CN111704460B - MgTiO for NP0 type MLCC 3 Base radio frequency ceramic powder and preparation method thereof - Google Patents
MgTiO for NP0 type MLCC 3 Base radio frequency ceramic powder and preparation method thereof Download PDFInfo
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Abstract
The invention discloses MgTiO 0 MLCC 3 Based radio frequency porcelain powder, MgTiO for NP0 type MLCC 3 The radio frequency ceramic powder comprises the following material components: a MgTiO 3 +b Mg 2 SiO 4 +c(Mg x Zn 1‑x )Al 2 O 4 +d(Ca y Sr 1‑y )(Ti z Zr 1‑z )O 3 + (1-a-b-c-d) TMs; wherein TMs is at least one of oxides or salts of Mn, Co and Zn, a is more than or equal to 0.65 and less than or equal to 0.85, b is more than or equal to 0.05 and less than or equal to 0.2, c is more than or equal to 0.07 and less than or equal to 0.25, d is more than or equal to 0.01 and less than or equal to 0.05, x is more than or equal to 0.1 and less than or equal to 0.9, y is more than or equal to 0.2 and less than or equal to 0.8, and z is more than or equal to 0.8 and less than or equal to 1. Meanwhile, the invention also discloses a preparation method of the NP0 type ceramic powder for MLCC.
Description
Technical Field
The invention belongs to the technical field of microwave dielectric materials, and particularly relates to MgTiO for NP0 type MLCC 3 A base radio frequency porcelain powder and a preparation method thereof.
Background
The information functional ceramic becomes a key basic material of a plurality of novel electronic components due to excellent performance, is widely applied to the fields of electronic information, communication technology, integrated circuits, aerospace and the like, and plays an important strategic position in national economy and national defense construction. With the development of surface mounting technology, almost all components have corresponding chip components, and strong requirements are put forward on miniaturization and high reliability of the chip components in some electronic equipment with special requirements such as military mobile communication, police pocket-sized electric bells, military computers and the like. The radio frequency MLCC device is widely applied to military and civil complete machine oscillation, coupling, filtering and bypass circuits due to the characteristics of small volume, light weight, stable performance, high reliability and the like. In addition, with the development of millimeter wave technology, the use of radio frequency MLCCs in the military and civilian fields will be more and more prominent. The radio frequency ceramic powder has the characteristics of low loss, good frequency and temperature stability, good insulating property and the like, and is a key base material for realizing high reliability of the radio frequency MLCC.
MgTiO 3 Has the characteristics of small dielectric loss, small temperature coefficient of dielectric constant (tau epsilon) and temperature coefficient of frequency (tau f), rich raw materials and low price, and is a class of products with excellent performance and applicationThe sintering temperature of the wide radio frequency MLCC material is higher (more than 1350 ℃), the sintering temperature zone is narrow, the sintering condition is difficult to control in practical application, and the pure MgTiO material with excellent comprehensive performance is difficult to prepare 3 A ceramic. Patent CN102964121A discloses that in MgTiO 3 Adding Mg 2 SiO 4 And Mn, Co, Nb and Al oxides are added to reduce dielectric loss, and glass powder is further added to reduce sintering temperature, so that microwave ceramic powder with a Qxf value higher than 100000 is obtained, but the sintering aid adopts glass, the preparation process is complex, and the material cost is increased to a certain extent. Patent CN103588477A discloses MgTiO 3 -CaAlTiO 3 The system is microwave ceramic powder, the Q multiplied by f value is close to 60000, but the sintering temperature is higher (> 1350 ℃). Therefore, how to prepare MgTiO with good performance at lower temperature and wider temperature range 3 Microwave-based porcelain powders have been the focus of attention in the industry.
Disclosure of Invention
Based on the above, the invention aims to overcome the defects of the prior art and provide MgTiO 0 type MLCC for the NP0 type MLCC 3 The material has the characteristics of low sintering temperature, low loss and nearly zero temperature coefficient of dielectric constant.
In order to realize the purpose, the technical scheme adopted by the invention is as follows: MgTiO for NP0 type MLCC 3 Based radio frequency porcelain powder, MgTiO for NP0 type MLCC 3 The radio frequency ceramic powder comprises the following material components: alpha MgTiO 3 +b Mg 2 SiO 4 +c(Mg x Zn 1-x )Al 2 O 4 +d(Ca y Sr 1-y )(Ti z Zr 1-z )O 3 + (1-a-b-c-d) TMs; wherein TMs is at least one of oxides or salts of Mn, Co and Zn, a is more than or equal to 0.65 and less than or equal to 0.85, b is more than or equal to 0.05 and less than or equal to 0.2, c is more than or equal to 0.07 and less than or equal to 0.25, d is more than or equal to 0.01 and less than or equal to 0.05, x is more than or equal to 0.1 and less than or equal to 0.9, y is more than or equal to 0.2 and less than or equal to 0.8, and z is more than or equal to 0.8 and less than or equal to 1.
MgTiO for NP0 type MLCC described in the present application 3 In the radio frequency ceramic powder, all components interact with each other, and the Q value of the ceramic powder can be improved and the temperature coefficient (tau) of the dielectric constant can be adjusted by adjusting the proportion of the components ε ) Near zero; wherein, MgTiO 3 Has high Q value characteristic and is used as a main materialThe material loss can be kept low; mg (magnesium) 2 SiO 4 The ceramic material has low dielectric loss and certain sintering aiding performance, and can reduce the system loss, reduce the sintering temperature and improve the density after being added; (Mg) x Zn 1-x )Al 2 O 4 The dielectric loss is low, the abnormal growth of crystal grains can be inhibited by adding the dielectric loss, and a ceramic sample with uniform crystal grain size is obtained, so that the loss of a system is reduced; (Ca) y Sr 1-y )(Ti z Zr 1-z )O 3 τ of ε Negative values, adding adjustable systems τ ε Near zero; in addition, the addition of oxides or salts of Mn, Co and Zn can further reduce the dielectric loss of the system and the sintering temperature, and the NP0 type MLCC ceramic powder with good comprehensive performance is obtained.
Meanwhile, the invention also provides MgTiO 0 for the MLCC 3 The preparation method of the base radio frequency ceramic powder comprises the following steps:
(1) MgTiO according to the stoichiometric ratio 3 Weighing raw materials, pouring the weighed raw materials into a ball milling tank, adding zirconia balls and deionized water, ball milling for 4-12h, taking out, drying, calcining the dried powder at 950-1150 ℃, preserving heat for 3-6h, cooling to room temperature to obtain MgTiO 3 Powder;
(2) according to stoichiometric ratio Mg 2 SiO 4 Weighing raw materials, pouring the weighed raw materials into a ball milling tank, adding zirconia balls and deionized water, carrying out planetary ball milling for 4-12h, taking out, drying, calcining the dried powder at 1100-1250 ℃, preserving heat for 6-12h, and cooling to room temperature to obtain Mg 2 SiO 4 Powder;
(3) according to the stoichiometric ratio (Mg) x Zn 1-x )Al 2 O 4 Weighing raw materials, pouring the weighed raw materials into a ball milling tank, adding zirconia balls and deionized water, performing planetary ball milling for 4-12h, taking out, drying, calcining the dried powder at 1350- x Zn 1-x )Al 2 O 4 Powder;
(4) according to the stoichiometric ratio (Ca) y Sr 1-y )(Ti z Zr 1-z )O 3 Weighing raw materials, pouring the weighed raw materials into a ball milling tank, adding zirconia balls and deionized water, carrying out planetary ball milling for 4-12h, taking out, drying, calcining the dried powder at 1050- y Sr 1-y )(Ti z Zr 1-z )O 3 Powder;
(5) according to the proportion of a MgTiO 3 +b Mg 2 SiO 4 +c(Mg x Zn 1-x )Al 2 O 4 +d (Ca y Sr 1-y )(Ti z Zr 1-z )O 3 + (1-a-b-c-d) TMs, weighing the MgTiO 3 Powder, Mg 2 SiO 4 Powder, (Mg) x Zn 1-x )Al 2 O 4 Powder, (Ca) y Sr 1-y )(Ti z Zr 1-z )O 3 Pouring weighed raw materials into a ball milling tank, adding zirconia balls and deionized water, carrying out planetary ball milling for 4-8h, taking out, drying and crushing to obtain MgTiO 0 powder for the NP0 type MLCC 3 And (3) base radio frequency ceramic powder.
The application adopts a solid phase method to synthesize MgTiO 3 、Mg 2 SiO 4 、(Mg x Zn 1-x )Al 2 O 4 And (Ca) y Sr 1-y )(Ti z Zr 1-z )O 3 By adjusting the proportion, the Q value of the porcelain powder is improved, and the temperature coefficient (tau) of the dielectric constant is adjusted ε ) Near zero; one or more of oxides or salts of Mn, Co and Zn are added to further improve the Q value and reduce the sintering temperature, so that the low-loss NP0 type MLCC ceramic powder is obtained.
Preferably, the raw material in the step (1) is Mg (OH) 2 And TiO 2 。
Preferably, the raw material in the step (2) is Mg (OH) 2 And SiO 2 。
Preferably, the raw material in the step (3) is Mg (OH) 2 ZnO and Al 2 O 3 。
Preferably, the raw material in the step (4) is CaCO 3 、SrCO 3 、ZrO 2 And TiO 2 。
In addition, the invention also provides NP0 type MLCC microwave dielectric ceramic, and MgTiO 0 type MLCC is used by the NP0 type MLCC 3 And preparing the base radio frequency ceramic powder.
The invention also provides a preparation method of the NP0 type MLCC microwave dielectric ceramic, which comprises the following steps: MgTiO for the NP0 type MLCC 3 And adding a PVA solution into the base radio frequency porcelain powder for granulation and pressing into a cylindrical block, sintering at the temperature of 1200-1300 ℃, and preserving heat for 3-7h to obtain an NP0 type MLCC microwave medium ceramic sample.
Preferably, the PVA solution contains 7-10 wt% of PVA.
Compared with the prior art, the invention has the beneficial effects that:
the invention uses MgTiO 3 Adding low-loss Mg as main phase 2 SiO 4 、(Mg x Zn 1-x )Al 2 O 4 The dielectric loss of the system is reduced; at the same time, Mg 2 SiO 4 Has the sintering-assistant characteristic, can reduce the sintering temperature, (Mg) x Zn 1-x )Al 2 O 4 Can inhibit abnormal growth of crystal grains and obtain ceramics with uniform crystal grain size; (Ca) y Sr 1-y )(Ti z Zr 1-z )O 3 Adjustable tau ε Obtaining NP0 characteristic material; the addition of Mn, Co and Zn oxide or salt can further raise the Q value of the material and lower the sintering temperature.
MgTiO synthesis by solid phase method 3 、Mg 2 SiO 4 、(Mg x Zn 1-x )Al 2 O 4 And (Ca) y Sr 1-y )(Ti z Zr 1-z )O 3 By adjusting the proportion, the Q value of the porcelain powder is improved, and the temperature coefficient (tau) of the dielectric constant is adjusted ε ) Near zero.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to specific examples.
MgTiO for NP0 type MLCC in examples of the present application 3 The radio frequency ceramic powder comprises the following material components: a MgTiO 3 +b Mg 2 SiO 4 +c(Mg x Zn 1-x )Al 2 O 4 +d(Ca y Sr 1-y )(Ti z Zr 1-z )O 3 + (1-a-b-c-d) TMs (TMs are one or a mixture of more of oxides or salts of Mn, Co and Zn); wherein a is more than or equal to 0.65 and less than or equal to 0.85, b is more than or equal to 0.05 and less than or equal to 0.2, c is more than or equal to 0.07 and less than or equal to 0.25, d is more than or equal to 0.01 and less than or equal to 0.05, x is more than or equal to 0.1 and less than or equal to 0.9, y is more than or equal to 0.2 and less than or equal to 0.8, and z is more than or equal to 0.8 and less than or equal to 1;
MgTiO for NP0 type MLCC in examples of the present application 3 The preparation method of the base radio frequency ceramic powder comprises the following steps:
(1) MgTiO according to the stoichiometric ratio 3 Weighing Mg (OH) 2 And TiO 2 Pouring weighed raw materials into a ball milling tank, adding zirconia balls and deionized water, performing planetary ball milling for 4-12h, taking out, drying, putting the dried powder into an alumina crucible, calcining in a muffle furnace at 950 plus 1150 ℃, preserving heat for 3-6h, cooling to room temperature to obtain MgTiO 3 Powder;
(2) according to the stoichiometric ratio of Mg 2 SiO 4 Weighing Mg (OH) 2 And SiO 2 Pouring weighed raw materials into a ball milling tank, adding zirconia balls and deionized water, carrying out planetary ball milling for 4-12h, taking out, drying, putting the dried powder into an alumina crucible, calcining at the temperature of 1100-1250 ℃ in a muffle furnace, preserving heat for 6-12h, cooling to room temperature to obtain Mg 2 SiO 4 Powder;
(3) according to the stoichiometric ratio (Mg) x Zn 1-x )Al 2 O 4 Weighing Mg (OH) 2 ZnO and Al 2 O 3 Pouring weighed raw materials into a ball milling tank, adding zirconia balls and deionized water, carrying out planetary ball milling for 4-12h, taking out, drying, putting the dried powder into an alumina crucible, calcining in a muffle furnace at 1350- x Zn 1-x )Al 2 O 4 Powder;
(4) according to the stoichiometric ratio (Ca) y Sr 1-y )(Ti z Zr 1-z )O 3 Weighing CaCO 3 、SrCO 3 、ZrO 2 And TiO 2 2 Raw materials, will weighPouring the raw materials into a ball milling tank, adding zirconia balls and deionized water, carrying out planetary ball milling for 4-12h, taking out, drying, putting the dried powder into an alumina crucible, calcining at 1050- y Sr 1-y )(Ti z Zr 1-z )O 3 Powder;
(5) according to the proportion of a MgTiO 3 +b Mg 2 SiO 4 +c(Mg x Zn 1-x )Al 2 O 4 +d (Ca y Sr 1-y )(Ti z Zr 1-z )O 3 + (1-a-b-c-d) TMs weighing the MgTiO 3 、Mg 2 SiO 4 、(Mg x Zn 1-x )Al 2 O 4 、 (Ca y Sr 1-y )(Ti z Zr 1-z )O 3 And TMs, pouring the weighed raw materials into a ball milling tank, adding zirconia balls and deionized water, carrying out planetary ball milling for 4-8h, taking out, drying and crushing to obtain the prepared NP0 type MLCC ceramic powder.
Adding 7-10 wt% of PVA solution into the ceramic powder, granulating, pressing into a wafer sample, sintering at 1200-1300 ℃, and keeping the temperature for 3-7h to obtain the ceramic sample.
The specific material components of each example and the electrical properties of the corresponding ceramic samples are shown in Table 1, and TMs in examples 1 and 3 are ZnO and MnO 2 Wherein ZnO and MnO 2 In the molar ratio of (1: 1), TMs in examples 2 and 4 are Co 2 O 3 In examples 5 and 6, TMs is MnCO 3 And Co 2 O 3 In which MnCO 3 、Co 2 O 3 In the molar ratio of 2:1, TMs in examples 7 and 8 is MnO 2 、Co 2 O 3 And ZnO, wherein MnO 2 、Co 2 O 3 The molar ratio of ZnO is 2:1: 1; wherein, the capacitance and the dielectric loss under 1MHz are tested by an Agilent E4980A precision bridge tester, and the dielectric constant is calculated according to a parallel plate capacitor formula; tau. ε According to the formula
Calculated, where T2 is-55 ℃ or 125 ℃, T1 is 20 ℃, ε 1 and ε 2 are the dielectric constants of the samples at temperatures T2 and T1, respectively.
TABLE 1 Material composition and corresponding ceramic sample Electrical Properties for each example (same methods of preparation and parameter selection for each example)
As can be seen from Table 1, by adjusting MgTiO 3 、Mg 2 SiO 4 、(Mg x Zn 1-x )Al 2 O 4 、 (Ca y Sr 1-y )(Ti z Zr 1-z )O 3 And TMs ratio, improves the Q value of the porcelain powder, and can adjust the temperature coefficient (tau) of the dielectric constant ε ) The method is near zero, and can be well applied to the fields of high-frequency communication and radio frequency.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (9)
1. MgTiO for NP0 type MLCC 3 The radio frequency porcelain powder is characterized in that MgTiO for NP0 type MLCC 3 The radio frequency ceramic powder comprises the following material components: alpha MgTiO 3 +b Mg 2 SiO 4 +c(Mg x Zn 1-x )Al 2 O 4 +d(Ca y Sr 1-y )(Ti z Zr 1-z )O 3 + (1-a-b-c-d) TMs; wherein TMs is at least one of oxides or salts of Mn, Co and Zn, a is more than or equal to 0.65 and less than or equal to 0.85, b is more than or equal to 0.05 and less than or equal to 0.2, and c is more than or equal to 0.07 and less than or equal to c0.25，0.01≤d≤0.05，0.1≤x≤0.9，0.2≤y≤0.8，0.8≤z≤1。
2. The MgTiO for NP0 type MLCC of claim 1 3 The preparation method of the base radio frequency ceramic powder is characterized by comprising the following steps:
(1) MgTiO according to stoichiometric ratio 3 Weighing raw materials, pouring the weighed raw materials into a ball milling tank, adding zirconia balls and deionized water, ball milling for 4-12h, taking out, drying, calcining the dried powder at 950-1150 ℃, preserving heat for 3-6h, cooling to room temperature to obtain MgTiO 3 Powder;
(2) according to stoichiometric ratio Mg 2 SiO 4 Weighing raw materials, pouring the weighed raw materials into a ball milling tank, adding zirconia balls and deionized water, carrying out planetary ball milling for 4-12h, taking out, drying, calcining the dried powder at 1100-1250 ℃, preserving heat for 6-12h, and cooling to room temperature to obtain Mg 2 SiO 4 Powder;
(3) according to the stoichiometric ratio (Mg) x Zn 1-x )Al 2 O 4 Weighing raw materials, pouring the weighed raw materials into a ball milling tank, adding zirconia balls and deionized water, performing planetary ball milling for 4-12h, taking out, drying, calcining the dried powder at 1350- x Zn 1-x )Al 2 O 4 Powder;
(4) according to the stoichiometric ratio (Ca) y Sr 1-y )(Ti z Zr 1-z )O 3 Weighing raw materials, pouring the weighed raw materials into a ball milling tank, adding zirconia balls and deionized water, carrying out planetary ball milling for 4-12h, taking out, drying, calcining the dried powder at 1050-1200 ℃, preserving heat for 3-6h, and cooling to room temperature to obtain (Ca) y Sr 1-y )(Ti z Zr 1-z )O 3 Powder;
(5) according to the proportion of alpha MgTiO 3 +b Mg 2 SiO 4 +c(Mg x Zn 1-x )Al 2 O 4 +d(Ca y Sr 1-y )(Ti z Zr 1-z )O 3 + (1-a-b-c-d) TMs, weighingMgTiO described above 3 Powder, Mg 2 SiO 4 Powder, (Mg) x Zn 1-x )Al 2 O 4 Powder, (Ca) y Sr 1-y )(Ti z Zr 1-z )O 3 Pouring weighed raw materials into a ball milling tank, adding zirconia balls and deionized water, carrying out planetary ball milling for 4-8h, taking out, drying and crushing to obtain MgTiO 0 type MLCC powder for the MLCC 3 And (3) base radio frequency ceramic powder.
3. The MgTiO of claim 2 for NP0 MLCC 3 The preparation method of the radio frequency porcelain powder is characterized in that the raw material in the step (1) is Mg (OH) 2 And TiO 2 2 。
4. The MgTiO of claim 2 for NP0 MLCC 3 The preparation method of the radio frequency porcelain powder is characterized in that the raw material in the step (2) is Mg (OH) 2 And SiO 2 。
5. The MgTiO 0 MLCC of claim 2, which is used for NPs 0 3 The preparation method of the radio frequency porcelain powder is characterized in that the raw material in the step (3) is Mg (OH) 2 ZnO and Al 2 O 3 。
6. The MgTiO 0 MLCC of claim 2, which is used for NPs 0 3 The preparation method of the base radio frequency ceramic powder is characterized in that the raw material in the step (4) is CaCO 3 、SrCO 3 、ZrO 2 And TiO 2 2 。
7. An NP0 type MLCC microwave dielectric ceramic, characterized in that MgTiO 3 for NP0 type MLCC according to claim 1 3 And preparing the base radio frequency ceramic powder.
8. The method for preparing NP0 type MLCC microwave dielectric ceramic according to claim 7, wherein the method is: MgTiO for NP0 type MLCC according to claim 1 3 Adding PVA solution into the base radio frequency ceramic powder for granulation and pressingAnd sintering the cylindrical block at the temperature of 1200-1300 ℃, and preserving the heat for 3-7h to obtain an NP0 type MLCC microwave dielectric ceramic sample.
9. The method for preparing NP0 type MLCC microwave dielectric ceramic of claim 8, wherein the PVA content in the PVA solution is 7-10 wt%.
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