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Microwave properties of composites with chromium dioxide
ARTICLE IN PRESS
Journal of Magnetism and Magnetic Materials 300 (2006) e70–e73 www.elsevier.com/locate/jmmm
Microwave properties of composites with chromium dioxide Sergey N. Starostenko, Konstantin N. Rozanov, Aleksey V. Osipov Institute for Theoretical and Applied Electromagnetics, 125412, Izhorskaya 13/19, Moscow, Russia Available online 18 November 2005
Abstract The permittivity and permeability of composites filled with CrO2 powder are measured within the frequency range from 0.05 to 12 GHz. A sharp line of magnetic absorption is detected near 8 GHz. The effects of magnetic bias and remanence on the permittivity and permeability spectra are analyzed. The hysteretic behavior of dynamic permeability is observed for both parallel and perpendicular bias orientations relative to the microwave magnetic field. The effect is due to switching of the magnetic texture under bias equal to coercive field. At 50 MHz the parallel bias close to coercive field affects permeability much stronger than the perpendicular one. At 10 GHz the effect of perpendicular bias is higher than that of the parallel one. The effect of remanence on the microwave permeability is negligible. The 3 kOe parallel bias suppresses the line of magnetic absorption and decreases the conductivity of the composite and its microwave permittivity. This can be attributed to the magnetostatic interaction of inclusions in the vicinity of the percolation threshold. r 2005 Elsevier B.V. All rights reserved. PACS: 78.70.Gq Keywords: Composite; Microwave permittivity; Microwave permeability; Impedance; Absorption spectrum
1. Introduction The study is inspired by the recent advances in development of composites with magnetically controlled attenuation. These composites are filled with wires that have the linear impedance dependent on permeability [1]. The permeability is affected by magnetic bias, thus giving the opportunity for magnetic control of complex permittivity of the composite, e.g., for the applications as screens with controlled microwave transmission. However, the above mechanism of attenuation control is indirect. Namely, the bias governs the parameters of ferromagnetic resonance (FMR), which determine the permeability of the wire. In turn, the permeability affects the skin depth and effective linear resistance of the wire. Finally, the wire resistance and length determine the frequency of dielectric absorption. The paper deals with a direct way of magnetic control of screen opacity at microwaves. Namely the feasibility of screen with magnetically controlled complex permeability Corresponding author. Tel.: +7 095 485 9945; fax: +7 095 484 2633.
E-mail address: [email protected] (S.N. Starostenko). 0304-8853/$ - see front matter r 2005 Elsevier B.V. All rights reserved. doi:10.1016/j.jmmm.2005.10.151
is considered. It is well known that the permeability m is a function of magnetic bias [2]. Conventionally (e.g. in FMR spectrometry) the bias field Hbias is applied perpendicularly to microwave magnetic field. In this case the resonance frequency Frez of a magnet is proportional to saturation magnetization Ms and to Hbias. A particular form of the relation depends on the shape and domain structure of the magnet, but the proportionality coefficient includes the gyromagnetic factor g ¼ 2:8 GHz=kOe. Hence the high perpendicular biasing fields Hbias are needed to obtain a noticeable shift of Frez at microwaves. On the other hand, the parallel bias is known to affect significantly the differential permeability mdiff of coercive magnetic materials [2]. Hence the microwave permeability of a composite magnet can be affected as well. Although magnetically bistable materials have low initial permeability, the differential permeability may be rather high, when magnetic biasing field equals to the coercive field Hcoerc. Therefore, for magnetic materials having square hysteresis loop and low switching field, the control of microwave permeability may be more efficient with the parallel bias than with the perpendicular one.
ARTICLE IN PRESS S.N. Starostenko et al. / Journal of Magnetism and Magnetic Materials 300 (2006) e70–e73
0.3
0.2
µ'-1
The study evaluates the feasibility of magnetic control of microwave attenuation of isotropic composites filled with coercive powders. The filler is selected bearing in mind practical tasks. Namely it is reasonable to control parameters of a composite that can be an effective absorber itself. Hence the filler should have high Ms, which excludes ferrites; its magnetic spectrum should be unmasked by skinning, which excludes permeable metals that are chemically unstable when the particle size is about the microwave skin depth. The filler should have a square hysteresis loop and it should be available from industry. From this standpoint the chromium dioxide CrO2 is a reasonable selection: it is magnetically bistable, it has Ms higher than that of ferrites, and skinning in CrO2 particles is negligible [3].
e71
0.1
2. Sample preparation and e and l measurement 0
The composites are prepared of CrO2 whiskers dispersed in paraffin wax. The whiskers have diameter about 0.02 mm and length about 0.5 mm. The specific resistance of CrO2 is about 0.02 O m. The composites comprise randomly oriented inclusions and resemble the microstructure of isotropic mixtures filled with carbon black (usually acetylene soot). The composites exhibit low percolation threshold (about 10% vol.) and are conductive for direct current (DC) at higher filling. The samples are shaped either by pressing as parallelepipeds with the dimensions fitted to a standard 10 23 mm rectangular waveguide, or by molding in form of a 10 mm sphere. The spherical samples are made for measurements at 50 MHz. They contain 30% vol. of CrO2 and have specific resistance of about 1 O m. The rectangular samples contain 20% of CrO2 and exhibit approximately 100 times higher resistance. The microwave permittivity e0 ie00 and permeability m0 im00 are determined by parametric reconstruction of e and m frequency dispersions from the scalar reflectivity spectrum measured of a sample shorted through known air gap [4]. The reflectivity measurements are made in a rectangular waveguide in the frequency range from 8 to 12 GHz. The quasistatic permeability m0 is measured at 50 MHz with a multiloop coil via the Q-meter technique. The magnetic bias varies in the range of 73 kOe and can be applied either parallel or perpendicular to the highfrequency magnetic field. 3. Experimental results and discussion The measurements at 50 MHz reveal the hysteretic behavior of permeability for both parallel and perpendicular bias directions (see Fig. 1). The effect of 3 kOe perpendicular bias is small: the susceptibility response is less than 5%. The parallel bias of the same 3 kOe strength saturates the sample and makes it practically impermeable with mdiffE1. The permeability difference between the degaussed and magnetized samples (i.e., the effect of remanence) is about
-2
0 H [kOe]
2
Fig. 1. Quasistatic permeability m0 as a function of bias strength for parallel and perpendicular bias directions (solid and dashed lines, respectively). Gray and black lines correspond to the bias sweep pointed by gray and black arrows.
3%. When bias is about coercive field (about 500 Oe), the difference in permeability between magnetizing and demagnetizing bias sweep is about 0.1. This difference is much lower than that expected from the static hysteresis loop [3]. The hysteresis loop at 50 MHz is flatter than the static one, and the differential permeability mdiff drops with increasing frequency until reaching the value of initial permeability. The hysteretic behavior of permeability should disappear at microwaves because the parallel bias results in decrease of the intensity of FMR line and the perpendicular bias results in increase of FMR frequency. Both effects are not inertial, as the contribution of domain wall motion is small at microwaves. However the reflectivity measurements at 10 GHz reveal the hysteretic behavior for both orientations of the bias field (see Fig. 2). The reason of the phenomenon is that the domain structure (the magnetic texture of a composite) is biasdependent and the parameters of FMR line do depend on this structure. When the increasing bias reaches the coercive field value, it switches the magnetic moments of domains. If the bias is parallel, then the reversing moments take the intermediate position that is perpendicular to the high-frequency magnetic field. This position corresponds to the maximal quasistatic permeability and to the maximal intensity of FMR line. If the bias field is decreasing, then the magnetic moments remain parallel to the high-frequency magnetic field and the quasistatic permeability is low. If the bias is increasing and perpendicular, then the effect is inverse: a part of switching moments takes the position parallel to highfrequency magnetic field that corresponds to the minimal quasistatic permeability, while the decreasing bias corre-
ARTICLE IN PRESS S.N. Starostenko et al. / Journal of Magnetism and Magnetic Materials 300 (2006) e70–e73
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-4
30
R [dB]
permittivity ε'-, ε''- -
-8
-12
20
10
-16 -2
0
2 0
H [kOe]
7
Fig. 2. The reflectivity of 1.5-mm-thick CrO2 composite sample shorted through 15 mm air gap as a function of bias strength for the parallel bias (solid lines) and for the perpendicular bias (dashed lines). Gray and black lines correspond to the direction of bias sweep indicated by the gray and black arrows.
9
10 11 frequency [GHz]
12
13
12
13
1.5
permeability µ' -, µ''- -
sponds to high permeability values. This portion of magnetic moments is at least twice smaller than that in the case of parallel bias, thus the effect is weaker. This is the very reason of the hysteretic behavior of differential permeability under perpendicular bias shown in Fig. 1 and of the hysteretic reflectivity curves in Fig. 2. The perpendicular bias affects both m0 and Frez, hence its total effect on absorption line is higher than that of the parallel bias. Since the intermediate position of magnetic moments is unstable, the phenomenon difficult to observe in measurements under fixed bias fields. The microwave measurements of degaussed samples reveal (see Fig. 3) the X-band line of magnetic absorption that is sharp relative to the absorption in ferrites or carbonyl iron. The parameters of the line correlate with FMR data [5]. The average X-band permeability of CrO2filled composite is close to that of composite equally filled with carbonyl iron (mE1i 0.4), while the permittivity is close to that of mixtures with carbon black (eE35i 8) [6]. A medium bias (p1 kOe) applied parallel to the long side of a waveguide has low effect on the magnetic spectrum. The 3 kOe bias transforms the Lorenzian FMR line into an asymmetric line, where the absorption stretches towards high-frequency and steeply falls below 8 GHz (see Fig. 3). Since the sample is resistive, the dielectric spectrum is a complicated multiline one. The dielectric absorption is located mainly beyond the experimental frequency band: the absorption arising due to DC conductivity is appears at lower frequency; the absorption attributed to resonance on whisker length appears at higher frequency. As a result the
8
1
0.5
0 7
8
9
10
11
frequency [GHz] Fig. 3. The permittivity and permeability spectra of a sample filled with 20% vol of CrO2. The black lines correspond to zero bias; the light gray lines correspond to 3 kOe bias parallel to magnetic vector, i.e., to the short side of the waveguide; the dark gray lines correspond to 3 kOe bias perpendicular to magnetic vector.
reconstructed permittivity dispersion is weak. The 3 kOe bias parallel to the short side of a waveguide saturates the sample which becomes impermeable. For low-coercive magnetic materials the saturating bias can be low enough to suit the practical applications. An unexpected observation is that this transformation is accompanied by significant permittivity change, similarly
ARTICLE IN PRESS S.N. Starostenko et al. / Journal of Magnetism and Magnetic Materials 300 (2006) e70–e73
to the bias effect on permittivity of composites with magnetic fibers [1]. The permittivity decrease correlates with DC measurements under bias: the mixture with 20% vol. of CrO2 exhibits magnetoimpedance coefficient about 100 times higher than that of the bulk CrO2 [3]. The coefficient is positive for the bias perpendicular to electric field and negative for the parallel bias. The coefficient drops drastically with filling increase. In a composite the effect is amplified relative to bulk CrO2 by magnetostatic interaction of neighboring inclusions. The effect should be maximal at the percolation threshold. 4. Conclusion The measurements reveal the hysteresis of microwave permeability of composites filled with CrO2. The hysteresis is attributed to switching of magnetic texture under bias equal to the coercive field. Within the X-waveband the composites under study are as effective absorbers as that filled with carbonyl iron. If the wideband absorbing performance is considered the CrO2-filled composites behave like soot-filled materials (composites with carbon black). The magnetic control of microwave permeability of
e73
CrO2-filled samples requires high bias strength (about 3 kOe) for arbitrary bias direction that is unfeasible for practice. At the percolation threshold the permittivity of composite may be sensitive to magnetic bias enough to suit the needs of practical applications.
Acknowledgments The work is partially supported by the Russian Foundation for Basic Research, Grant No 05-08-01212.
References [1] S.N. Starostenko, K.N. Rozanov, A.V. Osipov, J. Magn. Magn. Mater. 298 (1) (2006) 56. [2] R.M. Bozorth, Ferromagnetism, IEEE Press, New York, 1993. [3] J. Dai, J. Tang, Phys. Rev. B 63 (2000) 54434. [4] S.N. Starostenko, A.P. Vinogradov, IEEE Trans. Instrum. Meas. 51 (1) (2002) 125. [5] B. Rameev, A. Gupta, G. Miao, Solid State Phys. A 201 (15) (2004) 3350. [6] J.C. Martin, J.M. Fornies-Marquina, A.M. Bottreau, Mol. Phys. 101 (2003) 1789.
Journal of Magnetism and Magnetic Materials 300 (2006) e70–e73 www.elsevier.com/locate/jmmm
Microwave properties of composites with chromium dioxide Sergey N. Starostenko, Konstantin N. Rozanov, Aleksey V. Osipov Institute for Theoretical and Applied Electromagnetics, 125412, Izhorskaya 13/19, Moscow, Russia Available online 18 November 2005
Abstract The permittivity and permeability of composites filled with CrO2 powder are measured within the frequency range from 0.05 to 12 GHz. A sharp line of magnetic absorption is detected near 8 GHz. The effects of magnetic bias and remanence on the permittivity and permeability spectra are analyzed. The hysteretic behavior of dynamic permeability is observed for both parallel and perpendicular bias orientations relative to the microwave magnetic field. The effect is due to switching of the magnetic texture under bias equal to coercive field. At 50 MHz the parallel bias close to coercive field affects permeability much stronger than the perpendicular one. At 10 GHz the effect of perpendicular bias is higher than that of the parallel one. The effect of remanence on the microwave permeability is negligible. The 3 kOe parallel bias suppresses the line of magnetic absorption and decreases the conductivity of the composite and its microwave permittivity. This can be attributed to the magnetostatic interaction of inclusions in the vicinity of the percolation threshold. r 2005 Elsevier B.V. All rights reserved. PACS: 78.70.Gq Keywords: Composite; Microwave permittivity; Microwave permeability; Impedance; Absorption spectrum
1. Introduction The study is inspired by the recent advances in development of composites with magnetically controlled attenuation. These composites are filled with wires that have the linear impedance dependent on permeability [1]. The permeability is affected by magnetic bias, thus giving the opportunity for magnetic control of complex permittivity of the composite, e.g., for the applications as screens with controlled microwave transmission. However, the above mechanism of attenuation control is indirect. Namely, the bias governs the parameters of ferromagnetic resonance (FMR), which determine the permeability of the wire. In turn, the permeability affects the skin depth and effective linear resistance of the wire. Finally, the wire resistance and length determine the frequency of dielectric absorption. The paper deals with a direct way of magnetic control of screen opacity at microwaves. Namely the feasibility of screen with magnetically controlled complex permeability Corresponding author. Tel.: +7 095 485 9945; fax: +7 095 484 2633.
E-mail address: [email protected] (S.N. Starostenko). 0304-8853/$ - see front matter r 2005 Elsevier B.V. All rights reserved. doi:10.1016/j.jmmm.2005.10.151
is considered. It is well known that the permeability m is a function of magnetic bias [2]. Conventionally (e.g. in FMR spectrometry) the bias field Hbias is applied perpendicularly to microwave magnetic field. In this case the resonance frequency Frez of a magnet is proportional to saturation magnetization Ms and to Hbias. A particular form of the relation depends on the shape and domain structure of the magnet, but the proportionality coefficient includes the gyromagnetic factor g ¼ 2:8 GHz=kOe. Hence the high perpendicular biasing fields Hbias are needed to obtain a noticeable shift of Frez at microwaves. On the other hand, the parallel bias is known to affect significantly the differential permeability mdiff of coercive magnetic materials [2]. Hence the microwave permeability of a composite magnet can be affected as well. Although magnetically bistable materials have low initial permeability, the differential permeability may be rather high, when magnetic biasing field equals to the coercive field Hcoerc. Therefore, for magnetic materials having square hysteresis loop and low switching field, the control of microwave permeability may be more efficient with the parallel bias than with the perpendicular one.
ARTICLE IN PRESS S.N. Starostenko et al. / Journal of Magnetism and Magnetic Materials 300 (2006) e70–e73
0.3
0.2
µ'-1
The study evaluates the feasibility of magnetic control of microwave attenuation of isotropic composites filled with coercive powders. The filler is selected bearing in mind practical tasks. Namely it is reasonable to control parameters of a composite that can be an effective absorber itself. Hence the filler should have high Ms, which excludes ferrites; its magnetic spectrum should be unmasked by skinning, which excludes permeable metals that are chemically unstable when the particle size is about the microwave skin depth. The filler should have a square hysteresis loop and it should be available from industry. From this standpoint the chromium dioxide CrO2 is a reasonable selection: it is magnetically bistable, it has Ms higher than that of ferrites, and skinning in CrO2 particles is negligible [3].
e71
0.1
2. Sample preparation and e and l measurement 0
The composites are prepared of CrO2 whiskers dispersed in paraffin wax. The whiskers have diameter about 0.02 mm and length about 0.5 mm. The specific resistance of CrO2 is about 0.02 O m. The composites comprise randomly oriented inclusions and resemble the microstructure of isotropic mixtures filled with carbon black (usually acetylene soot). The composites exhibit low percolation threshold (about 10% vol.) and are conductive for direct current (DC) at higher filling. The samples are shaped either by pressing as parallelepipeds with the dimensions fitted to a standard 10 23 mm rectangular waveguide, or by molding in form of a 10 mm sphere. The spherical samples are made for measurements at 50 MHz. They contain 30% vol. of CrO2 and have specific resistance of about 1 O m. The rectangular samples contain 20% of CrO2 and exhibit approximately 100 times higher resistance. The microwave permittivity e0 ie00 and permeability m0 im00 are determined by parametric reconstruction of e and m frequency dispersions from the scalar reflectivity spectrum measured of a sample shorted through known air gap [4]. The reflectivity measurements are made in a rectangular waveguide in the frequency range from 8 to 12 GHz. The quasistatic permeability m0 is measured at 50 MHz with a multiloop coil via the Q-meter technique. The magnetic bias varies in the range of 73 kOe and can be applied either parallel or perpendicular to the highfrequency magnetic field. 3. Experimental results and discussion The measurements at 50 MHz reveal the hysteretic behavior of permeability for both parallel and perpendicular bias directions (see Fig. 1). The effect of 3 kOe perpendicular bias is small: the susceptibility response is less than 5%. The parallel bias of the same 3 kOe strength saturates the sample and makes it practically impermeable with mdiffE1. The permeability difference between the degaussed and magnetized samples (i.e., the effect of remanence) is about
-2
0 H [kOe]
2
Fig. 1. Quasistatic permeability m0 as a function of bias strength for parallel and perpendicular bias directions (solid and dashed lines, respectively). Gray and black lines correspond to the bias sweep pointed by gray and black arrows.
3%. When bias is about coercive field (about 500 Oe), the difference in permeability between magnetizing and demagnetizing bias sweep is about 0.1. This difference is much lower than that expected from the static hysteresis loop [3]. The hysteresis loop at 50 MHz is flatter than the static one, and the differential permeability mdiff drops with increasing frequency until reaching the value of initial permeability. The hysteretic behavior of permeability should disappear at microwaves because the parallel bias results in decrease of the intensity of FMR line and the perpendicular bias results in increase of FMR frequency. Both effects are not inertial, as the contribution of domain wall motion is small at microwaves. However the reflectivity measurements at 10 GHz reveal the hysteretic behavior for both orientations of the bias field (see Fig. 2). The reason of the phenomenon is that the domain structure (the magnetic texture of a composite) is biasdependent and the parameters of FMR line do depend on this structure. When the increasing bias reaches the coercive field value, it switches the magnetic moments of domains. If the bias is parallel, then the reversing moments take the intermediate position that is perpendicular to the high-frequency magnetic field. This position corresponds to the maximal quasistatic permeability and to the maximal intensity of FMR line. If the bias field is decreasing, then the magnetic moments remain parallel to the high-frequency magnetic field and the quasistatic permeability is low. If the bias is increasing and perpendicular, then the effect is inverse: a part of switching moments takes the position parallel to highfrequency magnetic field that corresponds to the minimal quasistatic permeability, while the decreasing bias corre-
ARTICLE IN PRESS S.N. Starostenko et al. / Journal of Magnetism and Magnetic Materials 300 (2006) e70–e73
e72
40
-4
30
R [dB]
permittivity ε'-, ε''- -
-8
-12
20
10
-16 -2
0
2 0
H [kOe]
7
Fig. 2. The reflectivity of 1.5-mm-thick CrO2 composite sample shorted through 15 mm air gap as a function of bias strength for the parallel bias (solid lines) and for the perpendicular bias (dashed lines). Gray and black lines correspond to the direction of bias sweep indicated by the gray and black arrows.
9
10 11 frequency [GHz]
12
13
12
13
1.5
permeability µ' -, µ''- -
sponds to high permeability values. This portion of magnetic moments is at least twice smaller than that in the case of parallel bias, thus the effect is weaker. This is the very reason of the hysteretic behavior of differential permeability under perpendicular bias shown in Fig. 1 and of the hysteretic reflectivity curves in Fig. 2. The perpendicular bias affects both m0 and Frez, hence its total effect on absorption line is higher than that of the parallel bias. Since the intermediate position of magnetic moments is unstable, the phenomenon difficult to observe in measurements under fixed bias fields. The microwave measurements of degaussed samples reveal (see Fig. 3) the X-band line of magnetic absorption that is sharp relative to the absorption in ferrites or carbonyl iron. The parameters of the line correlate with FMR data [5]. The average X-band permeability of CrO2filled composite is close to that of composite equally filled with carbonyl iron (mE1i 0.4), while the permittivity is close to that of mixtures with carbon black (eE35i 8) [6]. A medium bias (p1 kOe) applied parallel to the long side of a waveguide has low effect on the magnetic spectrum. The 3 kOe bias transforms the Lorenzian FMR line into an asymmetric line, where the absorption stretches towards high-frequency and steeply falls below 8 GHz (see Fig. 3). Since the sample is resistive, the dielectric spectrum is a complicated multiline one. The dielectric absorption is located mainly beyond the experimental frequency band: the absorption arising due to DC conductivity is appears at lower frequency; the absorption attributed to resonance on whisker length appears at higher frequency. As a result the
8
1
0.5
0 7
8
9
10
11
frequency [GHz] Fig. 3. The permittivity and permeability spectra of a sample filled with 20% vol of CrO2. The black lines correspond to zero bias; the light gray lines correspond to 3 kOe bias parallel to magnetic vector, i.e., to the short side of the waveguide; the dark gray lines correspond to 3 kOe bias perpendicular to magnetic vector.
reconstructed permittivity dispersion is weak. The 3 kOe bias parallel to the short side of a waveguide saturates the sample which becomes impermeable. For low-coercive magnetic materials the saturating bias can be low enough to suit the practical applications. An unexpected observation is that this transformation is accompanied by significant permittivity change, similarly
ARTICLE IN PRESS S.N. Starostenko et al. / Journal of Magnetism and Magnetic Materials 300 (2006) e70–e73
to the bias effect on permittivity of composites with magnetic fibers [1]. The permittivity decrease correlates with DC measurements under bias: the mixture with 20% vol. of CrO2 exhibits magnetoimpedance coefficient about 100 times higher than that of the bulk CrO2 [3]. The coefficient is positive for the bias perpendicular to electric field and negative for the parallel bias. The coefficient drops drastically with filling increase. In a composite the effect is amplified relative to bulk CrO2 by magnetostatic interaction of neighboring inclusions. The effect should be maximal at the percolation threshold. 4. Conclusion The measurements reveal the hysteresis of microwave permeability of composites filled with CrO2. The hysteresis is attributed to switching of magnetic texture under bias equal to the coercive field. Within the X-waveband the composites under study are as effective absorbers as that filled with carbonyl iron. If the wideband absorbing performance is considered the CrO2-filled composites behave like soot-filled materials (composites with carbon black). The magnetic control of microwave permeability of
e73
CrO2-filled samples requires high bias strength (about 3 kOe) for arbitrary bias direction that is unfeasible for practice. At the percolation threshold the permittivity of composite may be sensitive to magnetic bias enough to suit the needs of practical applications.
Acknowledgments The work is partially supported by the Russian Foundation for Basic Research, Grant No 05-08-01212.
References [1] S.N. Starostenko, K.N. Rozanov, A.V. Osipov, J. Magn. Magn. Mater. 298 (1) (2006) 56. [2] R.M. Bozorth, Ferromagnetism, IEEE Press, New York, 1993. [3] J. Dai, J. Tang, Phys. Rev. B 63 (2000) 54434. [4] S.N. Starostenko, A.P. Vinogradov, IEEE Trans. Instrum. Meas. 51 (1) (2002) 125. [5] B. Rameev, A. Gupta, G. Miao, Solid State Phys. A 201 (15) (2004) 3350. [6] J.C. Martin, J.M. Fornies-Marquina, A.M. Bottreau, Mol. Phys. 101 (2003) 1789.