minisize pH transducer production method according to claim 5, which is characterized in that described in the conductive silver collodion silk
It is bonded Ag/AgCl reference electrode and hydrogen ion sensitive sense electrode on wire mark brush layer, specifically includes:
The Ag/AgCl reference electrode is bonded in first electrode bonding printing layer；The Ag/AgCl reference electrode includes
Reference electrode matrix and the AgCl layer for being deposited on the reference electrode matrix surface；
The hydrogen ion sensitive sense electrode is bonded in second electrode bonding printing layer.
7. minisize pH transducer production method according to claim 6, which is characterized in that be bonded and print in the first electrode
Before the step of being bonded the Ag/AgCl reference electrode on brush layer, further includes:
The Ag/AgCl reference electrode is prepared using electrochemical workstation chronoptentiometry.
8. minisize pH transducer production method according to claim 6, which is characterized in that be bonded and print in the second electrode
Before the step of being bonded the hydrogen ion sensitive sense electrode on brush layer, further includes:
Prepare titanium sheet；
The titanium sheet is pre-processed, the first matrix is formed；
First hydrogen ion sensitive materials are prepared using Via Polymeric Precursor Method；The first hydrogen ion sensitive materials are RuO2With
IrO2Composition；
The first hydrogen ion sensitive materials are coated on first matrix, form the hydrogen ion sensitive sense electrode.
9. minisize pH transducer production method according to claim 6, which is characterized in that be bonded and print in the second electrode
Before the step of being bonded the hydrogen ion sensitive sense electrode on brush layer, further includes:
Prepare silicon chip；
The silicon chip is cleaned, second matrix is formed；
Second hydrogen ion sensitive materials are prepared using Via Polymeric Precursor Method；The second hydrogen ion sensitive materials are RuO2；
The second hydrogen ion sensitive materials are deposited in second matrix surface using magnetron sputtering technique, formed the hydrogen from
Sub- sensitive electrode.
10. minisize pH transducer production method according to claim 9, which is characterized in that described in the polyimides
Polyurethane is coated in sheet substrate, is formed polyurethane interlayer, is specifically included:
The polyurethane is coated in the polyurethane interlayer coating zone of the polyimide substrate surface, forms the poly- ammonia
Ester interlayer；The polyurethane interlayer coating zone is in the polyimide upper surface of base plate except electrode bonding printing
Region other than layer and the solder joint printing layer.
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| CN110018215A (en) * | 2019-04-01 | 2019-07-16 | 南京航空航天大学 | Miniature chloride ion sensor and its method based on Fick diffusion law |
| WO2021087569A1 (en) * | 2019-11-06 | 2021-05-14 | Commonwealth Scientific And Industrial Research Organisation | A multi-layered electrode for sensing ph |
| CN113295743A (en) * | 2021-04-13 | 2021-08-24 | 中国农业大学 | Preparation method of pH flexible sensor and passive sensing detection method |
| CN113567523A (en) * | 2020-04-29 | 2021-10-29 | 中国科学院海洋研究所 | Device and method for measuring pH value of electrode solution interface |
| WO2021218628A1 (en) * | 2020-04-30 | 2021-11-04 | 深圳安吉尔饮水产业集团有限公司 | Water ph detection sensor and use of ruthenium-iridium electrode as ph sensing material |
| WO2024039810A1 (en) * | 2022-08-18 | 2024-02-22 | Kenneth Edward Salsman | Flexible ph sensor and improved methods of manufacture |
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