JP2768068B2 - Manufacturing method of PZT piezoelectric plate - Google Patents
Manufacturing method of PZT piezoelectric plateInfo
- Publication number
- JP2768068B2 JP2768068B2 JP19944091A JP19944091A JP2768068B2 JP 2768068 B2 JP2768068 B2 JP 2768068B2 JP 19944091 A JP19944091 A JP 19944091A JP 19944091 A JP19944091 A JP 19944091A JP 2768068 B2 JP2768068 B2 JP 2768068B2
- Authority
- JP
- Japan
- Prior art keywords
- powder
- sintering
- piezoelectric plate
- calcining
- manufacturing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- 239000000843 powder Substances 0.000 claims description 38
- 238000001354 calcination Methods 0.000 claims description 27
- 238000005245 sintering Methods 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 9
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 8
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 8
- 238000010298 pulverizing process Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- 239000011812 mixed powder Substances 0.000 claims description 5
- NKZSPGSOXYXWQA-UHFFFAOYSA-N dioxido(oxo)titanium;lead(2+) Chemical compound [Pb+2].[O-][Ti]([O-])=O NKZSPGSOXYXWQA-UHFFFAOYSA-N 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium(II) oxide Chemical compound [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 claims 2
- 238000002441 X-ray diffraction Methods 0.000 description 7
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 7
- 239000002245 particle Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 229910000464 lead oxide Inorganic materials 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Oxide Ceramics (AREA)
- Powder Metallurgy (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は酸化鉛（ＰｂＯ）、酸化
チタン（ＴｉＯ2 ）及び酸化ジルコニウム（ＺｒＯ2 ）
の焼結体（ＰＺＴ）からなる圧電板の製造方法に関す
る。The present invention relates to lead oxide (PbO), titanium oxide (TiO 2 ) and zirconium oxide (ZrO 2 ).
The present invention relates to a method for manufacturing a piezoelectric plate made of a sintered body (PZT).
【０００２】[0002]
【従来の技術】ＰＺＴ系圧電材料は優れた圧電特性を示
し、圧電アクチュエ−タ等に広く用いられている。この
圧電アクチュエ−タを製造するには、ＰＺＴ圧電板と電
極板とを交互に複数個積層して用いることが行われてい
る。このＰＺＴ圧電板を製造するには、酸化鉛、酸化チ
タン及び酸化ジルコニウムを含む原料粉末を所定量秤量
し混粉し、成形体を成形し、その成形体を焼結すること
で製造することができる。しかしながら混粉された混粉
粉末を直ちに焼結すると、組成の均一性が不十分となり
所望の性能が得られない場合がある。そこで、例えば特
開平２ー２８８３８１号公報に開示されているように、
混粉粉末を仮焼する仮焼工程を行い、得られた仮焼粉末
を粉砕した粉末を用いて成形し焼結する工程が採用され
ている。このように本焼に先立って仮焼を行うことによ
り、組成の均一化を図ることができる。2. Description of the Related Art PZT-based piezoelectric materials exhibit excellent piezoelectric characteristics and are widely used in piezoelectric actuators and the like. In order to manufacture this piezoelectric actuator, a plurality of PZT piezoelectric plates and electrode plates are alternately laminated and used. In order to manufacture this PZT piezoelectric plate, a raw material powder containing lead oxide, titanium oxide and zirconium oxide is weighed and mixed in a predetermined amount, a compact is formed, and the compact is sintered. it can. However, if the mixed powder is immediately sintered, the uniformity of the composition becomes insufficient, and the desired performance may not be obtained. Therefore, for example, as disclosed in Japanese Patent Laid-Open No. 2-288381,
A calcining step of calcining the mixed powder is performed, and the obtained calcined powder is molded and sintered using the pulverized powder. By performing the calcination prior to the main firing in this manner, the composition can be made uniform.
【０００３】[0003]
【発明が解決しようとする課題】ところが、仮焼を行
い、得られた仮焼粉末を粉砕し、その粉砕粉末から成形
し焼結する方法においては、成形体内に空孔が生じ易く
その空孔が焼結後に欠陥として残るという不具合があっ
た。このように空孔が生じると、焼結体の抗折強度が低
下し、圧電体駆動時の耐久性が低下するという不具合が
ある。However, in the method of performing calcination, pulverizing the obtained calcined powder, and molding and sintering from the pulverized powder, voids are easily generated in the molded body, and the voids are easily formed. However, there was a defect that sintering remained as a defect after sintering. When such voids are generated, there is a problem that the transverse rupture strength of the sintered body is reduced and the durability at the time of driving the piezoelectric body is reduced.
【０００４】本発明は上記した事情に鑑みてなされたも
のであり、成形時の空孔の発生を防止することを目的と
する。[0004] The present invention has been made in view of the above circumstances, and has as its object to prevent generation of voids during molding.
【０００５】[0005]
【課題を解決するための手段】本発明者等は、仮焼工程
における条件により焼結体の焼結密度が変動することを
発見した。そして鋭意研究の結果、仮焼工程で未反応部
が残存する程度の仮焼条件とすることにより、仮焼粉末
を粉砕した粉末の粒径が細かくなり焼結密度が向上する
ことを発見して本発明を完成したものである。Means for Solving the Problems The present inventors have found that the sintering density of the sintered body varies depending on the conditions in the calcination step. As a result of diligent research, they found that by setting the calcination conditions to the extent that unreacted portions remain in the calcination process, the particle size of the powder obtained by pulverizing the calcined powder was improved and the sintering density was improved. The present invention has been completed.
【０００６】すなわち、上記課題を解決する本発明のＰ
ＺＴ圧電板の製造方法は、酸化鉛（ＰｂＯ）、酸化チタ
ン（ＴｉＯ2 ）及び酸化ジルコニウム（ＺｒＯ2 ）を含
む原料粉末を所定量秤量し混粉する混粉工程と、得られ
た混粉粉末を仮焼する仮焼工程と、得られた仮焼粉末を
粉砕する粉砕工程と、得られた粉砕粉末から成形体を形
成する成形工程と、成形体を焼結する焼結工程と、から
なるＰＺＴ圧電板の製造方法において、仮焼工程で得ら
れる仮焼粉末には、チタン酸鉛（ＰｂＴｉＯ3 ）、酸化
ジルコニウム（ＺｒＯ2 ）及び酸化鉛（ＰｂＯ）から選
ばれる未反応部が残存していることを特徴とする。That is, the P of the present invention which solves the above-mentioned problems.
A method for manufacturing a ZT piezoelectric plate includes a powder mixing step of weighing and mixing a predetermined amount of a raw material powder containing lead oxide (PbO), titanium oxide (TiO 2 ), and zirconium oxide (ZrO 2 ); And a sintering step of sintering the molded body, and a sintering step of sintering the molded body, and a sintering step of sintering the molded body. In the method for manufacturing a PZT piezoelectric plate, unreacted portions selected from lead titanate (PbTiO 3 ), zirconium oxide (ZrO 2 ) and lead oxide (PbO) remain in the calcined powder obtained in the calcining step. It is characterized by being.
【０００７】混粉工程、粉砕工程、成形工程および焼結
工程は従来と同様に行うことができる。本発明の最大の
特徴は仮焼工程にある。すなわち仮焼工程で得られる仮
焼粉末には、チタン酸鉛、酸化ジルコニウムおよび酸化
鉛から選ばれる未反応部が残存するように、仮焼工程を
行う。例えばこのように未反応部を残すには、仮焼温度
を６５０〜８００℃とし、仮焼時間を６〜８時間とする
ことで行うことができる。[0007] The powder mixing step, the pulverizing step, the forming step and the sintering step can be carried out in the same manner as in the prior art. The greatest feature of the present invention lies in the calcining step. That is, the calcining step is performed so that unreacted portions selected from lead titanate, zirconium oxide, and lead oxide remain in the calcined powder obtained in the calcining step. For example, the unreacted portion can be left by setting the calcination temperature to 650 to 800 ° C. and the calcination time to 6 to 8 hours.
【０００８】この仮焼工程で得られる仮焼粉末中の未反
応部は、仮焼粉末全体の１０〜４０モル％とすることが
望ましい。１０モル％より少ない場合および４０モル％
より多い場合には、焼結体の焼結密度が低下し、製造さ
れる圧電アクチュエ−タの圧電特性が低下するようにな
る。[0008] The unreacted portion in the calcined powder obtained in the calcining step is desirably 10 to 40 mol% of the entire calcined powder. Less than 10 mol% and 40 mol%
If it is larger, the sintered density of the sintered body is reduced, and the piezoelectric characteristics of the manufactured piezoelectric actuator are reduced.
【０００９】[0009]
【発明の作用および効果】仮焼工程において完全なＰＺ
Ｔの結晶層を形成すると、得られる仮焼粉末は大きな凝
集体となるために、粉砕工程に大きな粉砕力が必要とな
る。さらに粉砕工程で粉砕しても、細かくするには限界
がある。例えば９００℃程度の高温で仮焼すると、チタ
ン酸鉛、酸化ジルコニウム及び酸化鉛の三成分が全て反
応するため、粉砕しても平均粒径を細かくすることは困
難となり、粉砕粉末の平均粒径は約０．４μｍである。
ところが７００℃程度で仮焼すると未反応部が残るた
め、粉砕した場合の粒径が小さくなり、粉砕粉末の平均
粒径は０．２μｍと約半分の大きさに細かくなることが
明らかとなった。Function and Effect of the Invention Complete PZ in the calcination process
When the crystal layer of T is formed, the calcined powder obtained becomes a large aggregate, so that a large crushing force is required in the crushing step. Furthermore, there is a limit to the fineness even when crushed in the crushing step. For example, when calcined at a high temperature of about 900 ° C., all three components of lead titanate, zirconium oxide and lead oxide react, so it is difficult to reduce the average particle size even when pulverized. Is about 0.4 μm.
However, when calcined at about 700 ° C., unreacted portions remain, so that the particle size in the case of pulverization becomes small, and the average particle size of the pulverized powder becomes 0.2 μm, which is about half as large. .
【００１０】すなわち成形工程における成形体では、粉
砕粉末の粒径が細かいため空孔が形成されにくく緻密な
成形体となる。また未反応部の存在により、焼結時に焼
結を促進する活性エネルギーが増大する。したがって従
来に比べて焼結体の焼結密度が向上する。したがって本
発明の製造方法によれば、焼結性が向上し焼結体の抗折
強度が向上する。これにより圧電アクチュエータとして
駆動時の耐久性が向上する。また仮焼温度が低くなるた
めに、仮焼中の鉛の蒸発飛散を防止することができる。
したがってＰＺＴ組成の変動を防止することもできる。That is, in the compact in the compacting step, since the particle size of the pulverized powder is small, pores are difficult to be formed and a compact compact is obtained. In addition, due to the presence of the unreacted portion, active energy for promoting sintering at the time of sintering increases. Therefore, the sintered density of the sintered body is improved as compared with the related art. Therefore, according to the production method of the present invention, the sinterability is improved and the bending strength of the sintered body is improved. Thereby, the durability at the time of driving as a piezoelectric actuator is improved. Further, since the calcining temperature is lowered, it is possible to prevent the lead from being evaporated and scattered during the calcining.
Therefore, fluctuation of the PZT composition can be prevented.
【００１１】[0011]
【実施例】以下実施例により具体的に説明する。 （実施例１） ＜混粉工程＞ＰｂＯ、ＴｉＯ2 およびＺｒＯ2 の各粉末
原料と、微量添加物（ＳｒＣＯ3 ，Ｎｂ2 Ｏ5 ）と、水
とを秤量し、ジルコニアボールとともに容器に入れボ−
ルミルにて湿式混合し、脱水乾燥して混粉粉末を得る。 ＜仮焼工程＞得られた混粉粉末をマグネシアの容器に入
れ、電気炉にて７００℃で８時間加熱し仮焼する。得ら
れた仮焼粉末中の未反応部をＸ線回折装置にて測定した
ところ、未反応部は全体の３０重量％残存していた。ま
た得られた仮焼粉末のＸ線回折チヤートを図３に示す。 ＜粉砕工程＞次にこの仮焼粉末をジルコニアボールとと
もにボ−ルミルにて湿式粉砕し、脱水乾燥して粉砕粉末
を形成する。この粉砕粉末の平均粒径は０．２μｍであ
った。 ＜成形工程・焼結工程＞得られた粉砕粉末からプレス機
を用いて所定の円盤形状に成形し、電気炉にて１２５０
℃で２時間保持して焼結し、ＰＺＴ圧電板を形成した。The present invention will be described more specifically with reference to the following examples. (Example 1) <Mixing step> Each powder raw material of PbO, TiO 2 and ZrO 2 , trace additives (SrCO 3 , Nb 2 O 5 ), and water were weighed, put in a container together with zirconia balls, and placed in a container. −
The mixture is wet-mixed with a mill and dehydrated and dried to obtain a mixed powder. <Calcination process> The obtained mixed powder is placed in a magnesia container, and heated in an electric furnace at 700 ° C for 8 hours to be calcined. When the unreacted portion in the obtained calcined powder was measured with an X-ray diffractometer, 30% by weight of the unreacted portion remained. FIG. 3 shows an X-ray diffraction chart of the obtained calcined powder. <Pulverization Step> Next, this calcined powder is wet-pulverized together with zirconia balls by a ball mill, and dehydrated and dried to form a pulverized powder. The average particle size of the pulverized powder was 0.2 μm. <Molding step and sintering step> The obtained crushed powder was formed into a predetermined disk shape using a press machine, and was then placed in an electric furnace at 1250.
C. for 2 hours while sintering to form a PZT piezoelectric plate.
【００１２】得られたＰＺＴ圧電板について焼結密度と
比誘電率および機械電気結合係数（Ｋｐ）を測定し結果
を表１に示す。 （実施例２）仮焼温度を８００℃としたこと以外は実施
例１と同様にして焼結体を得た。得られた焼結体につい
て実施例１と同様に測定し結果を表１に示す。また仮焼
粉末のＸ線回折チヤートを図４に示す。 （比較例１）仮焼温度を９００℃としたこと以外は実施
例１と同様にして焼結体を形成した。得られた焼結体に
ついて実施例１と同様に測定し結果を表１に示す。また
仮焼粉末のＸ線回折チヤートを図５に示す。 （比較例２）仮焼温度を６５０℃としたこと以外は実施
例１と同様にして焼結体を形成した。得られた焼結体に
ついて実施例１と同様に測定し結果を表１に示す。With respect to the obtained PZT piezoelectric plate, the sintering density, the relative dielectric constant and the mechanical electric coupling coefficient (Kp) were measured, and the results are shown in Table 1. (Example 2) A sintered body was obtained in the same manner as in Example 1 except that the calcination temperature was 800 ° C. The obtained sintered body was measured in the same manner as in Example 1, and the results are shown in Table 1. FIG. 4 shows an X-ray diffraction chart of the calcined powder. (Comparative Example 1) A sintered body was formed in the same manner as in Example 1 except that the calcination temperature was 900 ° C. The obtained sintered body was measured in the same manner as in Example 1, and the results are shown in Table 1. FIG. 5 shows an X-ray diffraction chart of the calcined powder. (Comparative Example 2) A sintered body was formed in the same manner as in Example 1 except that the calcination temperature was 650 ° C. The obtained sintered body was measured in the same manner as in Example 1, and the results are shown in Table 1.
【００１３】[0013]
【表１】 （評価）表１より、仮焼温度が７００〜８００℃の実施
例１および実施例２では、仮焼粉末中に未反応部が１０
〜３０モル％残存している。そして未反応部が多い実施
例１の方が焼結密度が向上し、比誘電率も高くなってい
ることがわかる。[Table 1] (Evaluation) From Table 1, in Examples 1 and 2 in which the calcining temperature was 700 to 800 ° C., the unreacted portion was 10% in the calcined powder.
~ 30 mol% remains. Further, it can be seen that Example 1 having more unreacted portions has higher sintering density and higher relative dielectric constant.
【００１４】一方、仮焼温度が９００℃の比較例１では
仮焼粉末中に未反応部がなく、そのため焼結密度が小さ
く比誘電率も小さくなっている。なお未反応部の量の変
化は図３〜５のＸ線回折チヤートからも明らかである。
また仮焼温度が６５０℃の比較例２では、未反応部は多
いものの焼結密度が低くＰＺＴ圧電体としての使用が困
難である。 （試験例）なお仮焼粉末中の未反応部の残存量と、得ら
れた焼結体の焼結密度および電気特性（比誘電率）との
関係を調査した。結果を図１に示す。また焼結密度とＰ
ＺＴ圧電板の耐久性（駆動回数）との関係を測定し、結
果を図２に示す。図２より焼結密度が高いほど耐久性が
向上することが確認されるが、駆動回数を３×１０ 8 回
以上とするためには、焼結密度が約７．５ｇ／ｃｍ3 以
上あることが必要であることがわかる。したがって図１
より、仮焼粉末中に未反応部が１０〜４０モル％あれば
よいことが明らかである。On the other hand, in Comparative Example 1 in which the calcination temperature was 900 ° C.
There is no unreacted part in the calcined powder, so the sintered density is low
The relative dielectric constant is also small. The change in the amount of unreacted
The transformation is also evident from the X-ray diffraction charts of FIGS.
In Comparative Example 2 in which the calcining temperature was 650 ° C., the unreacted portion was large.
However, the sintering density is low, making it difficult to use as a PZT piezoelectric material.
It is difficult. (Test Example) The remaining amount of the unreacted portion in the calcined powder and the obtained value
Density and electrical characteristics (relative permittivity) of the sintered body
The relationship was investigated. The results are shown in FIG. Also, the sintered density and P
The relationship between the durability of the ZT piezoelectric plate (number of times of driving) was measured and the results were measured.
The results are shown in FIG. 2, the higher the sintered density, the higher the durability
It is confirmed that the number of driving is 3 × 10 8Times
To achieve the above, the sintered density is about 7.5 g / cm.ThreeLess than
It turns out that it is necessary to be above. Therefore, FIG.
If the unreacted portion in the calcined powder is 10 to 40 mol%,
It is clear that it is good.
【図１】未反応部の残存量と、焼結密度および電気特性
（比誘電率）との関係を示すグラフである。FIG. 1 is a graph showing a relationship between a remaining amount of an unreacted portion, a sintering density, and electrical characteristics (relative permittivity).
【図２】焼結密度とＰＺＴ圧電板の耐久性（駆動回数）
との関係を示すグラフである。FIG. 2 Sintering density and durability of PZT piezoelectric plate (number of operations)
6 is a graph showing a relationship with the graph.
【図３】実施例１の製造方法で得られた仮焼粉末のＸ線
回折チャートである。FIG. 3 is an X-ray diffraction chart of a calcined powder obtained by the production method of Example 1.
【図４】実施例２の製造方法で得られた仮焼粉末のＸ線
回折チャートである。4 is an X-ray diffraction chart of a calcined powder obtained by the production method of Example 2. FIG.
【図５】比較例の製造方法で得られた仮焼粉末のＸ線回
折チャートである。FIG. 5 is an X-ray diffraction chart of a calcined powder obtained by a production method of a comparative example.
Claims (1)
2 ）及び酸化ジルコニウム（ＺｒＯ2 ）を含む原料粉末
を所定量秤量し混粉する混粉工程と、得られた混粉粉末
を仮焼する仮焼工程と、得られた仮焼粉末を粉砕する粉
砕工程と、得られた粉砕粉末から成形体を形成する成形
工程と、該成形体を焼結する焼結工程と、からなるＰＺ
Ｔ圧電板の製造方法において、 前記仮焼工程で得られる前記仮焼粉末には、チタン酸鉛
（ＰｂＴｉＯ3 ）、酸化ジルコニウム（ＺｒＯ2 ）及び
酸化鉛（ＰｂＯ）から選ばれる未反応部が残存している
ことを特徴とするＰＺＴ圧電板の製造方法。1. Lead oxide (PbO), titanium oxide (TiO)
2 ) A powder mixing step of weighing and mixing predetermined amounts of raw material powders containing zirconium oxide (ZrO 2 ), a calcining step of calcining the obtained mixed powder, and pulverizing the calcined powder obtained. PZ comprising a pulverizing step, a forming step of forming a compact from the obtained pulverized powder, and a sintering step of sintering the compact.
In the method for manufacturing a T piezoelectric plate, an unreacted portion selected from lead titanate (PbTiO 3 ), zirconium oxide (ZrO 2 ), and lead oxide (PbO) remains in the calcined powder obtained in the calcining step. A method for manufacturing a PZT piezoelectric plate, comprising:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19944091A JP2768068B2 (en) | 1991-08-08 | 1991-08-08 | Manufacturing method of PZT piezoelectric plate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19944091A JP2768068B2 (en) | 1991-08-08 | 1991-08-08 | Manufacturing method of PZT piezoelectric plate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0543910A JPH0543910A (en) | 1993-02-23 |
| JP2768068B2 true JP2768068B2 (en) | 1998-06-25 |
Family
ID=16407855
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19944091A Expired - Lifetime JP2768068B2 (en) | 1991-08-08 | 1991-08-08 | Manufacturing method of PZT piezoelectric plate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2768068B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112063881B (en) * | 2020-08-18 | 2021-07-09 | 北京科技大学 | High-thermal-conductivity adjustable-thermal-expansion copper-based composite material and preparation method thereof |
-
1991
- 1991-08-08 JP JP19944091A patent/JP2768068B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0543910A (en) | 1993-02-23 |
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