JPH0524855B2 - - Google Patents
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- Publication number
- JPH0524855B2 JPH0524855B2 JP20305287A JP20305287A JPH0524855B2 JP H0524855 B2 JPH0524855 B2 JP H0524855B2 JP 20305287 A JP20305287 A JP 20305287A JP 20305287 A JP20305287 A JP 20305287A JP H0524855 B2 JPH0524855 B2 JP H0524855B2
- Authority
- JP
- Japan
- Prior art keywords
- nitrogen
- temperature
- composite carbonitride
- vacuum
- composite
- 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
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 43
- 239000002131 composite material Substances 0.000 claims description 27
- 229910052757 nitrogen Inorganic materials 0.000 claims description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 14
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 5
- 239000007858 starting material Substances 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 4
- 238000005520 cutting process Methods 0.000 description 16
- 229910052799 carbon Inorganic materials 0.000 description 15
- 239000000956 alloy Substances 0.000 description 14
- 229910045601 alloy Inorganic materials 0.000 description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 13
- 229910052760 oxygen Inorganic materials 0.000 description 13
- 239000001301 oxygen Substances 0.000 description 13
- 239000000843 powder Substances 0.000 description 13
- 239000011195 cermet Substances 0.000 description 11
- 239000002994 raw material Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 238000006722 reduction reaction Methods 0.000 description 7
- 238000005245 sintering Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 5
- 238000003763 carbonization Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- -1 Ni and Co Chemical class 0.000 description 2
- 238000000889 atomisation Methods 0.000 description 2
- 238000005256 carbonitriding Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 150000004767 nitrides Chemical group 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Description
〔産業上の利用分野〕
本発明は、極めて強靭で高品質な窒素含有サー
メツトの製造に必要とする硬質原料の、Ti，
Nb，Ｗの複合炭窒化物の製造法に関する。本発
明による複合炭窒化物を原料とした窒素含有サー
メツトは例えば高速、高送り条件下で使用する切
削工具等に有効に利用できる。
〔従来の技術〕
Ti，Nb，Ｗ等の炭窒化物をNiやCo等の金属
で結合した窒素含有サーメツトは、従来の窒素を
含有しないサーメツトに比べ、その硬質分散相が
著しく微粒になるため、切削工具としての耐塑性
変形性，耐熱疲労性が大幅に改善さることが知ら
れている（特公昭49−1364号公報）。
ところで、この種のサーメツトの作製におい
て、真空中での焼結を行うと、サーメツト合金中
に含有される炭窒化物が分解し、いわゆる脱窒現
象が起きて窒素添加の効果が減少したり、また、
その際に生じた窒素ガスが焼結体から充分に抜け
ずに焼結後にポアとして残存し、いずれも窒素含
有サーメツトの工具としての信頼性を著しく低下
させることになる。
そのために、上記特公昭49−1364号公報には、
該サーメツトを真空中ではなく窒素雰囲気中で焼
結することにより、窒化物の分解を抑えるという
技術が開示されている。
さらに、含有窒素量が増すと脱窒量も増すた
め、その抑制のためには雰囲気窒素圧を80Torr
以上必要とするが、焼結時の該サーメツトからの
脱ガスが不充分となる欠点があつた。
その克服法として、サーメツト中に含有される
金属元素の複合炭窒化物を予め製造して、窒素解
離圧を下げ、焼結中の脱窒を極力抑える方法が提
案されている（例えば特公昭56−51201号公報
等）。
さらに、該複合炭窒化物の粉末を微粒にするた
めに、酸化物を出発原料とし、これに炭素粉末を
混合し、窒素気流中にて加熱させるという試みが
なされている（例えば特開昭61−291408号公報
等）。
また、このような従来の複合炭窒化物の製造法
は、開放型ボート送りの連続炉で、窒素を流した
ままの状態にして、ボートを順次送つていく方式
で行なうのが一般的であつた。
〔発明が解決しようとする問題点〕
しかしながら、従来の酸化物と炭素との混合物
に窒素を流して複合炭窒化物を作製するという方
法では、遊離炭素，酸素が残存し、得られた複合
炭窒化物を原料に用いたサーメツトを作製する際
の焼結過程における焼結性を劣化させ、その結
果、工具としての特性である耐摩耗性や靭性を低
下させてしまうという問題があつた。
本発明はこの問題点を解決して、金属酸化物と
炭素粉末を原料として、酸素や遊離炭素の残存を
防止し、しかも微細な粉末で焼結性の良いTi，
Nb，Ｗの複合炭窒化物の製造法を提案すること
を目的とするものである。
〔問題点を解決するための手段及び作用〕
上記の問題点の解決手段を求めて、本発明者ら
は、酸化物を出発原料とした複合炭窒化物の生成
過程について詳細な検討を行つた。
その結果、前記のように窒素を流した状態で開
放型ボート送り方式で、酸化物原料から複合炭窒
化物を作製する従来法は、明らかに製造工程が簡
略化されており、かつ酸化物原料自体が元来微粒
な粉末であるため、生成する複合炭窒化物粉末も
微粒になる点で有効なものであるが、その反応は
非常に複雑であることが判つた。これは、還元反
応に加え、炭化、窒化各反応が起こり、さらに固
溶化反応も生じるためであり、加熱に伴いまず各
酸化物の還元反応がCOガスの発生として進行し、
引き続き窒化、炭化が重なり合うように起こるも
のであるという知見を得た。
従つてこの知見によれば、酸素を完全除去する
ためには、還元終了温度まで高真空に保ち、その
後窒素を供給するのが理想的手段であるといえ
る。しかし、実際には窒素を流さなければ、ある
温度から粒成長が始まり、当初の目的である微粒
化が充分には図れない。
本発明者らは、これらの状況に鑑みて、酸化物
を原料として、酸素除去、遊離炭素の残留防止と
微粒化の両方を達成できるような加熱方法、特に
雰囲気条件と温度条件について研究を重ね、
TiO2，Nb2O5，WO3及び炭素粉末を出発原料と
して混合し、該混合物を真空中で加熱した後、
1200℃以上1500℃以下の温度で雰囲気中に窒素供
給を開始し、引き続き該窒素雰囲気中で1500℃以
上2100℃以下の温度に保持して反応せしめること
を特徴とするTi，Nb，Ｗの複合炭窒化物の製造
法である本発明に到達したのである。
本発明はTi，Nb，Ｗを、それぞれTiO2，
Nb2O5，WO3という酸化物で供給し、これに炭
素粉体を混合し、これを加熱処理するに際し、ま
ず還元反応が進行する低温側では真空雰囲気で加
熱し、加熱昇温を続けて1200℃以上1500℃以下ま
での範囲において雰囲気への窒素供給を開始し、
引き続きこの窒素雰囲気中で1500℃以上2100℃以
下で加熱することにより、炭窒化反応をさせて
Ti，Nb，Ｗの複炭窒化物を得る方法である。窒
素雰囲気圧力を30Torr以上10気圧以下とするこ
とが特に好ましい。
このように酸化物を出発原料に用いることで、
微粉末が得られる。また、酸化物の還元反応中は
充分に真空を保持するので、酸素含有量を著しく
低下させることができ、かつ、酸素はCOガスと
して抜けるため、炭化するために必要な量の炭素
以外に還元のために混合しておいた炭素も、その
役割を果して抜けてゆく。その結果、残留酸素や
遊離炭素の著しく少ない良質な複合炭窒化物が得
られる。
従つて、本発明の複合炭窒化物を用いてサーメ
ツトを作製すると、非常に焼結性が良く、切削特
性においても耐摩耗性，靭性，耐熱亀裂性の極め
て優れた、信頼性の高い合金が得られるのであ
る。
以下、本発明における一般的方法と制限理由を
述べる。
１ 真空加熱条件
真空度は10-3Torr以上10Torr以下とする。
10-3Torr未満では効果に差異がなく、10Torrを
越えると酸素，遊離炭素を充分に除去することが
できない。真空に保持する時間については特に制
限するところはない。
２ 昇温速度
常温（加熱処理開始）から1500℃以上2100℃以
下の最高到達温度までの全温度域で１〜100℃／
分が好ましい。１℃／分より小さいと粒成長する
し、100℃／分より大きいと、酸素，遊離炭素を
充分に除去することができない。
３ 窒素供給開始温度
1200℃以上1500℃以下で窒素供給を開始する。
1200℃未満で供給すると、該複合炭窒化物中に酸
素が残留し、1500℃を越えても窒素供給しないで
おくと粒成長をきたし、合金の硬度を低下させる
ことになるので好ましくない。
４ 加熱処理中の窒素雰囲気圧力
30Torr以上10気圧以下とする。30Torr未満で
は窒素供給による微細化の効果が得られず、また
10気圧を越えてもその効果に差異はないに加え、
設備的に無駄が生じるので好ましくない。
５ 反応温度
窒素雰囲気中で1500℃以上2100℃以下で保持し
反応させる。1500℃未満では固溶が不充分で好ま
しくなく、一方、2100℃を越えると粒生長が著し
くなるので好ましくない。
６ 最高到達温度での保持時間
10分以上５時間以下が好ましい。10分未満では
還元反応が不充分であり、５時間を越えると粒成
長をきたすので好ましくない。
〔実施例〕
以下、実施例により本発明を具体的に説明す
る。各実施例・比較例において、真空度は炉から
排気管に20cm入つた位置で測定した。
実施例 １
TiO2粉末，Nb2O5粉末，WO3粉末とＣ粉末を
混合して水練り造粒し、1400℃まで0.1Torrの真
空中で加熱の後、PN2＝１気圧の窒素を導入し、
1700℃でで１時間保持し、本発明の複合炭窒化物
Ａを得た。なお、加熱処理開始から1700℃までの
昇温速度は10℃／分で行なつた。
比較として、同様に造粒したものをPN2＝１気
圧の窒素雰囲気下で1700℃まで10℃／分の昇温速
度で加熱し、この条件で１時間保持した比較品Ｂ
を得た。
Ａ，Ｂ各試料の分析結果を第１表に示す。第１
表から、方発明品Ａと比較品Ｂは粒度では殆んど
差がないものの、本発明品Ａでは遊離炭素及び酸
素量が著しく減少していることが、明らかに判
る。
得られた複合炭窒化物Ａ，ＢにそれぞぞれNi，
Coを８重量ずつ添加して、サーメツト合金を作
製すべく、1450℃で１時間焼結した。得られた合
金は、本発明品Ａを原料としたものには巣が殆ん
ど存在しなかつたのに対し、比較品Ｂを原料とし
たものは、A06タイプ（超硬工具協会規格CIS
006B−1983）の巣が認められた。
実施例 ２
Ti：Nb：Ｗ＝0.76：0.09：0.06，Ｃ：Ｎ＝
0.52：0.48、非金属成分／金属成分の比が1.0とな
るように、第１表のように金属又は酸化物，炭化
物，炭窒化物を混合し、各試料について1320℃ま
で0.2Torrの真空加熱後、1320℃からPN2＝１気
圧で窒素を導入し、この窒素雰囲気下1600℃で２
時間保持した。加熱処理開始から1600℃までの昇
温は12℃／分で行なつた。
得られた本発明品Ｃと比較品Ｄ，Ｅの複合炭窒
化物についての分析結果を第２表に示す。
この結果、本発明品Ｃは酸化物原料を用いず金
属粉を用いた比較品Ｄに比べ粒度がはるかに小さ
く遊離炭素量が減少していること、また炭窒化物
や炭化物を原料とする比較品Ｅに比べて酸素量は
少なく遊離炭素量は多いとはいえ0.01以下であ
り、粒度は非常に小さいことが判る。すなわち本
発明品が最も微細であることが認められた。
[Industrial Field of Application] The present invention is directed to hard raw materials such as Ti,
This article relates to a method for producing a composite carbonitride of Nb and W. The nitrogen-containing cermet made from composite carbonitride according to the present invention can be effectively used, for example, in cutting tools used under high-speed, high-feed conditions. [Prior art] Nitrogen-containing cermets, which are made by bonding carbonitrides such as Ti, Nb, and W with metals such as Ni and Co, have significantly finer particles in their hard dispersed phase compared to conventional cermets that do not contain nitrogen. It is known that the plastic deformation resistance and thermal fatigue resistance of cutting tools are significantly improved (Japanese Patent Publication No. 1364/1983). By the way, when sintering in a vacuum in the production of this type of cermet, the carbonitrides contained in the cermet alloy decompose, a so-called denitrification phenomenon occurs, and the effect of nitrogen addition decreases. Also,
The nitrogen gas generated at this time does not escape sufficiently from the sintered body and remains as pores after sintering, which significantly reduces the reliability of the nitrogen-containing cermet as a tool. For this purpose, the above-mentioned Japanese Patent Publication No. 1364-1987 states that
A technique has been disclosed in which the decomposition of nitrides is suppressed by sintering the cermet in a nitrogen atmosphere rather than in a vacuum. Furthermore, as the amount of nitrogen content increases, the amount of denitrification also increases, so in order to suppress this, it is necessary to increase the atmospheric nitrogen pressure to 80 Torr.
Although the above is necessary, there is a drawback that degassing from the cermet during sintering is insufficient. As a method to overcome this problem, a method has been proposed in which a composite carbonitride of the metal elements contained in the cermet is produced in advance to lower the nitrogen dissociation pressure and to minimize denitrification during sintering (for example, −51201, etc.). Furthermore, in order to make the composite carbonitride powder into fine particles, attempts have been made to use an oxide as a starting material, mix carbon powder with it, and heat it in a nitrogen stream (for example, in JP-A-61 −291408, etc.). In addition, conventional methods for producing composite carbonitrides are generally carried out in an open boat-fed continuous furnace, in which the boats are fed one after another while nitrogen is kept flowing. Ta. [Problems to be solved by the invention] However, in the conventional method of producing composite carbonitride by flowing nitrogen through a mixture of oxide and carbon, free carbon and oxygen remain, and the resulting composite carbon There has been a problem in that the sinterability in the sintering process when producing cermets using nitrides as a raw material deteriorates, and as a result, the wear resistance and toughness, which are characteristics of tools, decrease. The present invention solves this problem and uses metal oxide and carbon powder as raw materials to prevent oxygen and free carbon from remaining.
The purpose of this study is to propose a method for producing composite carbonitrides of Nb and W. [Means and effects for solving the problems] In search of a means for solving the above problems, the present inventors conducted a detailed study on the production process of composite carbonitrides using oxides as starting materials. . As a result, the conventional method of producing composite carbonitride from oxide raw materials using the open boat feeding method under flowing nitrogen as described above clearly simplifies the manufacturing process and Since the composite carbonitride powder itself is originally a fine powder, it is effective in that the resulting composite carbonitride powder also becomes fine, but the reaction was found to be very complicated. This is because, in addition to the reduction reaction, carbonization and nitridation reactions occur, as well as a solid solution reaction. As the heating progresses, the reduction reaction of each oxide first proceeds as CO gas is generated.
Subsequently, we obtained the knowledge that nitridation and carbonization occur in a superimposed manner. Therefore, according to this knowledge, in order to completely remove oxygen, it can be said that the ideal means is to maintain a high vacuum until the reduction end temperature and then supply nitrogen. However, in reality, unless nitrogen is flowed, grain growth begins at a certain temperature, and the original objective of atomization cannot be achieved sufficiently. In view of these circumstances, the present inventors have conducted repeated research on heating methods that can achieve both oxygen removal, prevention of residual free carbon, and atomization using oxides as raw materials, particularly on atmospheric conditions and temperature conditions. ,
After mixing TiO 2 , Nb 2 O 5 , WO 3 and carbon powder as starting materials and heating the mixture in vacuum,
A composite of Ti, Nb, and W, characterized in that nitrogen supply is started in the atmosphere at a temperature of 1200°C or more and 1500°C or less, and the reaction is continued by maintaining the temperature in the nitrogen atmosphere at a temperature of 1500°C or more and 2100°C or less. The present invention, which is a method for producing carbonitrides, has been achieved. The present invention replaces Ti, Nb, and W with TiO 2 and
Oxides such as Nb 2 O 5 and WO 3 are supplied, carbon powder is mixed with this, and when this is heat-treated, first, it is heated in a vacuum atmosphere on the low temperature side where the reduction reaction proceeds, and then the heating temperature is continued to rise. Start supplying nitrogen to the atmosphere in the range of 1200℃ to 1500℃.
Subsequently, by heating in this nitrogen atmosphere at a temperature of 1500°C or more and 2100°C or less, a carbonitriding reaction is caused.
This is a method for obtaining a double carbonitride of Ti, Nb, and W. It is particularly preferable that the nitrogen atmosphere pressure be 30 Torr or more and 10 atmospheres or less. By using oxides as starting materials in this way,
A fine powder is obtained. In addition, since a sufficient vacuum is maintained during the oxide reduction reaction, the oxygen content can be significantly reduced, and since oxygen escapes as CO gas, it is reduced to other than the amount of carbon required for carbonization. The carbon that has been mixed in for this purpose also plays its role and escapes. As a result, a high-quality composite carbonitride containing significantly less residual oxygen and free carbon can be obtained. Therefore, when a cermet is made using the composite carbonitride of the present invention, a highly reliable alloy with very good sinterability and excellent cutting properties such as wear resistance, toughness, and heat cracking resistance can be obtained. You can get it. The general method and reasons for limitations in the present invention will be described below. 1 Vacuum heating conditions The degree of vacuum should be 10 -3 Torr or more and 10 Torr or less.
At less than 10 -3 Torr, there is no difference in effectiveness, and at more than 10 Torr, oxygen and free carbon cannot be removed sufficiently. There is no particular restriction on the time for holding in vacuum. 2 Temperature increase rate: 1 to 100℃/in the entire temperature range from room temperature (start of heat treatment) to the maximum temperature of 1500℃ or higher and 2100℃ or lower.
Minutes are preferred. If it is less than 1°C/min, grains will grow, and if it is more than 100°C/min, oxygen and free carbon cannot be removed sufficiently. 3 Nitrogen supply start temperature Start nitrogen supply at a temperature of 1200°C or higher and 1500°C or lower.
If nitrogen is supplied at a temperature lower than 1200°C, oxygen will remain in the composite carbonitride, and if nitrogen is not supplied even if the temperature exceeds 1500°C, grain growth will occur and the hardness of the alloy will decrease, which is not preferable. 4 Nitrogen atmosphere pressure during heat treatment: 30 Torr or more and 10 atmospheres or less. If it is less than 30Torr, the effect of refinement by nitrogen supply cannot be obtained, and
In addition to the fact that there is no difference in the effect even if the pressure exceeds 10 atmospheres,
This is not preferable because it causes waste in terms of equipment. 5 Reaction temperature The reaction is maintained at 1500°C or higher and 2100°C or lower in a nitrogen atmosphere. If the temperature is lower than 1500°C, the solid solution will be insufficient, which is undesirable. On the other hand, if the temperature exceeds 2100°C, grain growth will become significant, which is undesirable. 6 Holding time at maximum temperature Preferably 10 minutes or more and 5 hours or less. If the reaction time is less than 10 minutes, the reduction reaction will be insufficient, and if it exceeds 5 hours, grain growth will occur, which is not preferable. [Example] Hereinafter, the present invention will be specifically explained with reference to Examples. In each Example and Comparative Example, the degree of vacuum was measured at a position 20 cm into the exhaust pipe from the furnace. Example 1 TiO 2 powder, Nb 2 O 5 powder, WO 3 powder and C powder were mixed and granulated by water kneading, heated to 1400°C in a vacuum of 0.1 Torr, and then nitrogen at P N2 = 1 atm was added. introduced,
The mixture was held at 1700° C. for 1 hour to obtain composite carbonitride A of the present invention. Note that the temperature increase rate from the start of the heat treatment to 1700°C was 10°C/min. For comparison, Comparative Product B was prepared by heating a similarly granulated product to 1700°C at a heating rate of 10°C/min in a nitrogen atmosphere of P N2 = 1 atm and holding it under these conditions for 1 hour.
I got it. The analysis results for each sample A and B are shown in Table 1. 1st
From the table, it is clearly seen that although there is almost no difference in particle size between Invention Product A and Comparative Product B, the amount of free carbon and oxygen is significantly reduced in Invention Product A. Ni and Ni were added to the obtained composite carbonitrides A and B, respectively.
Co was added in 8 weight portions and sintered at 1450° C. for 1 hour to produce a cermet alloy. The obtained alloy had almost no cavities in the alloy made from product A of the present invention, whereas the alloy made from comparison product B had A06 type (Cemented Carbide Tool Association standard CIS).
006B-1983) nests were observed. Example 2 Ti:Nb:W=0.76:0.09:0.06, C:N=
Mix metals, oxides, carbides, and carbonitrides as shown in Table 1 so that the ratio of nonmetallic components/metallic components is 0.52:0.48 and 1.0, and heat each sample in vacuum at 0.2 Torr to 1320°C. After that, nitrogen was introduced from 1320℃ at P N2 = 1 atm, and 2 at 1600℃ under this nitrogen atmosphere.
Holds time. The temperature was raised from the start of the heat treatment to 1600°C at a rate of 12°C/min. Table 2 shows the analysis results for the composite carbonitrides of product C of the present invention and comparative products D and E. As a result, the particle size of product C of the present invention is much smaller than that of comparative product D, which uses metal powder without using oxide raw materials, and the amount of free carbon is reduced. It can be seen that although the amount of oxygen is lower and the amount of free carbon is higher than Product E, it is less than 0.01, and the particle size is extremely small. In other words, the product of the present invention was found to be the finest.
【表】【table】
【表】
実施例 ３
TiO2，Nb2O5，WO3，Ｃの各粉末を第３表の
如く配合し、加熱、還元、炭窒化処理を施した。
このときの昇温速度は12℃／分、真空度は0.1〜
0.5Torr、PN2は全て400Torrとした。得られた本
発明品Ｆ〜Ｉ及び比較品Ｊ〜Ｏの複合炭窒化物の
分析結果も合せて第３表に示す。[Table] Example 3 TiO 2 , Nb 2 O 5 , WO 3 , and C powders were blended as shown in Table 3, and subjected to heating, reduction, and carbonitriding treatments.
At this time, the temperature increase rate is 12℃/min, and the degree of vacuum is 0.1~
0.5Torr and P N2 were all set to 400Torr. Table 3 also shows the analysis results of the composite carbonitrides of the products F to I of the present invention and comparative products J to O.
【表】
実施例 ４
実施例１〜３で得た複合炭窒化物Ａ，Ｂ，Ｅ，
Ｈ，Ｍ，Ｎを原料として用い、これ等にNi，Co
を10％重量ずつ添加し、混合してプレス後、1420
℃、PN2＝3Torrの窒素雰囲気下で１時間焼結し
てサーメツト合金を作製した。得られた合金をそ
れぞれＰ，Ｑ，Ｒ，Ｓ，Ｔ，Ｕとする。各合金の
硬度、抗折力を第４表に示す。[Table] Example 4 Composite carbonitrides A, B, E, obtained in Examples 1 to 3,
H, M, and N are used as raw materials, and Ni and Co are added to these.
After adding 10% by weight, mixing and pressing, 1420
A cermet alloy was produced by sintering in a nitrogen atmosphere at ℃ and P N2 =3 Torr for 1 hour. The obtained alloys are designated as P, Q, R, S, T, and U, respectively. Table 4 shows the hardness and transverse rupture strength of each alloy.
【表】【table】
【表】
さらに原料Ｅ，Ｎを用いて、硬度を向上させる
べく、Ni，Coの添加量を７重量％ずつにして、
1450℃、PN2＝5Torrで１時間焼結し、合金Ｖ，
Ｗを得た。これ等の合金の硬度、抗折力を第５表
に示すが、抗折力が著しく低下した。[Table] Furthermore, using raw materials E and N, in order to improve the hardness, the amounts of Ni and Co added were changed to 7% by weight each.
Alloy V,
I got a W. The hardness and transverse rupture strength of these alloys are shown in Table 5, and the transverse rupture strength was significantly reduced.
【表】
次に上記Ｐ〜Ｗの合金について、下記の条件で
切削試験を行つた。試験結果を第６表に示すが、
本発明の複合炭窒化物を原料とした合金がフラン
ク摩耗量、断続切削での欠損数、フライス断続切
削での熱亀裂発生本数のいずれの項目においても
優れていることが判る。
条件１ 連続切削
被削材 SCM440（HB＝280）
切削速度 180m／min
送 り 0.36mm／rev
切り込み 1.5mm
チツプ形状 SNGN120408
ホルダー FNllR−44A
切削時間 ５分間
条件２ 断続切削
被削材 SCM435（HB＝250）、４溝材
切削速度 100m／min
送 り 0.25mm／rev
切り込み 2.0mm
チツプ形状 SNGN120408
ホルダー FNllR−44A
切削時間 欠損まで。最大２分間。
条件３ フライス断続切削
被削材 SCM435（HB＝250）50mm×150mm
の角材
切削速度 150m／min
送 り 0.15mm／刃
切り込み 4.0mm
チツプ形状 SNGN120408
ホルダー DNF460R
切削時間 ７分間[Table] Next, cutting tests were conducted on the alloys P to W above under the following conditions. The test results are shown in Table 6.
It can be seen that the alloy made from the composite carbonitride of the present invention is superior in terms of flank wear amount, number of defects in interrupted cutting, and number of thermal cracks generated in interrupted milling cutting. Condition 1 Continuous cutting workpiece SCM440 (H B = 280) Cutting speed 180m/min Feed 0.36mm/rev Depth of cut 1.5mm Chip shape SNGN120408 Holder FNllR-44A Cutting time 5 minutes Condition 2 Intermittent cutting workpiece SCM435 (H B = 250), 4-groove material cutting speed 100m/min Feed 0.25mm/rev Depth of cut 2.0mm Chip shape SNGN120408 Holder FNllR-44A Cutting time Until chipping. Maximum of 2 minutes. Condition 3 Milling interrupted cutting workpiece material SCM435 (H B = 250) 50mm x 150mm
Cutting speed of square material 150m/min Feed 0.15mm/blade depth of cut 4.0mm Chip shape SNGN120408 Holder DNF460R Cutting time 7 minutes
以上説明したように、本発明の複合炭窒化物の
製造法は、微細な粉末で、かつ酸素や遊離炭素の
著しく少ない良質なTi，Nb，Ｗの複合炭窒化物
が得られるという効果がある。さらに本発明によ
るTi，Nb，Ｗの複合炭窒化物の粉末を用いてサ
ーメツトを作製すると、非常に焼結性が良く、切
削工具特性においても耐摩耗性、靭性、耐熱亀裂
性に極めて優れた合金になるという効果がある。
As explained above, the method for producing a composite carbonitride of the present invention has the effect of obtaining a fine powder composite carbonitride of Ti, Nb, and W of high quality with significantly less oxygen and free carbon. . Furthermore, when a cermet is made using the composite carbonitride powder of Ti, Nb, and W according to the present invention, it has very good sinterability and has extremely excellent cutting tool properties such as wear resistance, toughness, and heat cracking resistance. It has the effect of forming an alloy.
Claims (1)
料として混合し、該混合物を真空中で加熱した
後、1200℃以上1500℃以下の温度で雰囲気中に窒
素供給を開始し、引き続き該窒素雰囲気中で1500
℃以上2100℃以下の温度に保持して反応せしめる
ことを特徴とするTi，Nb，Ｗの複合炭窒化物の
製造法。 ２ 加熱処理中の窒素雰囲気圧力を30Torr以上
10気圧以下とする特許請求の範囲第１項に記載さ
れるTi，Nb，Ｗの複合炭窒化物の製造法。[Claims] 1. Mix TiO 2 , Nb 2 O 5 , WO 3 and carbon powder as starting materials, heat the mixture in vacuum, and then add nitrogen to the atmosphere at a temperature of 1200°C to 1500°C. Start supplying and continue to supply 1500 ml in the nitrogen atmosphere.
A method for producing a composite carbonitride of Ti, Nb, and W, characterized in that the reaction is carried out while maintaining the temperature at a temperature of ℃ to 2100℃. 2.Nitrogen atmosphere pressure during heat treatment is 30Torr or more.
A method for producing a composite carbonitride of Ti, Nb, and W as set forth in claim 1, wherein the pressure is 10 atmospheres or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20305287A JPS6445705A (en) | 1987-08-17 | 1987-08-17 | Production of composite carbon nitride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20305287A JPS6445705A (en) | 1987-08-17 | 1987-08-17 | Production of composite carbon nitride |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6445705A JPS6445705A (en) | 1989-02-20 |
| JPH0524855B2 true JPH0524855B2 (en) | 1993-04-09 |
Family
ID=16467545
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20305287A Granted JPS6445705A (en) | 1987-08-17 | 1987-08-17 | Production of composite carbon nitride |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6445705A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5756410A (en) * | 1997-02-27 | 1998-05-26 | The Dow Chemical Company | Method for making submicrometer transition metal carbonitrides |
-
1987
- 1987-08-17 JP JP20305287A patent/JPS6445705A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6445705A (en) | 1989-02-20 |
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