Sensor and method for monitoring the evolution of the viscoelastic properties of a material.

Abstract

A sensor for measuring the viscoelastic properties of a material comprises a rigid support (10) and a membrane (11) fixed on the support (10), the material being intended to come into contact on an external face (111) of the membrane (11). The sensor further comprises an active assembly (12) comprising at least one piezoelectric element bonded to an internal face of the membrane (11), the active assembly (12) being configured to generate the oscillation of the membrane (11) according to a resonance mode greater than or equal to the second resonance mode of the membrane (11). Method for measuring the viscoelastic properties of a material and method for monitoring the coagulation of milk using such a sensor. Figure for the abstract: Fig. 2

Description

Title of the invention: Sensor and method for monitoring the evolution of the viscoelastic properties of a material. Technical field

[0001] The invention relates to a sensor dedicated to monitoring the evolution of the viscoelastic characteristics of a material. It also relates to a method for monitoring the evolution of the viscoelastic properties of a material, in particular milk in the coagulation phase. • Prior art

[0002] Among the key stages of cheese making, milk coagulation is of particular interest to professionals. This stage consists of transforming the milk into a gel, the curdled milk, thanks to the action of a coagulating agent. This coagulation stage requires special attention. Indeed, the cheesemaker must make a multitude of observations at short and regular intervals to be able to detect the change in state of the milk and the evolution of the firmness of the gel thus formed. This transition will have an impact on all the stages that will follow, such as cutting the gel, draining, acidification or even ripening and finally on the quality of the finished product. Consequently, during the milk coagulation stage, the cheesemaker must detect certain parameters that are essential such as: • measuring the setting time when transforming milk into gel, • the measurement of an optimal value of gel firmness corresponding to the moment of the cutting of this gel, this optimum being a function of the type of cheese technology.

[0003] The characterization of milk during its processing thus plays a key role. It is therefore necessary to propose instrumentation integrating a sensor adapted to the production conditions.

[0004] Different methods exist for simultaneously measuring the coagulation time and the properties of the gel. A technique commonly used in the field of dairy products is implemented by a device called "Formagraph". This device, designed in the early 1980s, sets in motion a container containing the product during coagulation and measures the transmission of this movement to a rod which is suspended in the liquid. The more viscous and gel-like the product becomes, the more movement is transmitted to the rod. Document FR 2 991 771 A1 uses this technique by perfecting the way of measuring the movement on the rod.

[0005] This method of measurement is not satisfactory since it is necessary to take samples of the milk and coagulation occurs in a separate volume of the one where the cheese is formed, with therefore potentially variations in ambient conditions. The coagulation conditions are therefore not identical, in particular the temperature can be different so that the coagulation of the sample does not necessarily represent the coagulation of the milk in the vat.

[0006] The same defects are found with the device described by document US 9,494,475 B1.

[0007] The document "PZN-PT based smart probe for high temperature fluid viscosity measurements" published by Chen Zhang et al in 2016 in Elsevier, Measurement 94 (2016) 753-758, shows a measurement technique with a plunger, which is set in oscillation. A piezoelectric cell is glued to the plunger with epoxy resin. The plunger allows access to the viscosity properties of the liquid in which the tip of the plunger is placed. The physical arrangement of the plunger does not allow the sensor to be placed in an interesting position for real-time monitoring of milk coagulation. • Presentation of the invention

[0008] The invention aims to provide a sensor and a method for monitoring the evolution of the viscoelastic properties of a material in situ.

[0009] With these objectives in view, the invention relates to a sensor for measuring the viscoelastic properties of a material, comprising a rigid support and a membrane fixed to the support, the material being intended to come into contact with an external face of the membrane, the sensor being characterized in that it further comprises an active assembly having at least one piezoelectric element glued to an internal face of the membrane, the active assembly being configured to generate the oscillation of the membrane according to a resonance mode greater than or equal to the second resonance mode of the membrane. By providing a sensor having a membrane that can be in contact with the material to be measured, the sensor can be placed directly in contact with the material. Thus, the evolution of the material in its container can be monitored in real time without having to take a sample.The first resonance mode of a membrane, or fundamental mode, is a mode in which, when looking at a section through the membrane, the formation of a single maximum displacement is observed between the two anchor points of the membrane on the support. The second resonance mode is characterized by the simultaneous presence of two displacement maxima on the membrane. The use of a resonance mode greater than or equal to the second resonance mode of the membrane allows an interaction of the membrane and the material with movements of lesser amplitude than with the first resonance mode. The inventors found that with such a resonance mode, the damping of the movement was less, whereas with the first resonance mode, the damping was such that the measurements became . difficult, or even insignificant. The inventors also found that the characteristics of the resonance mode evolved according to the properties of the material. Knowledge of the characteristics of the resonance mode thus provides access to the properties of the material.

[0010] According to a constructive arrangement, the membrane has the shape of a disc embedded by its periphery on the support. This shape is simple to produce and has shown good results. It also makes it possible to obtain a waterproof sensor with good resistance.

[0011] According to a constructive arrangement, the active assembly only partially covers the internal face of the membrane. The addition of piezoelectric elements to the surface of the membrane stiffens it. By minimizing the surface occupied by the piezoelectric elements, the increase in the rigidity of the membrane is also minimized, which makes it possible to be more in agreement with the frequencies usable for characterizing the material.

[0012] According to one embodiment, the membrane has a center and the active assembly is off-center on said internal face. By having an active assembly off-center relative to the center of the membrane, the appearance of an operating mode superior to the fundamental resonance mode is favored. This increases the sensitivity of the sensor.

[0013] According to one embodiment, the active element is arranged to generate differential oscillations of the membrane. By generating differential oscillations is meant the act of moving the membrane in one direction at one location and in an opposite direction at another location. The generation of differential oscillations directly forces the membrane into a particular resonance mode.

[0014] According to an improvement, the external face has a wettability characterized by a contact angle of a drop of distilled water of 1 qL less than 20°, preferably less than 10°. It has been found that when the external face has a low wettability, the measurements could be, under certain conditions, erroneous. The inventors believe that this is perhaps due to poor coupling between the fluid and the membrane. By working the surface to improve the wettability, they found that these effects no longer occurred.

[0015] According to a constructive arrangement, the external face of the membrane comprises a coating or a treatment for improving wettability.

[0016] According to one embodiment, the coating is chosen from a polymer coating, a silicon oxide deposit or an epoxy resin incorporating or not titanium oxide nanoparticles. A coating with silicon oxide is for example obtained from a precursor, tetraethyl orthosilicate.

[0017] According to one embodiment, the external face is polished. This reduces the roughness of the surface, which improves wettability. For example, an in- roughness is obtained less than 20 nanometers.

[0018] According to one embodiment, the sensor is intended for use in monitoring milk coagulation. The sensor may be of dimensions adapted to this measurement and to environmental constraints, in particular hygiene. It may be used in the manufacture of dairy products of any type.

[0019] According to one embodiment, the sensor is intended for use in monitoring cheese production. The sensor can in fact be involved in monitoring production and in decision-making, particularly regarding the time of implementation of certain operations.

[0020] The invention also relates to a method for measuring the viscoelastic properties of a material, characterized in that a sensor as described above is used, the material is placed in contact with the external face of the membrane and the electrical characteristics of the piezoelectric element are measured when it is supplied at a frequency capable of inducing for the membrane a resonance mode greater than or equal to the second mode. The measurements on the piezoelectric element are affected by the behavior of the membrane which is itself affected by the presence and the properties of the material in contact with the membrane. It is therefore possible to go back to the properties of the material as a function of the electrical measurements at the terminals of the piezoelectric element.

[0021] The invention also relates to a method for monitoring milk coagulation, according to which the impedance of the active assembly is measured at different frequencies, at least one of the parameters is determined among the maximum phase q> max(t) of the impedance or the admittance, the maximum modulus Z max(t) of the impedance or the admittance, an offset of the anti-resonance frequency AFa or resonance AFr and the pseudo-resonance frequency for the phase Fq>max(t), and it is determined that the milk is sufficiently curdled when the monitored parameter(s) have changed by a predetermined value or in a predetermined ratio. When a voltage at a predetermined frequency is applied to the terminals of the active assembly, an electric current is observed having an intensity and a phase related to the voltage supplied. This ratio is called the impedance which is broken down into a phase q> and a module Z. We can also work with the admittance which is the inverse ratio of the impedance.By changing the frequency close to the frequency corresponding to a resonance mode, we see that the phase and the modulus also change. We can thus determine a maximum for the phase as well as for the modulus. The frequency at which the maximum for the phase or for the modulus is observed also changes according to the properties of the milk in the coagulation phase. The resonance frequency Fr is the frequency at which the minimum of the modulus is reached. The anti-resonance frequency Fa is the frequency at which the maximum of the modulus is reached. reached. The shift of the anti-resonance frequency AFa is the difference between the anti-resonance frequency between the initial moment and the moment when the measurement is made. Similarly, the shift of the resonance frequency AFr is the difference between the resonance frequency between the initial moment and the moment when the measurement is made. The pseudo-resonance frequency for the phase Fq>max(t) is the frequency at which the maximum is observed for the phase at a given moment. We can determine different criteria to consider that the milk is sufficiently curdled, for example on the pseudo-resonance frequency for the phase in an absolute manner, or in offset from the start of the curdling phase, or even in relative value always in relation to the start of the curdling phase. The criteria can also be a relative or absolute variation on the maximum modulus, or on the relative or absolute variation of phase for this maximum.The criteria must be adapted to the type of cheese being made. • Brief description of the figures

[0022] The invention will be better understood and other features and advantages will appear on reading the description which follows, the description making reference to the appended drawings among which: • [Fig.l] is a view of a cheese-making vat in which a sensor according to the invention is mounted; • [Fig.2] is a sectional view of the sensor of [Fig.l]; • [Fig.3] is a top view of a membrane of the sensor of [Fig.2] according to different versions; • [Fig.4] is a view of the membrane representing different vibration modes; • [Fig.5] is a curve representing the evolution of the sensor impedance modulus as a function of frequency; • [Fig.6] is a curve representing the evolution of the phase of the sensor impedance as a function of frequency; • [Fig.7] is a view showing the evolution of a parameter measured by the sensor as a function of time during milk coagulation. • Detailed description

[0023] A viscoelastic property measuring sensor according to the invention can be implemented during cheese production, in particular during the milk coagulation step and during the evolution of the firmness of the gel. [Fig.l] shows an example of a tank 2 into which the milk is poured at a controlled temperature, and coagulant is added to trigger the coagulation step. The tank 2 is equipped with a sensor 1 according to the invention by being arranged in the tank 2.

[0024] As shown in detail in [Fig.2], the sensor 1 for measuring the visco- elastics comprises a rigid support 10 of annular shape and a membrane 11 in the form of a disc fixed on the support 10. The support 10 and the membrane 11 are made of stainless steel. The support 10 comprises a rebate 100 at the connection between an end face 101 and an internal bore 102. The membrane 11 is housed in this rebate 100 in such a way that it comprises an external face 111 substantially aligned with the end face 101. For the manufacture of the sensor 1, a continuous weld is carried out between the periphery of the membrane 11 and the support 10 in such a way that the membrane 11 is embedded in a sealed manner on the support 10. The external face 111 of the membrane 11 receives a surface treatment so as to improve its wettability.

[0025] An active assembly 12 is also fixed on the internal face of the membrane 11 opposite the external face 111. In the example which is shown the active assembly only comprises a piezoelectric element 12 in the form of a pellet with a diameter smaller than the radius of the membrane 11. This pellet 12 has substantially the same thickness as the membrane 11 and is fixed on the membrane 11 by means of an epoxy type glue in an off-center manner.

[0026] The cavity behind the membrane 11 can receive electronic elements 13 necessary for the connection and power supply of the piezoelectric element. A cable, not shown, with electrical conductors passes radially through the support 10, the electrical conductors being connected to the electronic elements. The cavity is closed by a bottom wall 14 opposite the membrane 11 and also sealed by its periphery. The active assembly 12 is thus configured to generate the oscillation of the membrane 11 according to a resonance mode greater than or equal to the second resonance mode of the membrane 11.

[0027] The material whose viscoelastic properties are to be evaluated is brought into contact in particular with the end face 101 and on the external face 111 of the membrane 11.

[0028] We will now describe a surface treatment which makes it possible to improve the wettability of the external face 111 of the sensor 1.

[0029] A coating is applied to the external face 111 of the membrane 11 by a sol-gel process. Sol-gel is a chemical reaction in solution which after gelling gives a solid matrix. This process, here based on titanium dioxide (TiO2) and silicon dioxide (SiO2), comprises four steps.

[0030] First, the preparation of a SiO2 solution, by mixing acidified water at pH 3 and tetraethyl orthosilicate (TEOS), according to a molar ratio of 1:20. It is stirred for a minimum of 18 hours. The hydrolysis of the precursor (TEOS), by reaction between silica and water, takes place according to the reaction:

[0031] Si(OEt)4 + 4 H2O —> Si(OH)4 + 4 EtOH where Et is an ethyl group C2H5.

[0032] This reaction is followed by a condensation reaction, allowing the formation of the SiO2:

[0033] 2 Si(OH)4 -> (OH)3-Si-O-Si(OH)3 + H2O

[0034] This condensation step results in the formation of gels in which the Si-O-Si complexes are linked together.

[0035] (OH)3-Si-O-Si(OH)3 -> 2 SiO2+ 3 H2O

[0036] The second step is the preparation of the TiO2 solution. This is prepared from a mixture of distilled water / hydrochloric acid / glacial acetic acid / titanium tetraisopropoxide (TTIP), at 60°C for 2 hours, in a molar ratio of 88.6:1.4:5:5. The solution is then stirred for a minimum of 16 hours at room temperature before use. The reaction between TTIP, of formula Ti[OCH(CH3 )2]4, and acidified water allows the formation of TiO2 according to the following reactions:

[0037] Ti[OCH(CH3)2]4 + H2O -> Ti(OH)4 + 4 (CH3)2CHOH

[0038] 2 Ti(OH)4 -> (OH)3-Ti-O-Ti(OH)3 + H2O 2 TiO2 + 3 H2O

[0039] Then, a TiO2 / SiO2 mixture is then prepared and stirred for at least 1 hour according to molar ratios 30:70 50:50 or 70:30.

[0040] The TiO2 / SiO2 mixture is deposited on the external face 111 of the membrane 11 of the sensor 1 by spin-coating. During spin-coating, the disc is positioned on a rotating support and a drop of solution is deposited in the center of the surface. The centrifugal force then distributes the solution uniformly over the entire surface.

[0041] The stainless steel membrane is pre-activated by O2 plasma before deposition. During spin coating, this is accelerated to a speed of 4000 rpm; a drop of 1 to 2 ml of TiO2 / SiO2 mixture is deposited once the speed of 4000 rpm is reached. The disc is rotated for a total time of 1 minute.

[0042] The last step consists of annealing. The solvents are evaporated by drying and a heat treatment will allow the densification of the film. After deposition, the disc is placed in an oven at 80°C for 15 minutes for the evaporation of the solvent, then a heat treatment at 120°C for 25 minutes is carried out. A super-hydrophilic coating with a thickness of a few tens of nanometers is obtained.

[0043] Different characterizations of the TiO2 / SiO2 coating on the disc are carried out to measure the wettability of the surface and its roughness.

[0044] The contact angle of a 1 pL drop of demineralized water deposited on the surface is measured with a goniometer. The roughness of the TiO2 / SiO2 film is determined by profilometry.

[0045] The angle of the drop is less than 20°.

[0046] [Fig.4] represents different resonance modes of the membrane 11. Figure 4a shows the fundamental resonance mode, or first mode, in which the amplitude maximum vibration appears at the center of the membrane 11. This resonance mode is not considered satisfactory for obtaining the measurements according to the invention. Figure 4b represents the second resonance mode, in which a bump 113 appears on one side of the membrane 11 while a symmetrical hollow 114 appears on the other side. Figure 4c represents the third resonance mode in which two bumps 113' appear symmetrically with respect to the center while two hollows 114' appear simultaneously, also symmetrical with respect to the center but offset by a quarter turn with respect to the bumps 113'. These resonance modes appear at different frequencies to which the membrane 11 is subjected by the active assembly 12.When a piezoelectric element is placed in a zone with high amplitudes in a specific resonance mode, this resonance mode is favored, meaning that the impedance obtained is particularly variable depending on the frequency.

[0047] To implement the method according to the invention, the material is placed in contact with the external face 111 of the membrane 11 and the electrical characteristics are measured at the terminals of the piezoelectric element. For this, an impedance measuring device is used which supplies the sensor 1 with an alternating voltage of adjustable frequency. The active assembly 12 is supplied at a frequency suitable for inducing for the membrane 11 a resonance mode greater than or equal to the second mode. The frequencies in the vicinity are explored by measuring, for example, the modulus and the phase shift of the impedance. Figures 5 and 6 show the evolution of the modulus and the phase respectively as a function of the frequency near the resonance. It can be seen that at the resonance frequency, Fr(t), the modulus is minimal Zmin(t) then increases to the maximum value Zmax(t) for the antiresonance frequency Fa(t) before decreasing.The diagram shows a second curve with roughly the same shape but flatter and shifted towards higher frequencies. This second curve corresponds to a measurement with the presence of a more viscous material than in the measurement obtained on the first curve. In [Fig.6], we see that the phase shift reaches a maximum. <e>max(t) for a frequency F <e>max(t), then decreases with increasing frequency. [Fig.6] also shows a first and a second curve corresponding to measurements with the same sensor 1 but a more viscous material in contact with the membrane 11.

[0048] These measurements are applied to a method for monitoring milk coagulation. Tank 2 is filled with milk at a controlled temperature, and measurements are started when the coagulant is added. [Fig.7] shows the measurement of the evolution of the maximum phase <e>max(t) as a function of the coagulation time, as well as a variation curve of this value (derivative with respect to time).

[0049] We note that the value is initially stable, then begins to change first fast, which corresponds to the setting time, then a little slower. We determine that the milk is sufficiently curdled when the maximum phase <e>max(t) has evolved to reach a predetermined value, for example 1.5°. This predetermined value is a setpoint defined by the cheesemaker.

[0050] In different variants of implantation of the assembly, as shown in [Fig. 3], the active assembly 12 is arranged to generate differential oscillations of the membrane 11. Example (c) is that which was used previously with a piezoelectric element in the form of a pellet with a diameter smaller than the radius of the membrane 11. In example (a), the surface of the membrane 11 is covered by an active assembly 12' comprising eight piezoelectric elements 120 in the form of sectors. The adjacent sectors are powered so that their action is in phase opposition. Example (b) comprises a piezoelectric element 12” in the form of a circular pellet centered on the membrane 11. In example (d), the active assembly 12'” comprises 4 piezoelectric pellets 121 of circular shape arranged at the top of a square and inscribed in the diameter of the membrane 11.

[0051] The invention is not limited to the embodiment just described. The coating to improve wettability could be a polymer coating. The external face 111 could be polished and bare. The evolution of the maximum of the modulus could be followed instead of that of the phase, or the evolution of the pseudoresonance frequency. These parameters could also be combined.< / e> < / e> < / e> < / e>

Claims

Claims

1. Sensor for measuring the viscoelastic properties of a material comprising a rigid support (10) and a membrane (11) fixed on the support (10), the material being intended to come into contact on an external face (111) of the membrane (11), the sensor being characterized in that it further comprises an active assembly (12) comprising at least one piezoelectric element bonded to an internal face of the membrane (11), the active assembly (12) being configured to generate the oscillation of the membrane (11) according to a resonance mode greater than or equal to a second resonance mode of the membrane (11).

2. Sensor according to claim 1, in which the membrane (11) has the shape of a disc embedded by its periphery on the support (10).

3. Sensor according to claim 1 or 2, in which the active assembly (12) only partially covers the internal face of the membrane (11).

4. Sensor according to one of claims 2 or 3, in which the membrane (11) has a center and the active assembly (12) is off-center on said internal face.

5. Sensor according to one of the preceding claims, in which the active assembly (12) is arranged to generate differential oscillations of the membrane (11).

6. Sensor according to one of the preceding claims, in which the external face (111) has a wettability characterized by a contact angle of a drop of distilled water of 1 qL less than 20°, preferably less than 10°.

7. A sensor according to claim 6, wherein the outer face (111) of the membrane (11) comprises a wettability-enhancing coating or treatment.

8. Sensor according to claim 7, in which the coating is chosen from a coating of polymers and a deposition of nanoparticles of titanium oxides and silicon oxide.

9. A sensor according to claim 7 or 8, wherein the outer face (111) is polished.

10. Sensor according to one of claims 1 to 9, intended for use in monitoring milk coagulation.

11. Sensor according to one of claims 1 to 9, intended for use in controlling cheese production.

12. A method of measuring the viscoelastic properties of a material, ca- characterized in that a sensor according to one of the preceding claims is used, the material is placed in contact with the external face (111) of the membrane (11) and the electrical characteristics of the piezoelectric element are measured when it is supplied at a frequency capable of inducing for the membrane (11) a resonance mode greater than or equal to the second mode.

13. Method for monitoring milk coagulation, characterized in that a measurement is carried out according to the method of claim 12 and according to which the impedance of the active assembly (12) is measured at different frequencies, at least one of the parameters is determined among the maximum phase q> max(t) of the impedance or the admittance, the maximum modulus Z max(t) of the impedance or the admittance, an offset of the anti-resonance frequency AFa or resonance AFr, the pseudo-resonance frequency for the phase Fq>max(t), and it is determined that the milk is sufficiently curdled when the parameter(s) monitored have changed by a predetermined value or in a predetermined ratio.

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