JP2019019026A - Sintering mold, and method for manufacturing the same - Google Patents
Sintering mold, and method for manufacturing the same Download PDFInfo
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- 238000005245 sintering Methods 0.000 title claims abstract description 264
- 238000000034 method Methods 0.000 title claims abstract description 36
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 93
- 239000010439 graphite Substances 0.000 claims abstract description 63
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 63
- QYEXBYZXHDUPRC-UHFFFAOYSA-N B#[Ti]#B Chemical compound B#[Ti]#B QYEXBYZXHDUPRC-UHFFFAOYSA-N 0.000 claims abstract description 52
- 229910033181 TiB2 Inorganic materials 0.000 claims abstract description 52
- 239000000843 powder Substances 0.000 claims abstract description 46
- 239000011812 mixed powder Substances 0.000 claims abstract description 22
- 239000011261 inert gas Substances 0.000 claims abstract description 6
- 239000002245 particle Substances 0.000 claims description 34
- 238000002156 mixing Methods 0.000 claims description 10
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 18
- 230000000694 effects Effects 0.000 abstract description 5
- 229910052799 carbon Inorganic materials 0.000 abstract 1
- 230000000593 degrading effect Effects 0.000 abstract 1
- 239000013078 crystal Substances 0.000 description 10
- 238000002490 spark plasma sintering Methods 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 239000000523 sample Substances 0.000 description 7
- 238000005336 cracking Methods 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 238000000280 densification Methods 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000003754 machining Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000011800 void material Substances 0.000 description 2
- 238000007088 Archimedes method Methods 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000009760 electrical discharge machining Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
Abstract
Description
本発明は、例えば放電プラズマ焼結法に用いられる焼結用金型及びその作製方法に関するものである。 The present invention relates to a sintering mold used for, for example, a discharge plasma sintering method and a method for producing the same.
従来、この種の焼結用金型にあっては、ダイ及び上下のパンチからなり、素材として、下記の表１に示すような諸物性を有する黒鉛（以下、「Ｇｒ又はグラファイト」ともいう。）を焼結してなるＧｒ焼結体や二硼化チタン（以下、「ＴｉＢ２」ともいう。）を焼結してなるＴｉＢ２焼結体からなる構造のものが知られている。 Conventionally, this type of sintering mold is composed of a die and upper and lower punches, and as a material, graphite having various physical properties as shown in Table 1 below (hereinafter also referred to as “Gr or graphite”). ) Sintered body and titanium diboride (hereinafter also referred to as “T i B 2 ”) have a structure composed of a T i B 2 sintered body. ing.
この表１において、Ｇｒは機械的強度が低くて高圧力条件における焼結処理に応用することが難しく、やむを得ない場合、金型の肉厚を厚くして機械的強度を増すことはできるものの、製品寸法の精度や製作コストに問題が生じ易く、一方、ＴｉＢ２は機械的強度、例えば、曲げ強度はＧｒより４倍以上、硬さはＧｒより３倍以上大きい材料であることから、焼結用金型の小型化が図れ、かつ、電気的特性ではＴｉＢ２の電気抵抗率はＧｒより小さいから、Ｇｒより電気を通し易く、ダイ及びパンチにおける温度分布は小さくできる。 In Table 1, Gr has a low mechanical strength and is difficult to apply to the sintering process under high pressure conditions. If it is unavoidable, the thickness of the mold can be increased to increase the mechanical strength. On the other hand, T i B 2 is a material having mechanical strength, for example, bending strength is 4 times or more than Gr, and hardness is 3 times or more than Gr. The sintering mold can be reduced in size, and in terms of electrical characteristics, the electrical resistivity of T i B 2 is smaller than Gr. Therefore, it is easier to conduct electricity than Gr, and the temperature distribution in the die and punch can be reduced.
しかしながら上記従来構造のうち、金型素材としてＴｉＢ２焼結体を用いたＴｉＢ２金型の場合、ＴｉＢ２は硬さがＨＶ３,０００程度あり、形状加工が難しく、加工コストが高くなり、金型としての応用分野が限られてしまうことがあるという不都合を有している。 However among the conventional structure, when the TiB 2 molds with TiB 2 sintered body as a mold material, TiB 2 hardness There are about HV3,000, difficult shaping, machining cost is high, gold There is an inconvenience that the application field as a mold may be limited.
本発明はこのような不都合を解決することを目的とするもので、本発明のうち、請求項１記載の発明は、焼結用の金型であって、上記金型は、黒鉛（以下、「Ｇｒ又はグラファイト」ともいう。）粉末と二硼化チタン（以下、「ＴｉＢ２」ともいう。）粉末との混合粉末（以下、「Ｇｒ−ＴｉＢ２混合粉末」ともいう。）を、放電プラズマ焼結法（以下、「ＳＰＳ法」ともいう。）を用いて焼結された、黒鉛二硼化チタン焼結体（以下、「Ｇｒ−ＴｉＢ２焼結体」ともいう。）からなることを特徴とする焼結用金型にある。 The present invention aims to solve such inconveniences. Among the present inventions, the invention according to claim 1 is a mold for sintering, and the mold is made of graphite (hereinafter, Also referred to as “Gr or graphite”.) Mixed powder of powder and titanium diboride (hereinafter also referred to as “T i B 2 ”) powder (hereinafter also referred to as “Gr-T i B 2 mixed powder”). It refers to, spark plasma sintering method (hereinafter, also referred to as "SPS method".) was sintered using a graphite titanium diboride sintered body (hereinafter, also referred to as "Gr-T i B 2 sintered body" .) In a sintering mold characterized by comprising:
又、請求項２記載の発明は、上記黒鉛粉末と上記二硼化チタン粉末との混合割合として、黒鉛粉末２５重量％〜８０重量％、二硼化チタン粉末２０重量％〜７５重量％であることを特徴とするものであり、又、請求項３記載の発明は、上記黒鉛粉末は、純度９９．９％以上、平均粒子サイズ６０μｍ以下、最大粒子サイズ１２０μｍ以下であることを特徴とするものであり、又、請求項４記載の発明は、上記二硼化チタン粉末は、純度９９．９％以上、平均粒子サイズ６０μｍ以下、最大粒子サイズ１２０μｍ以下であることを特徴とするものであり、又、請求項５記載の発明は、上記焼結の条件は、焼結温度１，７００℃以上２，１００℃以下、焼結圧力２０ＭＰａ以上１００ＭＰａ以下であることを特徴とするものであり、又、請求項６記載の発明は、上記黒鉛二硼化チタン焼結体の相対密度は理論密度の９５％以上であることを特徴とするものである。 According to a second aspect of the present invention, the mixing ratio of the graphite powder and the titanium diboride powder is 25 wt% to 80 wt% of the graphite powder and 20 wt% to 75 wt% of the titanium diboride powder. Further, the invention according to claim 3 is characterized in that the graphite powder has a purity of 99.9% or more, an average particle size of 60 μm or less, and a maximum particle size of 120 μm or less. The invention according to claim 4 is characterized in that the titanium diboride powder has a purity of 99.9% or more, an average particle size of 60 μm or less, and a maximum particle size of 120 μm or less. The invention of claim 5 is characterized in that the sintering conditions are a sintering temperature of 1,700 ° C. to 2,100 ° C. and a sintering pressure of 20 MPa to 100 MPa, , Claim 6 The invention, the relative density of the graphite titanium diboride sintered body is characterized in that at least 95% of the theoretical density.
又、請求項７記載の方法の発明は、焼結用の金型の作製方法であって、黒鉛粉末と二硼化チタン粉末との混合粉末を、放電プラズマ焼結法を用いて焼結された、黒鉛二硼化チタン焼結体からなる金型を作製することを特徴とする焼結用金型の作製方法にある。 The invention of claim 7 is a method for producing a mold for sintering, wherein a mixed powder of graphite powder and titanium diboride powder is sintered using a discharge plasma sintering method. Further, the present invention provides a method for producing a sintering mold, which comprises producing a mold comprising a graphite titanium diboride sintered body.
又、請求項８記載の方法の発明は、上記焼結雰囲気は、真空雰囲気であることを特徴とするものであり、又、請求項９記載の方法の発明は、上記焼結雰囲気は、不活性ガス雰囲気であることを特徴とするものである。 The invention of the method according to claim 8 is characterized in that the sintering atmosphere is a vacuum atmosphere, and the invention of the method according to claim 9 is characterized in that the sintering atmosphere is not suitable. It is an active gas atmosphere.
本発明は上述の如く、請求項１又は請求項７記載の発明にあっては、黒鉛粉末と二硼化チタン粉末との混合粉末を、放電プラズマ焼結法を用いて焼結された、黒鉛二硼化チタン焼結体からなる焼結用金型であるから、放電プラズマ焼結法により作製することにより短時間焼結が可能となり、焼結用金型のコスト低減を図ることができ、例えば約２，０００℃程度の高温、約２５０ＭＰａ程度の高圧の焼結条件でのプラズマ焼結用金型として使用したとしても、焼結用金型の変形がきわめて少なく、焼結用金型の変形による焼結体の寸法精度の低下を防ぐことができ、他の焼結に再利用することもできる。 As described above, the present invention is the graphite as claimed in claim 1 or claim 7, wherein the mixed powder of graphite powder and titanium diboride powder is sintered using a discharge plasma sintering method. Since it is a sintering die made of a titanium diboride sintered body, it can be sintered for a short time by producing by a discharge plasma sintering method, and the cost of the sintering die can be reduced. For example, even if it is used as a plasma sintering die under a high temperature of about 2,000 ° C. and a high pressure sintering temperature of about 250 MPa, the deformation of the sintering die is extremely small, The deterioration of the dimensional accuracy of the sintered body due to deformation can be prevented, and it can be reused for other sintering.
又、請求項２記載の発明にあっては、上記黒鉛粉末と上記二硼化チタン粉末との混合割合として、黒鉛粉末２５重量％〜８０重量％、二硼化チタン粉末２０重量％〜７５重量％であるから、黒鉛二硼化チタン焼結体の機械的強度の低下を防いで過酷な焼結条件に応用することができ、加工コストの低減を図ることができ、又、請求項３記載の発明にあっては、上記黒鉛粉末は、純度９９．９％以上、平均粒子サイズ６０μｍ以下、最大粒子サイズ１２０μｍ以下であるから、黒鉛二硼化チタン焼結体の機械的強度の低下を防ぎ、高温高圧下の焼結用の金型として利用することができ、又、請求項４記載の発明にあっては、上記二硼化チタン粉末は、純度９９．９％以上、平均粒子サイズ６０μｍ以下、最大粒子サイズ１２０μｍ以下であるから、黒鉛二硼化チタン焼結体の機械的強度の低下を防ぎ、高温高圧下の焼結用の金型として利用することができ、又、請求項５記載の発明にあっては、上記焼結の条件は、焼結温度１，７００℃以上２，１００℃以下、焼結圧力２０ＭＰａ以上１００ＭＰａ以下であるから、Ｇｒ−ＴｉＢ２焼結体の機械的強度の低下を防止することができ、高精度の焼結用金型を得ることができ、又、請求項６記載の発明にあっては、上記黒鉛二硼化チタン焼結体の相対密度は理論密度の９５％以上であるから、熱伝導率の低下を防いで焼結用金型の温度むらを防ぐことができ、焼結用金型の割れを防ぐことができる。 In the invention of claim 2, the mixing ratio of the graphite powder and the titanium diboride powder is 25 wt% to 80 wt% of the graphite powder and 20 wt% to 75 wt% of the titanium diboride powder. Therefore, it is possible to prevent the mechanical strength of the graphite diboride sintered body from being lowered and to apply to severe sintering conditions, and to reduce the processing cost. In the present invention, the graphite powder has a purity of 99.9% or more, an average particle size of 60 μm or less, and a maximum particle size of 120 μm or less, thereby preventing a decrease in mechanical strength of the graphite titanium diboride sintered body. The titanium diboride powder has a purity of not less than 99.9% and an average particle size of 60 μm. Since the maximum particle size is 120 μm or less The graphite titanium diboride sintered body is prevented from lowering the mechanical strength, and can be used as a mold for sintering under high temperature and high pressure. conditions, the sintering temperature 1,700 ° C. or higher 2,100 ° C. or less, since it is less sintering pressure 20MPa or more 100 MPa, it is possible to prevent a reduction in the mechanical strength of Gr-T i B 2 sintered body In addition, in the invention according to claim 6, the relative density of the graphite titanium diboride sintered body is 95% or more of the theoretical density. Further, it is possible to prevent the temperature of the sintering mold from being uneven by preventing a decrease in thermal conductivity, and to prevent cracking of the sintering mold.
又、請求項８記載の方法の発明にあっては、上記焼結雰囲気は、真空雰囲気としているから、酸化反応を防ぐことができ、高品質の焼結用金型を作製することができ、又、請求項９記載の方法の発明にあっては、上記焼結雰囲気は、不活性ガス雰囲気であることとしているから、酸化反応を防ぐことができ、高品質の焼結用金型を作製することができる。 Further, in the invention of the method according to claim 8, since the sintering atmosphere is a vacuum atmosphere, an oxidation reaction can be prevented, and a high-quality sintering mold can be produced. In the method invention of claim 9, since the sintering atmosphere is an inert gas atmosphere, an oxidation reaction can be prevented and a high-quality sintering mold is produced. can do.
図１乃至図６は本発明の実施の形態例を示し、Ｍは焼結用金型であって、図１の如く、ダイＭ１及び上下のパンチＭ２・Ｍ２から構成され、この場合、ダイＭ１及び上下のパンチＭ２・Ｍ２のいずれにあっても、黒鉛（以下、「Ｇｒ又はグラファイト」ともいう。）粉末と二硼化チタン（以下、「ＴｉＢ２」ともいう。）粉末との混合粉末（以下、「Ｇｒ−ＴｉＢ２混合粉末」ともいう。）Ｗを、放電プラズマ焼結法（以下、「ＳＰＳ法」ともいう。）を用いて焼結された、黒鉛二硼化チタン焼結体（以下、「Ｇｒ−ＴｉＢ２焼結体」ともいう。）により作製されている。 1 to 6 show an embodiment of the present invention, M is a sintered mold, as shown in FIG. 1, is composed of a die M 1 and the upper and lower punches M 2 · M 2, in this case In any of the die M 1 and the upper and lower punches M 2 and M 2 , graphite (hereinafter also referred to as “Gr or graphite”) powder and titanium diboride (hereinafter also referred to as “T i B 2 ”). .) mixing of the powder powder (hereinafter, also referred to as "Gr-T i B 2 mixed powder".) W, spark plasma sintering method (hereinafter, also referred to as "SPS method".) was sintered using a , graphite titanium diboride sintered body (hereinafter, also referred to as "Gr-T i B 2 sintered body".) has been prepared by.
この場合、焼結用金型Ｍの作製において、例えば、パンチＭ２・Ｍ２の作製にあっては、図２、図３の如く、グラファイトからなるダイＤ及びダイＤの穴Ｄ１に挿入された上下のグラファイトからなるパンチＰ・Ｐにより構成されるグラファイト製の焼結型Ｓを用意し、このダイＤの穴Ｄ１とパンチＰ・Ｐにより形成された空間に焼結材料としての黒鉛粉末と二硼化チタン粉末との混合粉末Ｗを充填し、例えば、密閉構造のチャンバーＣ内に焼結型Ｓを配置し、上部電極ＰＵ、下部電極ＰＤ及び上部電極ＰＵを上下加圧動作させる加圧機構Ｋ、上部電極ＰＵ及び下部電極ＰＤ間にパルス電流を流すパルス電源ユニットＵ、制御ユニットＧ等を備えてなる通電加圧焼結機Ｔを用意し、通電加圧焼結機Ｔを用いて、上記グラファイトからなる焼結型Ｓ内に充填されたＧｒ−ＴｉＢ２混合粉末ＷをパンチＰ・Ｐにより圧力を加えながらパルス電流を流して焼結材料としてのＧｒ−ＴｉＢ２混合粉末Ｗ及び焼結型Ｓの自己発熱効果（ジュール発熱効果）により焼結する放電プラズマ焼結法により作製するようにしている。尚、ダイＭ１の作製にあっては、例えば、図２、図３のダイＤの穴Ｄ１に図示省略の中子を装入して上記同様に焼結してリング状に作製したり、又は、円柱状に焼結後にダイＭ１に穴を追加加工により形成して作製することもある。この焼結用金型Ｍの形状や構造は上記実施の形態例に限られるものではない。 In this case, in the production of the sintering mold M, for example, in the production of the punches M 2 and M 2 , as shown in FIGS. 2 and 3, the die D made of graphite and the hole D 1 of the die D are inserted. been by upper and lower punches P · P consisting of graphite prepared sintered S made consisting of graphite, graphite as a sintering material in a space formed by the holes D 1 and the punch P · P of the die D Filled with a mixed powder W of powder and titanium diboride powder, for example, the sintered mold S is disposed in a chamber C having a sealed structure, and the upper electrode PU, the lower electrode PD, and the upper electrode PU are vertically pressurized. An electric pressure sintering machine T comprising a pressure mechanism K, a pulse power supply unit U for passing a pulse current between the upper electrode PU and the lower electrode PD, a control unit G, etc. is prepared. Use the above-mentioned firing made of graphite Gr-T i B 2 mixed powder W and sintered in a sintering type S Gr-T i B 2 mixed powder W filled in as a sintering material by supplying a pulse current while applying a pressure by the punch P · P It is made by a discharge plasma sintering method in which sintering is performed by the self-heating effect of S (joule heating effect). Incidentally, in the manufacturing of the die M 1, for example, to prepare in a ring shape 2, by charging a not shown of the core into the hole D 1 of the die D in Figure 3 is sintered in the same manner described above or, also be produced by forming the addition process a hole in the die M 1 after sintering a cylindrical shape. The shape and structure of the sintering mold M are not limited to the above embodiment.
ここにおいて、上記黒鉛粉末と上記二硼化チタン粉末との混合割合は、黒鉛粉末２５重量％〜８０重量％、二硼化チタン粉末２０重量％〜７５重量％である。その理由は、黒鉛粉末が２５重量％以下になると、難加工焼結体ができてしまい、それによって加工コストが必要以上に高くなり、黒鉛粉末が８０重量％以上になると、従来の黒鉛製品と変わらない低機械強度の製品になるので過酷な焼結条件に応用することができない。又、二硼化チタン粉末が２０重量％以下になると、従来の黒鉛製品と変わらない低機械強度の製品になるので過酷な焼結条件に応用することができず、二硼化チタン粉末が７５重量％以上になると、難加工焼結体ができてしまい、それによって加工コストが必要以上に高くなるからである。 Here, the mixing ratio of the graphite powder and the titanium diboride powder is 25 wt% to 80 wt% of the graphite powder and 20 wt% to 75 wt% of the titanium diboride powder. The reason is that when the graphite powder is 25 wt% or less, a difficult-to-process sintered body is formed, which increases the processing cost more than necessary, and when the graphite powder exceeds 80 wt%, Since it is a product with low mechanical strength that does not change, it cannot be applied to severe sintering conditions. On the other hand, when the titanium diboride powder is 20% by weight or less, it becomes a low mechanical strength product which is not different from the conventional graphite product, so it cannot be applied to severe sintering conditions. This is because, if the amount is more than% by weight, a difficult-to-process sintered body is formed, which increases the processing cost more than necessary.
又、上記Ｇｒ−ＴｉＢ２混合粉末Ｗの黒鉛粉末は、純度９９．９％以上、平均粒子サイズ６０μｍ以下、最大粒子サイズ１２０μｍ以下である。その理由は、純度９９．９％以下の原料を用いた場合、不純物の含有量が多くなり、不純物の種類によっては焼結体の焼結反応を促進し、黒鉛二硼化チタン焼結体の粒子が大きく成長し、その結果、黒鉛二硼化チタン焼結体の機械的強度が低下し、高温高圧下の焼結用の金型として利用できないことになり、純度９９．９％以上であれば黒鉛二硼化チタン焼結体への不純物の影響を無視することができ、又、平均粒子サイズが６０μｍを超えると焼結反応速度が遅くなり、結晶粒子も大きく成長し、緻密な焼結体が得られず、結晶粒子の大きいＧｒ−ＴｉＢ２焼結体は機械的強度が低くなり、高温高圧下の焼結用の金型として利用できないことになり、又、最大粒子サイズが１２０μｍを超えるとＧｒ−ＴｉＢ２焼結体の機械的強度が著しく低下するからである。なお、上記黒鉛粉末の最大粒子サイズは１００μｍ以下が好ましい。その理由は焼結体の機械強度の低下を考慮したからである。 The graphite powder of the Gr—TiB 2 mixed powder W has a purity of 99.9% or more, an average particle size of 60 μm or less, and a maximum particle size of 120 μm or less. The reason for this is that when a raw material having a purity of 99.9% or less is used, the content of impurities increases, and depending on the type of impurities, the sintering reaction of the sintered body is promoted. As a result, the mechanical strength of the graphite titanium diboride sintered body is reduced and it cannot be used as a mold for sintering under high temperature and high pressure, and the purity is 99.9% or more. For example, the influence of impurities on the sintered titanium diboride can be neglected, and if the average particle size exceeds 60 μm, the sintering reaction rate becomes slow, the crystal grains grow large, and the dense sintering body can not be obtained, large Gr-T i B 2 sintered crystal grains is low mechanical strength, it can not be used as a mold for sintering under high temperature and high pressure, also the maximum particle size it exceeds 120μm the mechanical strength of Gr-T i B 2 sintered body is authored This is because it drops. The maximum particle size of the graphite powder is preferably 100 μm or less. The reason is that a decrease in mechanical strength of the sintered body is taken into consideration.
又、上記Ｇｒ−ＴｉＢ２混合粉末Ｗの二硼化チタン粉末は純度９９．９％以上、平均粒子サイズ６０μｍ以下、最大粒子サイズ１２０μｍ以下である。その理由は、純度９９．９％以下の原料を用いた場合、不純物の含有量が多くなり、不純物の種類によっては焼結体の焼結反応を促進し、黒鉛二硼化チタン焼結体の粒子が大きく成長し、その結果、黒鉛二硼化チタン焼結体の機械的強度が低下し、高温高圧下の焼結用の金型として利用できないことになり、純度９９．９％以上であれば黒鉛二硼化チタン焼結体への不純物の影響を無視することができ、又、平均粒子サイズが６０μｍを超えると焼結反応速度が遅くなり、結晶粒子も大きく成長し、緻密な焼結体が得られず、結晶粒子の大きいＧｒ−ＴｉＢ２焼結体は機械的強度が低くなり、高温高圧下の焼結用の金型として利用できないことになり、又、最大粒子サイズが１２０μｍを超えるとＧｒ−ＴｉＢ２焼結体の機械的強度が著しく低下するからである。なお、上記二硼化チタン粉末の最大粒子サイズは１００μｍ以下が好ましい。その理由は焼結体の機械強度の低下を考慮したからである。 The titanium diboride powder of the Gr—TiB 2 mixed powder W has a purity of 99.9% or more, an average particle size of 60 μm or less, and a maximum particle size of 120 μm or less. The reason for this is that when a raw material having a purity of 99.9% or less is used, the content of impurities increases, and depending on the type of impurities, the sintering reaction of the sintered body is promoted. As a result, the mechanical strength of the graphite titanium diboride sintered body is reduced and it cannot be used as a mold for sintering under high temperature and high pressure, and the purity is 99.9% or more. For example, the influence of impurities on the sintered titanium diboride can be neglected, and if the average particle size exceeds 60 μm, the sintering reaction rate becomes slow, the crystal grains grow large, and the dense sintering body can not be obtained, large Gr-T i B 2 sintered crystal grains is low mechanical strength, it can not be used as a mold for sintering under high temperature and high pressure, also the maximum particle size it exceeds 120μm the mechanical strength of Gr-T i B 2 sintered body is authored This is because it drops. The maximum particle size of the titanium diboride powder is preferably 100 μm or less. The reason is that a decrease in mechanical strength of the sintered body is taken into consideration.
又、上記焼結の条件は、焼結温度１，７００℃以上２，１００℃以下、焼結圧力２０ＭＰａ以上１００ＭＰａ以下である。その理由は、焼結温度が１，７００℃未満になると焼結反応の速度が極端に遅くなり、焼結の生産コストが高くなり、焼結温度が２，１００℃を超えると焼結速度が速くなるが、焼結体結晶粒子のサイズが大きく成長し、Ｇｒ−ＴｉＢ２焼結体の機械的強度が低下し、焼結用金型Ｍの焼結にあたっては、通常、グラファイトからなる焼結型Ｓを使用することがあり、そのグラファイトからなる焼結型Ｓの変形量が許容範囲を超えるおそれがあり、高精度の焼結用金型Ｍを得ることができず、又、焼結圧力が２０ＭＰａ未満になると焼結反応は生じても緻密化時間が極端に長くなり、製造コストが高くなり、又、焼結圧力が１００ＭＰａを超えると緻密化時間は短くなるが、上記グラファイトからなる焼結型Ｓの変形量が許容範囲を超えるおそれがあり、量産性が低下するからである。なお、焼結温度は１，８００℃以上２，０００℃以下、焼結圧力は３０ＭＰａ以上８０ＭＰａ以下が好ましい。その理由は焼結反応の速度の低下を防いで生産コストの低減及び上記グラファイトからなる焼結型Ｓの変形を考慮し、高品質の焼結用金型Ｍの作製を考慮したからである。 The sintering conditions are a sintering temperature of 1,700 ° C. to 2,100 ° C. and a sintering pressure of 20 MPa to 100 MPa. The reason is that if the sintering temperature is less than 1,700 ° C, the rate of the sintering reaction becomes extremely slow, the production cost of the sintering becomes high, and if the sintering temperature exceeds 2,100 ° C, the sintering rate is increased. becomes faster, the size of the sintered body grains grow significantly, reduces the mechanical strength of Gr-T i B 2 sintered body, when sintering of the sintered mold M, usually made of graphite The sintering mold S may be used, and the deformation amount of the sintering mold S made of graphite may exceed the allowable range, and a high-precision sintering mold M cannot be obtained. If the sintering pressure is less than 20 MPa, the densification time will be extremely long even if the sintering reaction occurs, and the production cost will be high, and if the sintering pressure exceeds 100 MPa, the densification time will be shortened. The amount of deformation of the sintered mold S exceeds the allowable range. To Le, it is because the productivity decreases. The sintering temperature is preferably 1,800 ° C. or more and 2,000 ° C. or less, and the sintering pressure is preferably 30 MPa or more and 80 MPa or less. The reason is that the reduction of the speed of the sintering reaction is prevented, the production cost is reduced, the deformation of the sintering mold S made of graphite is taken into consideration, and the production of a high-quality sintering mold M is considered.
又、上記黒鉛二硼化チタン焼結体の相対密度は理論密度の９５％以上である。その理由は、相対密度が９５％以下になると、空隙率が大きくなって焼結用金型Ｍの熱伝導率が悪くなり、熱伝導率の低下により焼結用金型Ｍの温度むらが強くなり、焼結用金型Ｍにより焼結される製品の精度が低下し、又、焼結中空隙に応力集中して外部から加えられる焼結圧力より金型の機械的強度以上の応力が発生する可能性があり、焼結中に金型が割れてしまう危険性があるからである。 The relative density of the graphite titanium diboride sintered body is 95% or more of the theoretical density. The reason is that when the relative density is 95% or less, the porosity is increased and the thermal conductivity of the sintering mold M is deteriorated, and the temperature unevenness of the sintering mold M is strong due to the decrease of the thermal conductivity. As a result, the accuracy of the product sintered by the sintering mold M is reduced, and stress more than the mechanical strength of the mold is generated due to the stress concentrated in the void during sintering and the externally applied sintering pressure. This is because there is a risk that the mold will break during sintering.
又、この場合、上記焼結雰囲気は、真空雰囲気、例えば、１０Ｐａ以下とされている。その理由は、真空雰囲気とすることにより、酸化反応を防ぐことができ、高品質の焼結用金型Ｍを作製することができるからである。又、上記焼結雰囲気として、不活性ガス雰囲気とすることもあり、その理由は、アルゴンガスや窒素ガスなどの不活性ガス雰囲気とすることにより、酸化反応を防ぐことができ、高品質の焼結用金型Ｍを作製することができるからである。 In this case, the sintering atmosphere is a vacuum atmosphere, for example, 10 Pa or less. The reason for this is that the oxidation reaction can be prevented and a high-quality sintering mold M can be produced by using a vacuum atmosphere. In addition, the sintering atmosphere may be an inert gas atmosphere, because the inert gas atmosphere such as argon gas or nitrogen gas can prevent oxidation reaction, and high quality firing. This is because the binding die M can be produced.
この実施の形態例は上記構成であるから、図１、図２、図３の如く、グラファイトからなるダイＤの穴Ｄ１及びグラファイトからなるパンチＰ・Ｐにより構成されるグラファイト製の焼結型Ｓの空間に焼結材料としてのＧｒ−ＴｉＢ２混合粉末Ｗを充填し、密閉構造のチャンバーＣ内に焼結型Ｓを配置し、加圧機構Ｋ、パルス電源ユニットＵ及び制御ユニットＧからなる通電加圧焼結機Ｔにより、上記焼結型Ｓ内に充填されたＧｒ−ＴｉＢ２混合粉末ＷをパンチＰ・Ｐにより圧力を加えながらパルス電流を流して焼結材料としてのＧｒ−ＴｉＢ２混合粉末Ｗ及び焼結型Ｓの自己発熱効果（ジュール発熱効果）により焼結する放電プラズマ焼結法により焼結され、しかして、黒鉛二硼化チタン焼結体からなる焼結用金型Ｍを作製することになるから、作製された焼結用金型Ｍにおいては、放電プラズマ焼結法により作製することにより短時間焼結が可能となり、焼結用金型Ｍのコスト低減を図ることができ、例えば約２，０００℃程度の高温、約２５０ＭＰａ程度の高圧の焼結条件でのプラズマ焼結用金型Ｍとして使用したとしても、焼結用金型Ｍの変形がきわめて少なく、焼結用金型Ｍの変形による焼結体の寸法精度の低下を防ぐことができ、他の焼結に再利用することもできる。 Since embodiments of the present is the configuration, FIG. 1, FIG. 2, as in FIG. 3, made of graphite sintered constituted by the punch P · P consisting hole D 1 and graphite die D consisting of graphite filled with Gr-T i B 2 mixed powder W as sintered material in the space S, a sintered type S was placed in a chamber C sealed pressing mechanism K, pulsed power unit U and the control unit G from the consisting current pressure sintering machine T, of the sintered type Gr-T filled in the S i B 2 mixed powder W as a sintering material by supplying a pulse current while applying a pressure by the punch P · P It is sintered by Gr-T i B 2 mixed powder W and a discharge plasma sintering method of sintering by self-heating effect of the sintered S (Joule heating effects), Thus, the graphite-made titanium diboride sintered body Producing sintering mold M Therefore, the produced sintering die M can be sintered for a short time by being produced by the discharge plasma sintering method, and the cost of the sintering die M can be reduced. Even if it is used as a plasma sintering mold M under high temperature sintering conditions of about 2,000 ° C. and high pressure of about 250 MPa, the sintering mold M has very little deformation. The deterioration of the dimensional accuracy of the sintered body due to the deformation of M can be prevented, and it can be reused for other sintering.
ここにおいて、焼結温度１，７００℃、圧力３０ＭＰａの低温低圧の焼結条件下で作製されたＧｒ−ＴｉＢ２焼結体の相対密度は理論密度の９０％となり、又、焼結温度１，８００℃、圧力３０ＭＰａの低温低圧の条件下で９５％となり、又、焼結温度２,１００℃、圧力１００ＭＰａの高温高圧の焼結条件下で作製されたＧｒ−ＴｉＢ２焼結体の相対密度が最大１００％となることが確認され、ここに、理論密度とは焼結体中に全く空隙がないと仮定したときの密度をいい、結晶構造を用いて計算される。計算においては、結晶構造の大きさ及び結晶構造を構成するすべての原子の重量を利用して計算する。相対密度とは焼結後の焼結体の密度をアルキメデス法などの密度測定方法によって測定した値を理論密度の割合として表すものである。 Here, the relative density of the sintering temperature 1,700 ℃, Gr-T i B 2 sintered body prepared by sintering under conditions of low temperature and low pressure of the pressure 30MPa stood 90% of the theoretical density, and the sintering temperature 1,800 ° C., becomes 95% under the conditions of low temperature and low pressure of the pressure 30 MPa, also the sintering temperature 2,100 ° C., high temperature and high pressure of Gr-T i B 2 sintered made by sintering under a pressure of 100MPa It is confirmed that the relative density of the body is 100% at the maximum. Here, the theoretical density means a density when it is assumed that there is no void in the sintered body, and is calculated using the crystal structure. In the calculation, the size is calculated using the size of the crystal structure and the weight of all atoms constituting the crystal structure. The relative density represents a value obtained by measuring a density of a sintered body after sintering by a density measuring method such as Archimedes method as a ratio of theoretical density.
この場合、上記黒鉛粉末と上記二硼化チタン粉末との混合割合として、黒鉛粉末２５重量％〜８０重量％、二硼化チタン粉末２０重量％〜７５重量％であるから、黒鉛二硼化チタン焼結体の機械的強度の低下を防いで過酷な焼結条件に応用することができ、加工コストの低減を図ることができる。 In this case, the mixing ratio of the graphite powder and the titanium diboride powder is 25% to 80% by weight of graphite powder and 20% to 75% by weight of titanium diboride powder. The mechanical strength of the sintered body can be prevented from being lowered and applied to severe sintering conditions, and the processing cost can be reduced.
又、この場合、上記黒鉛粉末は、純度９９．９％以上、平均粒子サイズ６０μｍ以下、最大粒子サイズ１２０μｍ以下であるから、黒鉛二硼化チタン焼結体の機械的強度の低下を防ぎ、高温高圧の焼結の金型として利用することができる。 In this case, since the graphite powder has a purity of 99.9% or more, an average particle size of 60 μm or less, and a maximum particle size of 120 μm or less, the mechanical strength of the graphite titanium diboride sintered body is prevented from being reduced. It can be used as a high-pressure sintering mold.
又、この場合、上記二硼化チタン粉末は、純度９９．９％以上、平均粒子サイズ６０μｍ以下、最大粒子サイズ１２０μｍ以下であるから、黒鉛二硼化チタン焼結体の機械的強度の低下を防ぎ、高温高圧下の焼結用の金型として利用することができる。 In this case, the titanium diboride powder has a purity of 99.9% or more, an average particle size of 60 μm or less, and a maximum particle size of 120 μm or less. It can be used as a mold for sintering under high temperature and pressure.
又、この場合、上記焼結の条件は、焼結温度１，７００℃以上２，１００℃以下、焼結圧力２０ＭＰａ以上１００ＭＰａ以下であるから、Ｇｒ−ＴｉＢ２焼結体の機械的強度の低下を防止することができ、高精度の焼結用金型Ｍを得ることができる。 Further, the mechanical strength of the case, the conditions of the sintering, the sintering temperature 1,700 ° C. or higher 2,100 ° C. or less, since it is less sintering pressure 20MPa or more 100MPa, Gr-T i B 2 sintered body Can be prevented, and a highly accurate sintering mold M can be obtained.
又、この場合、上記黒鉛二硼化チタン焼結体の相対密度は、理論密度の９５％以上であるから、熱伝導率の低下を防いで焼結用金型Ｍの温度むらを防ぐことができ、焼結用金型Ｍの割れを防ぐことができる。 In this case, since the relative density of the graphite titanium diboride sintered body is 95% or more of the theoretical density, it is possible to prevent the thermal conductivity from decreasing and to prevent temperature unevenness of the sintering mold M. And cracking of the sintering mold M can be prevented.
又、この場合、上記焼結雰囲気は、真空雰囲気とされているから、酸化反応を防ぐことができ、高品質の焼結用金型Ｍを作製することができ、又、上記焼結雰囲気として、不活性ガス雰囲気とすることにより、同じく、酸化反応を防ぐことができ、高品質の焼結用金型Ｍを作製することができる。 In this case, since the sintering atmosphere is a vacuum atmosphere, an oxidation reaction can be prevented, and a high-quality sintering mold M can be produced. By using an inert gas atmosphere, the oxidation reaction can be similarly prevented, and a high-quality sintering mold M can be produced.
この実施の形態例により作製されたＧｒ−ＴｉＢ２焼結体からなる焼結用金型Ｍは、図４のＸ線回折パターン図によれば、いずれのピークも黒鉛結晶とＴｉＢ２結晶に同定していることがわかり、ここに、Ｘ線回折パターンの測定にあっては、放電プラズマ焼結法を用いてＧｒ−ＴｉＢ２バルクサンプルを作製し、そのバルクサンプルを粉砕して結晶相同定のためのＸ線回折用サンプルとし、株式会社リガク製のＵｌｔｉｍａＩＶのＸ線回折装置を用い、回折角度（２θ）５°〜８５°の範囲で測定を行った。その結果、ＧｒとＴｉＢ２の二相であることがわかった。 Sintering mold M consisting of Gr-T i B 2 sintered body produced by the embodiment of this embodiment, according to the X-ray diffraction pattern diagram of FIG. 4, one of the peaks graphite crystal and T i B It shows that we identified two crystals, here, in the measurement of X-ray diffraction pattern, to produce a Gr-T i B 2 bulk sample using a discharge plasma sintering method, grinding the bulk sample Then, an X-ray diffraction sample for crystal phase identification was used, and measurement was performed in a diffraction angle (2θ) range of 5 ° to 85 ° using an Ultimate IV X-ray diffraction apparatus manufactured by Rigaku Corporation. As a result, it was found to be a two-phase of Gr and T i B 2 .
又、図５のＳＥＭによる組織写真によれば、（イ）のＧｒ−ＴｉＢ２焼結体の組織が緻密化していることがわかり、さらに、フレーク組織を示す（ロ）の市販黒鉛金型と異なり、（イ）のＧｒ−ＴｉＢ２焼結体においては、フレーク組織を示さないこともわかる。 Further, according to the structure photograph by SEM of Figure 5, you notice that the organized densification of Gr-T i B 2 sintered body (a), further, a commercially available graphite gold showing a flake tissue (b) Unlike the mold, in the Gr-T i B 2 sintered body (a), it can be seen to show no flakes tissue.
又、図６の電気抵抗の温度依存性を示す図によれば、金属特性を示す素材であることがわかる。この電気抵抗の温度依存性の測定にあっては、放電プラズマ焼結法を用いて作製したＧｒ−ＴｉＢ２焼結体を放電加工により長さ３０ｍｍ、直径６ｍｍに切断してサンプルを得て、その後、四端子法によりサンプルの電流と電圧の関係の温度依存性を測定した。電流、電圧測定には、ＡＤＣＭＴ製６２４２直流電圧電流電源及びモニターを用い、各温度における電流、電圧のプロットからサンプルの電気抵抗を測定した。 Further, according to the graph showing the temperature dependence of the electrical resistance in FIG. 6, it can be seen that the material shows the metal characteristics. The electric In the measurement of the temperature dependence of the resistance, length 30mm by electrical discharge machining Gr-T i B 2 sintered body prepared by using a discharge plasma sintering method, to obtain a sample was cut into a diameter of 6mm Thereafter, the temperature dependence of the relationship between the current and voltage of the sample was measured by the four probe method. For the current and voltage measurement, an ACMT 6242 DC voltage current power source and a monitor were used, and the electric resistance of the sample was measured from plots of current and voltage at each temperature.
[実施例１]
純度９９．９％、平均粒子サイズ６０μｍ以下のＧｒ粉末及び純度９９．９％、平均粒子サイズ６０μｍ以下のＴｉＢ２粉末を用い、黒鉛粉末と上記二硼化チタン粉末とを黒鉛粉末５０重量％、二硼化チタン粉末５０重量％の混合割合で混合し、このＧｒ−ＴｉＢ２混合粉末Ｗを、放電プラズマ焼結法を用いて焼結してＧｒ−ＴｉＢ２焼結体からなる焼結用金型Ｍを作製した。焼結後の金型寸法は、ダイＭ１にあっては、外径５０．００ｍｍ、内径２０．０５ｍｍ、高さ４０．００ｍｍ、各パンチＭ２・Ｍ２にあっては、それぞれ外径２０．００ｍｍ、長さ２５．００ｍｍである。上記焼結の条件は、焼結温度２,０００℃、焼結圧力４０ＭＰａ、焼結時間２０分及び焼結雰囲気は真空雰囲気である。作製した焼結用金型Ｍの相対密度は９８％であった。
[Example 1]
99.9% purity, mean particle size 60 [mu] m following Gr powder and 99.9% purity, using the following T i B 2 powder having an average particle size 60 [mu] m, the graphite powder and the titanium diboride powder and the graphite powder 50 weight %, titanium diboride powder 50 are mixed in the mixing ratio of the weight%, the Gr-T i B 2 mixed powder W, and sintered using spark plasma sintering method Gr-T i B 2 sintered body A sintering mold M comprising: Mold dimensions after sintering, in the die M 1, the outer diameter of 50.00 mm, an inner diameter 20.05Mm, height 40.00 mm, with the respective punches M 2 · M 2, respectively outer diameter 20 0.000 mm and length 25.00 mm. The sintering conditions are a sintering temperature of 2,000 ° C., a sintering pressure of 40 MPa, a sintering time of 20 minutes, and the sintering atmosphere is a vacuum atmosphere. The relative density of the produced sintering mold M was 98%.
[焼結例１]
この実施例１で作製したＧｒ−ＴｉＢ２焼結体を放電加工により仕上して焼結用金型Ｍを作製し、この焼結用金型Ｍを用い、焼結用金型Ｍ内に焼結材料を充填しない状態（ブランク焼結）で、真空雰囲気、温度１,９００℃、圧力２０ＭＰａ、焼結時間６０分の焼結条件で焼結テストを試みた。上記焼結条件で三サイクルを繰り返し行ったが、焼結前後のＧｒ−ＴｉＢ２焼結体から作製した焼結用金型Ｍの割れや焼結用金型Ｍの寸法変形はないことを確認した。
[Sintering Example 1]
The Gr-T i B 2 sintered body produced in this Example 1 were top by electric discharge machining to prepare a sintered mold M, using the sintering mold M, sintering mold in M In a state in which no sintered material was filled (blank sintering), a sintering test was attempted under a vacuum atmosphere, a temperature of 1,900 ° C., a pressure of 20 MPa, and sintering conditions of 60 minutes. Three cycles were repeated under the above sintering conditions, but it was confirmed that there was no crack in the sintering mold M produced from the Gr-TiB 2 sintered body before and after sintering and no dimensional deformation of the sintering mold M. did.
［比較例１］
市販の黒鉛金型を用い、黒鉛金型内に焼結材料を充填しない状態（ブランク焼結）で、焼結例１に記載した焼結条件と同じ焼結条件で三セットの金型で焼結テストを試みた。上記焼結条件で三サイクルを繰り返し行い、焼結前後の黒鉛金型の割れや黒鉛金型の寸法変形はないことを確認したが、変形に関して、パンチ直径は０．３３０ｍｍ太くなり、パンチ長さは０．７９０ｍｍ短くなり、一方、ダイの内径は０．３３５ｍｍ大きくなり、黒鉛金型の変形量が許容範囲外であることを確認した。
[Comparative Example 1]
Using commercially available graphite molds, firing with three sets of molds under the same sintering conditions as described in Sintering Example 1 with no sintering material filled in the graphite mold (blank sintering) I tried the result test. Three cycles were repeated under the above sintering conditions, and it was confirmed that there was no cracking of the graphite mold before and after sintering and no dimensional deformation of the graphite mold, but regarding the deformation, the punch diameter became 0.330 mm thicker and the punch length Was shortened by 0.790 mm, while the inner diameter of the die was increased by 0.335 mm, confirming that the amount of deformation of the graphite mold was outside the allowable range.
[実施例２]
純度９９．９％、平均粒子サイズ６０μｍのＧｒ粉末及び純度９９．９％、平均粒子サイズ６０μｍのＴｉＢ２粉末を用い、黒鉛粉末と上記二硼化チタン粉末とを黒鉛粉末５０重量％、二硼化チタン粉末５０重量％の混合割合で混合し、このＧｒ−ＴｉＢ２混合粉末Ｗを放電プラズマ焼結法を用いて焼結してＧｒ−ＴｉＢ２焼結体からなる焼結用金型Ｍを作製した。焼結後の金型寸法は、ダイＭ１にあっては、外径５０．００ｍｍ、内径２０．０５ｍｍ、高さ４０．００ｍｍ、各パンチＭ２・Ｍ２にあっては、それぞれ外径２０．００ｍｍ、長さ２５．００ｍｍである。焼結条件は、焼結温度２，０００℃、圧力６０ＭＰａ、焼結時間３０分及び焼結雰囲気は真空雰囲気である。作製した焼結用金型Ｍの相対密度は９９％であった。
[Example 2]
Using a Gr powder having a purity of 99.9% and an average particle size of 60 μm and a TiB 2 powder having a purity of 99.9% and an average particle size of 60 μm, the graphite powder and the titanium diboride powder were mixed with 50% by weight of graphite powder. for sintering made of titanium powder 50 is mixed in a mixing ratio of the weight%, the Gr-T i B 2 mixed powder W sintered using spark plasma sintering method Gr-T i B 2 sintered body A mold M was produced. Mold dimensions after sintering, in the die M 1, the outer diameter of 50.00 mm, an inner diameter 20.05Mm, height 40.00 mm, with the respective punches M 2 · M 2, respectively outer diameter 20 0.000 mm and length 25.00 mm. The sintering conditions are a sintering temperature of 2,000 ° C., a pressure of 60 MPa, a sintering time of 30 minutes, and the sintering atmosphere is a vacuum atmosphere. The relative density of the produced sintering mold M was 99%.
［焼結例２］
この実施例２で作製したＧｒ−ＴｉＢ２焼結体からなる焼結用金型Ｍを用い、焼結用金型Ｍ内に焼結材料を充填しない状態（ブランク焼結）で、真空雰囲気、温度２，０００℃、焼結圧力２５０ＭＰａ、焼結時間３０分の焼結条件で焼結テストを三セットで試みた。上記焼結例１と同様に、上記焼結条件で三サイクルを繰り返し行ったが、焼結後のＧｒ−ＴｉＢ２焼結体から作製した焼結用金型Ｍの割れや焼結用金型Ｍの寸法変形はないことを確認した。
[Sintering Example 2]
A sintered mold M consisting of Gr-T i B 2 sintered body prepared in Example 2, with no filling the sintered material in the sintering mold M (blank sintering), vacuum Three sets of sintering tests were attempted under the sintering conditions of atmosphere, temperature of 2,000 ° C., sintering pressure of 250 MPa, and sintering time of 30 minutes. Similar to the above-mentioned sintering example 1, three cycles were repeated under the above-mentioned sintering conditions. However, cracks in the sintering mold M produced from the sintered Gr-TiB 2 sintered body and sintering molds were obtained. It was confirmed that there was no dimensional deformation of M.
［比較例２］
市販の黒鉛金型を用い、黒鉛金型内に焼結材料を充填しない状態（ブランク焼結）で、焼結例２と同じ焼結条件で焼結テストを試みた。上記焼結条件で三サイクルを繰り返し行った焼結例１と同様に焼結後の黒鉛金型の割れや焼結前後の黒鉛金型の寸法変化を確認した。焼結圧力８０ＭＰａで割れが発生することを確認した。
[Comparative Example 2]
Using a commercially available graphite mold, a sintering test was attempted under the same sintering conditions as in Sintering Example 2 with no sintering material filled in the graphite mold (blank sintering). Cracking of the graphite mold after sintering and dimensional changes of the graphite mold before and after sintering were confirmed in the same manner as in sintering example 1 in which three cycles were repeated under the above sintering conditions. It was confirmed that cracking occurred at a sintering pressure of 80 MPa.
［実施例３］
純度９９．９％、平均粒子サイズ６０μｍのＧｒ粉末及び純度９９．９％、平均粒子サイズ６０μｍ以下のＴｉＢ２粉末を用い、黒鉛粉末と上記二硼化チタン粉末とを黒鉛粉末２５重量％、二硼化チタン粉末７５重量％の混合割合で混合し、このＧｒ−ＴｉＢ２混合粉末Ｗを放電プラズマ焼結法を用いて焼結してＧｒ−ＴｉＢ２焼結体からなる焼結用金型Ｍを作製した。焼結用金型Ｍの金型寸法は、ダイＭ１にあっては、外径５０．００ｍｍ、内径２０．０５ｍｍ、高さ４０．００ｍｍ、各パンチＭ２・Ｍ２にあっては、それぞれ外径２０．００ｍｍ、長さ２５．００ｍｍである。焼結条件は、焼結温度２，０００℃、圧力６０ＭＰａ、焼結時間３０分及び焼結雰囲気は真空雰囲気である。作製した焼結用金型Ｍの相対密度は９９％であった。
[Example 3]
Using a Gr powder having a purity of 99.9% and an average particle size of 60 μm and a TiB 2 powder having a purity of 99.9% and an average particle size of 60 μm or less, the graphite powder and the titanium diboride powder were mixed by 25% by weight. They were mixed in a mixing ratio of titanium boride powder 75 wt%, consisting of Gr-T i B 2 sintered body of this Gr-T i B 2 mixed powder W sintered using spark plasma sintering sintering A metal mold M was produced. Mold dimensions of the sintered mold M is, in the die M 1, the outer diameter 50.00 mm, in the inner diameter 20.05Mm, height 40.00 mm, each punch M 2 · M 2, respectively The outer diameter is 20.00 mm and the length is 25.00 mm. The sintering conditions are a sintering temperature of 2,000 ° C., a pressure of 60 MPa, a sintering time of 30 minutes, and the sintering atmosphere is a vacuum atmosphere. The relative density of the produced sintering mold M was 99%.
［焼結例３］
この実施例３で作製したＧｒ−ＴｉＢ２焼結体からなる焼結用金型Ｍを用い、焼結用金型Ｍ内に焼結材料としてのタングステン粉末を充填し、真空雰囲気、焼結温度２，４００℃、圧力４０ＭＰａ、焼結時間１５分の焼結条件で焼結テストを試みた。上記焼結条件で三サイクルを繰り返し行ったが焼結前後の焼結用金型Ｍの割れや焼結用金型Ｍの寸法変形はないことを確認した。
[Sintering Example 3]
A sintered mold M consisting of Gr-T i B 2 sintered body prepared in Example 3, was filled with a tungsten powder as a sintering material in a sintering mold in the M, a vacuum atmosphere, baked A sintering test was attempted under sintering conditions of a sintering temperature of 2,400 ° C., a pressure of 40 MPa, and a sintering time of 15 minutes. Three cycles were repeated under the above sintering conditions, but it was confirmed that there were no cracks in the sintering mold M and dimensional deformation of the sintering mold M before and after sintering.
［比較例３］
市販の黒鉛金型を用い、黒鉛金型内に焼結材料としてのタングステン粉末を充填し、焼結例３と同じ焼結条件で焼結テストを試みた。上記焼結例１及び焼結例２と同様に焼結前後の黒鉛金型の割れ及び黒鉛金型の寸法の変形量を確認した。黒鉛金型の割れはなかったが、黒鉛金型の寸法はダイ内径は０．４７０ｍｍ大きくなり、パンチ直径は０．４６０ｍｍ太くなり、パンチ長さは１．０９２ｍｍ短くなったことを確認した。
[Comparative Example 3]
A commercially available graphite mold was used, tungsten powder as a sintering material was filled in the graphite mold, and a sintering test was attempted under the same sintering conditions as in Sintering Example 3. Similarly to the above-mentioned sintering example 1 and sintering example 2, cracks in the graphite mold before and after sintering and the deformation amount of the dimensions of the graphite mold were confirmed. Although the graphite mold was not cracked, it was confirmed that the size of the graphite mold was 0.470 mm larger for the die inner diameter, 0.460 mm thicker for the punch diameter, and 1.092 mm shorter for the punch length.
［実施例４］
純度９９．９％、平均粒子サイズ６０μｍ以下のＧｒ粉末及び純度９９．９％、平均粒子サイズ６０μｍのＴｉＢ２粉末を用い、黒鉛粉末と上記二硼化チタン粉末とを黒鉛粉末８０重量％、二硼化チタン粉末２０重量％の混合割合で混合し、このＧｒ−ＴｉＢ２混合粉末Ｗを放電プラズマ焼結法を用いて焼結してＧｒ−ＴｉＢ２焼結体からなる焼結用金型Ｍを作製した。焼結後の金型寸法は、ダイＭ１にあっては、外径５０．００ｍｍ、内径２０．０５ｍｍ、高さ４０．００ｍｍ、各パンチＭ２・Ｍ２にあっては、それぞれ外径２０．００ｍｍ、長さ２５．００ｍｍである。焼結条件は、焼結温度２，０００℃、圧力６０ＭＰａ、焼結時間３０分及び焼結雰囲気は真空雰囲気である。作製した焼結用金型Ｍの相対密度は９９％であった。
[Example 4]
Using a Gr powder having a purity of 99.9% and an average particle size of 60 μm or less and a TiB 2 powder having a purity of 99.9% and an average particle size of 60 μm, the graphite powder and the titanium diboride powder were mixed with 80% by weight of graphite powder. They were mixed in a mixing ratio of titanium boride powder 20 wt%, consisting of Gr-T i B 2 sintered body of this Gr-T i B 2 mixed powder W sintered using spark plasma sintering sintering A metal mold M was produced. Mold dimensions after sintering, in the die M 1, the outer diameter of 50.00 mm, an inner diameter 20.05Mm, height 40.00 mm, with the respective punches M 2 · M 2, respectively outer diameter 20 0.000 mm and length 25.00 mm. The sintering conditions are a sintering temperature of 2,000 ° C., a pressure of 60 MPa, a sintering time of 30 minutes, and the sintering atmosphere is a vacuum atmosphere. The relative density of the produced sintering mold M was 99%.
［焼結例４］
この実施例４で作製したＧｒ−ＴｉＢ２焼結体からなる焼結用金型Ｍを用い、焼結用金型Ｍ内に焼結材料としてのタングステン粉末を充填し、真空雰囲気、焼結温度２，４００℃、圧力２５０ＭＰａ、焼結時間１５分の焼結条件で焼結テストを試みた。焼結後の焼結用金型Ｍの割れや焼結前後の焼結用金型Ｍの寸法変化はないことを確認した。
[Sintering Example 4]
A sintered mold M consisting of Gr-T i B 2 sintered body produced in this Example 4, was filled with tungsten powder as a sintering material in a sintering mold in the M, a vacuum atmosphere, baked A sintering test was attempted under sintering conditions of a sintering temperature of 2,400 ° C., a pressure of 250 MPa, and a sintering time of 15 minutes. It was confirmed that there was no crack in the sintering mold M after sintering and no dimensional change of the sintering mold M before and after sintering.
［比較例４］
市販の黒鉛金型を用い、黒鉛金型内に焼結材料としてのタングステン粉末を充填し、焼結例４と同じ焼結条件で焼結テストを試みた。上記焼結例１及び焼結例２と同様に焼結前後の黒鉛金型の割れ及び黒鉛金型の寸法の変形量を確認した。焼結圧力８０ＭＰａ程度で割れが発生することを確認した。
[Comparative Example 4]
A commercially available graphite mold was used, tungsten powder as a sintering material was filled in the graphite mold, and a sintering test was attempted under the same sintering conditions as in Sintering Example 4. Similarly to the above-mentioned sintering example 1 and sintering example 2, cracks in the graphite mold before and after sintering and the deformation amount of the dimensions of the graphite mold were confirmed. It was confirmed that cracking occurred at a sintering pressure of about 80 MPa.
尚、本発明は上記実施の形態例に限られるものではなく、例えば、放電プラズマ焼結法以外の焼結法に用いられる焼結用金型Ｍに適用することもあり、又、焼結用金型ＭのダイＭ１やパンチＭ２・Ｍ２の形状等は適宜変更して設計されるものである。 The present invention is not limited to the above embodiment, and may be applied to, for example, a sintering mold M used in a sintering method other than the spark plasma sintering method. die M 1 and the shape of the punch M 2 · M 2 of the mold M is intended to be designed appropriately changed.
以上の如く、所期の目的を充分達成することができる。 As described above, the intended purpose can be sufficiently achieved.
Ｗ Ｇｒ−ＴｉＢ２混合粉末
Ｍ 焼結用金型
W Gr-T i B 2 mixed powder M sintering mold
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| JP2022533706A (en) * | 2019-05-20 | 2022-07-25 | バテル エナジー アライアンス，エルエルシー | Spark plasma sintering method for making dense graphite |
| CN116000431A (en) * | 2022-12-21 | 2023-04-25 | 中国核动力研究设计院 | Method and device for rapidly welding ODS steel at low temperature by adopting discharge plasma diffusion welding technology |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2022533706A (en) * | 2019-05-20 | 2022-07-25 | バテル エナジー アライアンス，エルエルシー | Spark plasma sintering method for making dense graphite |
| JP7455864B2 (en) | 2019-05-20 | 2024-03-26 | バテル エナジー アライアンス，エルエルシー | Spark plasma sintering method for producing dense graphite |
| CN116000431A (en) * | 2022-12-21 | 2023-04-25 | 中国核动力研究设计院 | Method and device for rapidly welding ODS steel at low temperature by adopting discharge plasma diffusion welding technology |
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