SUBSTITUTED BARIUM TITANATE AND BARIUM STRONTIUM TITANATE FERROELECTRIC COMPOSITIONS

Abstract: This invention provides the three novel La,Fe, La,Cr and Sm,Fe substituted barium titanate solid solution ferroelectric compositions with the formula Ba1-xLnxTi1-xMxO3 wherein when Ln is La, M is Fe or Cr, when Ln is Sm, M is Fe and x is from about 0.02 to about 0.06 and mixtures thereof, the novel La,Fe substituted barium strontium titanate solid solution ferroelectric compositions with the formula (Ba1-ySry)1-xLaxTi1-xFexO3 wherein y is greater than zero and less than about 0.6 and x is from about 0.01 to about 0.06 and the novel La,Al substituted barium strontium titanate solid solution ferroelectric compositions with the formula (Ba1-ySry)1-xLaxTi1-x/4-3a/4Alca(x-a)/4O3 wherein c denotes a vacancy, y is greater than zero and less than about 0.6, a is from about 0.01 to about 0.06 and x is from 0.02 to about 0.10 with the proviso that x is greater than or equal to a.These low loss tunable ferroelectric compositions are especially useful in tunable microwave thin film devices which fall into three types: interdigital and trilayer capacitors, coplanar waveguides and microstrips.

Description: TITLE SUBSTITUTED BARIUM TITANATE AND BARIUM STRONTIUM TITANATE FERROELECTRIC COMPOSITIONS FIELD OF THE INVENTION This invention relates to La,Fe, La,Cr and Sm,Fe substituted barium titanate and La,Fe and La,Al substituted barium strontium titanate ferroelectric compositions that have useful dielectric properties. BACKGROUND OF THE INVENTION The use of dielectric materials to increase capacitance is well-known. Earlier capacitor dielectrics fell into two categories. The first category of dielectrics has a relatively temperature-independent dielectric constant but the value of the dielectric constant is low, e.g., 5-10. Materials such as electrical porcelain and mica fall in this category. The second category of dielectrics has very high dielectric constant, e.g., 1000 or more, but they are quite temperature dependent. ■ An example is barium titanate, BaTiO 3 . Since capacitance of a dielectric material is proportional to its dielectric constant, high dielectric constant materials are desired. In order to perform acceptably in tuning or resonance circuits, the dielectric must also have a dielectric constant that exhibits minimal temperature dependence; otherwise, small changes in ambient temperature will throw the circuit out of resonance. Other applications require a ■ dielectric constant that exhibits minimal frequency dependence. It is also desirable to have the loss or dissipation factor as small as possible. For many microwave devices, the important material features are the dielectric tunability, i.e., the change in dielectric constant with applied voltage, and low dielectric loss. Barium strontium titanate, Ba^xSr^TiOs, has been used in some such applications (see US5427998), but the need persists for materials with better properties. Ismailzade et al., Phvs. Stat. Sol, fa), 59, K191 (1980), studies the ferroelectric transitions of the system (l-x)BaTiθ 3 _ x BiFeO 3 (x = 0.05 and 0.08) and reported transition temperatures of 106°C and 85°C, respectively. Hagemann et al., J. Amer. Ceramic Soc, 64 (10) 590 (1981), studied the defect chemistry of BaTiO 3 doped with acceptors Cr, Mn, Fe, Co and Ni. They note that conventional titanate formulations usually contain donor dopants like Nb or La, requiring that sintering and all subsequent high temperature treatments be performed at high partial pressure of oxygen. Inoue et al., Jpn. J. Appl. Phvs.. 30 (9B), 2388 (1991), measured the dielectric constant and losses in BaTiO 3 ceramics doped with acceptors Fe, Ni, Cu and Nb. Skapin et al., J. Solid State Chem.. 129, 223 (1997) found that the solid (Ba,La)(Ti,Al)O 3 exhibits relatively low permittivities and very low dielectric losses. Sengupta et al., Mat. Res. Innovat, 2, 278 (1999), investigate the effects of acceptor and donor doping on the electronic properties of barium strontium titanate thin films by doping with 1 mole% of Mg, La, Ta and Al. They state that MgO doping produced the best effect on lowering the loss tangents at microwave frequencies while maintaining tunability. Sengupta et al., US5427988, disclose ceramic ferroelectric composite material consisting essentially of barium strontium titanate, Ba^ x Sr x TiOs, wherein x is greater than 0.0 and less than or equal to 0.75, and magnesium oxide, MgO, in amounts to provide a composite having a low dielectric constant, low loss tangent and high tunability. Their preferred weight ratio of Baι_ x Sr x TiO 3 to MgO ranges from approximately 99%-40% Ba ! . x Sr 3 χTiO to l%-60% MgO. Yandrofski et al., U.S. 5,472,935, disclose tuneable microwave devices incorporating tuneable ferroelectrics. SUMMARY OF THE INVENTION This invention provides the three novel La,Fe, La,Cr and Sm,Fe substituted barium titanate solid solution ferroelectric compositions with the formula Ba xLn x Tii. x MxOs wherein when Ln is La, M is Fe or Cr, when Ln is Sm, M is Fe and x is from about 0.02 to about 0.06 and mixtures thereof. Preferably, x is from about 0.03 to about 0.05. Most preferred is x = 0.04. This invention also provides novel La,Fe and La,Al substituted barium strontium titanate solid solution ferroelectric compositions. The La,Fe substituted composition has the formula (Baι_ y Sr y )ι_χLa x Tiι_χFeχθ 3 wherein y is greater than zero and less than about 0.6 and x is from about 0.01 to about 0.06. Preferably, y is from about 0.2 to about 0.5 and x is from about 0.03 to about 0.05. Most preferred is y about 0.4 and x = 0.04. The La,Al substituted composition has the formula (Ba 1 . y Sr y )ι.χLa x Tiι.χ /4 - 3aΛ |Al a D (x - a)/4 θ 3 wherein □ denotes a vacancy, y is greater than zero and less than about 0.6, a is from about 0.01 to about 0.06 and x is from 0.02 to about 0.10 with the proviso that x is greater than or equal to a. Preferably, y is from about 0.2 to about 0.5, a is from about 0.01 to about 0.04 and x is from about 0.03 to about 0.10. Most preferred is the composition with y about 0.4, a = 0.02 and x = 0.06. These low loss tunable ferroelectric compositions are especially useful in tunable microwave thin film devices devices which are tuneable as a result of the use of these ferroelectric compositions. Such devices fall into three types: interdigital and trilayer capacitors, coplanar waveguides and microstrips. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The solid solution ferroelectric oxide compositions of this invention have dielectric properties that provide advantages in tunable microwave devices over the commonly used Bao .δ Sro. 4 Tiθ 3 . Baj_ x Ln x Tiι_χM x θ 3 compositions can be synthesized by the following procedure. Stoichiometric amounts of the precursors are thoroughly mixed. The precursors BaTiO 3 , Ln 2 O 3 and M 2 O 3 are preferred. The mixed precursor powder is calcined at about 1000°C for about 8 hours. The calcined powder is reground and pressed to 12.7 mm diameter/1-2 mm thick disks. The disks are sintered in air at about 1275°C for 20 hours. In both the calcining and sintering steps, the temperature ramping up rate is about 200°C/hour from room temperature, i.e., about 20°C, to the calcining or sintering temperature and the cooling rate is about 150°C/hour from the calcining or sintering temperature to room temperature, i.e., about 20°C . (Ba 1 . y Sr y ) 1 . x LaχTi 1 . x FeχO 3 and (Ba 1 . y Sr y )ι. x La x Tiι.χ /4 _ 3a/4 Al a D ( χ- a ) /4 θ 3 compositions can be synthesized by the following procedure. Stoichiometric amounts of the precursors are thoroughly mixed. The precursors BaTiU 3 , SrCO 3 , TiO 2 , La 2 O 3 and Fe 2 O 3 or Al 2 O 3 respectively are preferred. The mixed precursor powder is calcined at about 1000°C for about 8 hours. The calcined powder is reground and pressed to 12.7 mm diameter/1-2 mm thick disks. The disks are sintered in air at about 1325°C for 20 hours. In both the calcining and sintering steps, the temperature ramping up rate is about 200°C/hour from room temperature, i.e., about 20°C, to the calcining or sintering temperature and the cooling rate is about 150°C/hour from the calcining or sintering temperature to room temperature, i.e., about 20°C . All of the substituted compositions of the invention crystallize in a pseudo-cubic or cubic perovskite related structure. Dielectric measurements were carried out on the disk samples. The faces of the disk-shaped samples were polished with a fine-grit sand or emery paper to produce flat uniform surfaces. Silver paint electrodes were applied on the faces and dried at 200°C. The capacitance and the dielectric loss measurements were performed by the two-terminal method using a Hewlett-Packard 4275A LCR bridge at room temperature, about 20°C, and at a frequency of 1 MHz and the capacitance, C, and the dissipation factor are read directly from the bridge. Below room temperature, a Hewlett-Packard 4284A LCR bridge was used. The dielectric constant (K) was calculated from the measured capacitance, C in picofarads, from the relationship, K = (100 C t)/(8.854 A), where t is thickness of the disk shaped sample in cm and A is the area of the electrode in cm2. Voltages of up to 100 Volts were applied across the flat electroded faces of the disks using a Keithley 228A voltage/current source and tunability was calculated by measuring the change in dielectric constant with applied voltage. The tunability, T, is calculated from the equation T = [K(0) - K(V)] / K(0)] where K(0) is the dielectric constant when there is no applied voltage and K(V) is the dielectric constant when there is an applied voltage V. The tunability is usually expressed as a percent for a given applied electric field so that the above result for T is multiplied by 100 or it is written as T = (constant) E where T is the tunability in %, E is the electric field and the constant is characteristic of the particular material. EXAMPLES OF THE INVENTION EXAMPLES 1-3. COMPARATIVE EXPERIMENTS A-G Bao.96Lao.04Tio.96Feo.04O3, Bao.96Smo.04 io.96Feo.04O3 and Bao. 96 Lao. 04 Tio. 96 Cro. 04 O 3 are the solid solution ferroelectric oxide compositions of Examples 1-3 respectively. Bai. x LnxTi^ x MxOs, wherein when Ln is Gd, Dy or Bi, M is Fe, when Ln is La, M is Al or Ga, and x is 0.04, are the solid solution oxide compositions of Comparative Experiments A-E. Solid solution oxide of the formula Baι_ x Ln 3+ x Tiι.χM 3+ χθ 3 , wherein Ln=La, Sm, Gd, Bi and M=A1, Ga, Fe, Cr, were prepared by the following procedure. Appropriate amounts of starting oxides BaTiθ 3 , Ln 2 O 3 and M 2 O 3 were weighed according to the stoichiometric ratios and mixed thoroughly in an agate mortar. The gram amounts of the precursors used in each instance are shown in Table 1. Table 1 Ex. or Composition Precursor! 5 Comp. BaTiO 3 (g) Fe 2 O 3 (g) Ln 2 O 3 (g) 1 Ba .96 La. 04 Ti. 96 Fe. 04 O 3 1.4376 0.0205 0.0418, Ln=La 2 Ba. 96 Sm. 04 Ti. 96 Fe. 04 O 3 1.4348 0.0204 0.0446, Ln=Sm A Ba .96 Gd. 04 Ti. 96 Fe. 04 O 3 1.4331 0.0204 0.0464, Ln=Gd B Ba. 96 Dy. 04 Ti. 96 Fe .04 O 3 1.4318 0.0204 0.0477, Ln=Dy C Ba. 96 Bi. 04 Ti. 96 Fe .04 O 3 1.4206 0.0591 0.0202, Ln=Bi BaTiO 3 (g) La 2 O 3 (g) M2O3 (g) D Ba. 96 La. 04 Ti. 96 Al. 04 O 3 1.4447 0.042 0.0131, M=A1 E Ba 96 La. 04 Ti. 96 Ga. 04 O 3 1.4342 0.0417 0.024, M=Ga 3 Ba. 9 La 04 Ti. 96 Cr .04 O 3 1.4385 0.0418 0.0195, M=Cr BaCO 3 (g) SrCO 3 (g) TiO 2 (g) F BaTiO 3 1.3539 - 0.548 G Ba 0 . 6 Sr 0 . 4 TiO 3 0.8325 0.4152 0.5616 The mixed powder of each Example was calcined at 1000°C for 8 hours. The calcined powder was reground and pressed to 12.7 mm dia 1-2 mm thick disks. The disks were sintered in air at 1275°C for 20 hours. In both the calcining and sintering steps, the temperature was increased from room temperature, i.e., about 20°C, to the calcining or sintering temperature at a rate of 200°C/hour and the temperature was decreased from the calcining or sintering temperature to room temperature, i.e., about 20°C, at a rate of 150°C/hour. Samples of BaTiθ 3 and Bao. 6 Sro. 4 Tiθ 3 were prepared for Comparative Experiments F and G using the precursors BaCO 3 , SrCO 3 and TiO 2 in the amounts shown in Table 1. The mixed powder was pressed to 12.7 mm dia/1-2 mm thick disks. The disks were sintered in air at 1450°C for 20 hours in the case of BaTiO 3 and at 1350°C for 20 hours in the case of Ba 0 . 6 Sr 0 . 4 TiO 3 . The temperature was increased from room temperature, i.e., about 20°C, to the sintering temperature at a rate of 200°C/hour and the temperature was decreased from the sintering temperature to room temperature, i.e., about 20°C, at a rate of 150°C/hour. X-ray powder diffraction patterns were recorded for each sample with a Siemens D5000 diffractometer. The data showed all the samples crystallized in a pseudo-cubic or cubic perovskite related structure and the lattice parameters are given in Table 2. Table 2 Example or Cubic Lattice Comparative : Experiment Parameter (nm) (±0.0003) 1 0.3999 2 0.4002 A 0.4000* B 0.4001* C 0.4011 D 0.4002 E 0.3998 3 0.4000 F 0.4009* G 0.3965 pseudo-cubic cell value. The disk samples were polished to produce flat uniform surfaces and the two flat surfaces were painted with silver paint to provide electrodes. The painted samples were dried at 70-100°C overnight. Capacitance and loss tangent measurements were taken on a HP-4275A LCR meter at room temperature, i.e., about 20°C, at a frequency of 1 MHz. Voltages up to 100V were applied across the flat electroded faces of the disks using an Keithley 228 A voltage/current source and the dielectric constant was measured as a function of applied voltage. The dielectric constant with no voltage applied, the loss tangent, the percent tunability and the applied electric filed to obtain that magnitude tunability are shown in Table 3. Measurements were carried out at room temperature, i.e., about 20°C, and at a frequency of 1 MHz. Table 3 Example or Comparative Dielectric Loss Tunability Electric Experiment Constant Tangent (Percent) Field (V/μm) 1 4350 0.0130 4.2 0.053 2 1857 0.0180 1.2 0.061 A 929 0.0309 1.2 0.063 B 525 0.0225 0 0.064 C 637.3 0.0156 0.6 0.066 D 1713 0.0127 0.8 0.073 E 1461 0.0111 0.2 0.073 3 536 0.0060 1.6 0.059 F 1195 0.0080 0 0.077 G 2551 0.0115 2.7 0.060 The tunability equation written in the form T = (constant) E is given in Table 4 for each Example and Comparative Experiment. Measurements were carried out at room temperature, i.e., about 20°C, and at a frequency of 1 MHz. Table 4 Example or Tunability Equation Comparative Experiment (T: tunability in %, E: electric field in V/μm) 1 T = 74.3 E 2 T = 21.0 E A Frequency dependent, tetragonal B No tuning C T = -10.6 E D T = 11.4 E E T = 2.6 E 3 T = 27.2 E F No tuning G T = 38.4 x (E) The results show that the composition Bao 9ό Lao o 4 Tio 9δ Feo 04 O 3 has a tunability of nearly twice that of Bao eSro 4 ΗO 3 along with a somewhat higher dielectric constant and a comparable dielectric loss. Bao 9δ Smo o 4 Tio 9ό Feo 04 O 3 has a tunability of about half that of Bao βSro 4 ΗO 3 along with a somewhat lower dielectric constant and a comparable dielectric loss. Bao 96 Lao o 4 Tio 9δ Cro 04 O 3 has a dielectric loss of about half, a dielectric constant about 1/5 and a tunability of about 7/10 that of Ba 0 6 Sr 0 4 TiO 3 . EXAMPLES 4-12, COMPARATIVE EXPERIMENTS H-K The compositions with the formula (Baι- y Sr y )o. 96 Lao.o 4 Ti 0 . 96 Feo.o 4 O 3 , alternatively written as (Baι- y Sr y )TiQ 3 : 4%La4%Fe, with y = 0.2, 0.4 and 0.6 are the solid solution ferroelectric oxide compositions of Examples 4, 5 and 6, respectively. The compositions with the formula (Ba 1 _ y Sr y )o. 96 La 0 .o 4 Tio. 96 Alo.o 4 O 3 , alternatively written as (Ba 1 . y Sr y )TiO 3 :4%La4%Al, with y = 0.2, 0.4 and 0.6 are the solid solution ferroelectric oxide compositions of Examples 7, 8 and 9, respectively. The compositions with the formula (Ba 1 . y Sr y )o. 4 Lao. 06 Tio. 97 Al 0 .o 2 Q 0 . 01 O 3 , alternatively written as (Ba 1 .ySr y )TiO 3 :6%La2%Al, with y = 0.2, 0.4 and 0.6 are the solid solution ferroelectric oxide compositions of Examples 10, 11 and 12, respectively. The solid solution oxides were prepared by the following procedure. Appropriate amounts of starting oxides BaTiO 3 , SrCO 3 , TiO 2 , La 2 O 3 , AI 2 O 3 and Fe 2 O 3 were weighed according to the stoichiometric ratios and mixed thoroughly in an agate mortar. The gram amounts of the precursors used in each instance are shown in Table 5. Table 5 Samples of barium strontium titanate were prepared as Comparative Experiments H-K using appropriate amounts of the precursors BaTiO 3 , SrCO 3 and TiO 2 which were weighed according to the stoichiometric ratios and mixed thoroughly in an agate mortar. The gram amounts of the precursors used in each instance are shown in Table 5. The mixed powder of each Example and Comparative Experiment was calcined at 1000°C for 8 hours. The calcined powder was reground and pressed to 12.7 mm dia/1-2 mm thick disks. The disks were sintered in air at 1325°C for 20 hours. In both the calcining and sintering steps, the temperature was increased from room temperature, i.e., about 20°C, to the calcining or sintering temperature at a rate of 200°C/hour and the temperature was decreased from the calcining or sintering temperature to room temperature, i.e., about 20°C, at a rate of 150°C/hour. X-ray powder diffraction patterns were recorded with a Siemens D5000 diffractometer. The data showed all the samples were crystallized in a pseudo- cubic or cubic perovskite related structure and the lattice parameters are given in Table 6. There are obvious BaAl 2 O 4 impurities in 4%La4%Al doped samples. The presence of this impurity is minimal in the 6%La2%Al doped samples. The disk samples were polished to produce flat uniform surfaces and the two flat surfaces were painted with silver paint to provide electrodes. The painted samples were dried at 70-100°C overnight. Capacitance and loss tangent measurements were taken on a HP-4275A LCR meter at room temperature. Voltage up to 100V was applied to the sample by Keithley 228A voltage/current source. Measurements were carried out at room temperature, i.e., about 20°C, and at a frequency of of 1 MHz. Results for the dielectric constants, loss tangents, and tunability equations for the samples are given in Table 6. Table 6 Tunability, T = [ε (v=0) - ε (v≠O)] / ε (v=0)] # pseudo-cubic cell value. The sample of Example 4, Bao. 8 Sr 0 . 2 TiO 3 : 4%La4%Fe has a tunability comparable to that of Comparative Experiment I sample of Bao. 6 Sr 0 . 4 TiO 3 . The Al-doped samples show low loss. The pure barium strontium titanate samples remain tetragonal up to about the composition of Comparative Experiment I, Bao. 6 Sro .4 TiO 3 . The doped samples are all cubic at room temperature. The substitution of La,Al and La,Fe lowers the Curie temperature of Bao .8 Sro. 2 TiO . The three phase transitions areas for the unsubstututed barium strontium titatante are spread into one for the La,Al and La,Fe substituted samples. La,Al substitution shows a larger decrease in the Curie temperature. La,Al substituted Bao. 6 Sro .4 TiO shows the transition peak around 80K. Substitution also changes the loss tangent. The loss tangents of La,Al substituted samples were lower than that of the unsubstututed samples, especially close to room temperature. The La,Fe substituted samples show lower loss in the low temperature region. However the La,Fe substitution results in the substituted composition being a semiconductor and so the loss tangents at room temperature are higher. The typical barium strontium titanate Ba x Sr^TiOs used at cryogenic temperatures, e.g., 80K, has low barium content with x less than 0.1. The properties of low Ba content samples are more dependent on the substrate and therefore higher Ba content would be advantageous. The substituted compositions of this invention and particularly the Bao. 6 Sr 0 . 4 TiO 3 : 6%La, 2%A1 sample shows the best effect on increasing tunability of higher Ba content samples at 80K and has a tunability comparable to that of Bao .2 Sr 0 . 8 TiO 3 . The effects of 4%La4%Al and 4%La4%Fe codoping are weaker. This might be caused by the impurity of BaAl 2 O 4 in the 4%La4%Al sample and the lower loss in La, Fe substituted sample at low temperature. The selected equations of some of the samples at 80K are shown in Table 7. Table 7: Tunability at 80K

Claims: What is claimed is: I . A ferroelectric composition chosen from the group consisting of the solid solutions with the formulas Bai.xLaxTii-xFexOs.Bai-xLa x Tii-xCr x O^Ba ! . xSmxTi^xFe x Os or mixtures thereof, wherein x is from about 0.02 to about 0.06. 2. The ferroelectric composition of Claim 1 wherein x is from about 0.03 to about 0.05. 3. The ferroelectric composition of Claim 2 wherein x is 0.04. 4. A fereoelectric composition with the formula (Baι_ y Sr y )ι_ x La x Tiι_ x Fe x θ3 wherein y is greater than zero and less than about 0.6 and x is from about 0.01 to about 0.06. 5. The fereoelectric composition of Claim 4 wherein y is from about 0.2 to about 0.5 and x is from about 0.03 to about 0.05. 6. The ferroelectric composition of Claim 5 wherein y is about 0.4 and x = 0.04. 7. A fereoelectric composition with the formula (Baι. y Sr y )ι. x La x Ti].χ / 4 -3a / 4Al a D ( χ- a ) /4 θ3 wherein Q denotes a vacancy, y is greater than zero and less than about 0.6, a is from about 0.01 to about 0.06 and x is from 0.02 to about 0.10 with the proviso that x is greater than or equal to a. 8. The ferroelectric composition of Claim 7 wherein y is from about 0.2 to about 0.5, a is from about 0.01 to about 0.04 and x is from about 0.03 to about 0.10. 9. The ferroelectric composition of Claim 8 wherein y is about 0.4, a = 0.02 and x = 0.06. 10. A tunable microwave thin film device comprising a ferroelectric composition chosen from the group consisting of the solid solutions with the formulas Baι. x La x Tij.χCr x θ3, Ba xSm x Ti xFexOs or mixtures thereof, wherein x is 0.02 to about 0.06. I I . The tunable microwave thin film device of Claim 10 wherein x is from about 0.03 to about 0.05. 12. The tunable microwave thin film device of Claim 11 wherein x is 0.04. 13. A tunable microwave thin film device comprising a ferroelectric composition with the formula (Baι_ y Sr y )ι. x La x Tiι_ x Fe x θ3 wherein y is greater than zero and less than about 0.6 and x is from about 0.01 to about 0.06. 14. The tunable microwave thin film device of Claiml 3 wherein y is from about 0.2 to about 0.5 and x is from about 0.03 to about 0.05. 15. The tunable microwave thin film device of Claim 14 wherein y is about 0.4 and x = 0.04. 16. A tunable microwave thin film device comprising a fereoelectric composition with the formula (Bai -ySry) 1 -xLaxTi 1 -x/4 -3 a/4Al a (x-a)/4O wherein denotes a vacancy, y is greater than zero and less than about 0.6, a is from about 0.01 to about 0.06 and x is from 0.02 to about 0.10 with the proviso that x is greater than or equal to a. 17. The tunable microwave thin film device of Claim 16 wherein y is from about 0.2 to about 0.5, a is from about 0.01 to about 0.04 and x is from about 0.03 to about 0.10. 18. The tunable microwave thin film device of Claim 17 wherein y is about 0.4, a = 0.02 and x = 0.06.

Inventors: LI DONG, SUBRAMANIAN MUNIRPALLAM APPADO, LI, DONG, SUBRAMANIAN, MUNIRPALLAM, APPADORAI
Applicants: DU PONT, LI DONG, SUBRAMANIAN MUNIRPALLAM APPADO, E.I. DU PONT DE NEMOURS AND COMPANY, LI, DONG, SUBRAMANIAN, MUNIRPALLAM, APPADORAI
Application year: 2001
Main classification: C04B35
IPC codes: C04B35, H01B3, H01P1, H01P3