JPS62287041A - Production of high-alloy steel sintered material - Google Patents
Production of high-alloy steel sintered materialInfo
- Publication number
- JPS62287041A JPS62287041A JP61129228A JP12922886A JPS62287041A JP S62287041 A JPS62287041 A JP S62287041A JP 61129228 A JP61129228 A JP 61129228A JP 12922886 A JP12922886 A JP 12922886A JP S62287041 A JPS62287041 A JP S62287041A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- alloy steel
- sintering
- molding
- hardness
- 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.)
- Pending
Links
- 229910000851 Alloy steel Inorganic materials 0.000 title claims abstract description 15
- 239000000463 material Substances 0.000 title claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 238000005245 sintering Methods 0.000 claims abstract description 23
- 239000000843 powder Substances 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims description 24
- 238000001513 hot isostatic pressing Methods 0.000 claims description 19
- 239000011812 mixed powder Substances 0.000 claims description 4
- 239000000956 alloy Substances 0.000 abstract description 12
- 150000001247 metal acetylides Chemical class 0.000 abstract description 12
- 238000000465 moulding Methods 0.000 abstract description 9
- 238000001816 cooling Methods 0.000 abstract description 3
- 238000007493 shaping process Methods 0.000 abstract description 3
- 229910052799 carbon Inorganic materials 0.000 abstract 2
- 229910052804 chromium Inorganic materials 0.000 abstract 2
- 150000001875 compounds Chemical class 0.000 abstract 2
- 230000002706 hydrostatic effect Effects 0.000 abstract 2
- 229910052750 molybdenum Inorganic materials 0.000 abstract 2
- 229910052721 tungsten Inorganic materials 0.000 abstract 2
- 229910052720 vanadium Inorganic materials 0.000 abstract 2
- 229910045601 alloy Inorganic materials 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 239000007791 liquid phase Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 229910000997 High-speed steel Inorganic materials 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000004663 powder metallurgy Methods 0.000 description 3
- 239000002131 composite material Substances 0.000 description 2
- 238000000280 densification Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000005204 segregation Methods 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910009043 WC-Co Inorganic materials 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 238000009694 cold isostatic pressing Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000009770 conventional sintering Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000007712 rapid solidification Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Powder Metallurgy (AREA)
Abstract
Description
【発明の詳細な説明】
３、発明の詳細な説明
〔産業上の利用分野〕
本発明は高合金鋼焼結材料の製造方法に関し、さらに詳
しくは、微細組織を持ち、ニアネットシエイブ（Ｎｅａ
ｒ Ｎｅｔ ５ｈａｐｅ） （７）”ｆ能な方法で低コ
ストに高合金の高硬度焼結材料を製造する方法を提供す
るものである。Detailed Description of the Invention 3. Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a method for producing a high-alloy steel sintered material, and more specifically, the present invention relates to a method for producing a high-alloy steel sintered material having a microstructure and a near net
r Net 5 hape) (7) "Providing a method for producing a high-alloy, high-hardness sintered material at a low cost and in an efficient manner.
高硬度材料の代表的なものに超硬合金があるが、これは
硬さは大Ｓい（ＨＲＣが７４以１−）反面、靭性が小（
シャルピー衝撃値が０．５ ｋ ｇ ｆ・ｍ／ｃｍ′程
度）であるという欠点を持ち、その上コスト高の材料で
ある。A typical example of high-hardness materials is cemented carbide, which has high hardness (HRC of 74 to 1-) but low toughness (
It has the drawback of having a Charpy impact value of about 0.5 kg f·m/cm'), and is also a high-cost material.
一方、靭性の高い高硬度材料としては高速度鋼が知られ
ている。この高速度鋼の硬さを大きくするためには、合
金成分の増量が考えられるが、溶製法では、炭化物の偏
析が避けられないため困難である。これに対し、急冷凝
固により合金ｊｌｌを過飽和に固溶させた銅粉を焼結き
せる粉末冶金法は、溶製法に比べて、炭化物の偏析の少
ない組織が得られる。On the other hand, high-speed steel is known as a high-hardness material with high toughness. In order to increase the hardness of this high-speed steel, it is possible to increase the amount of alloying components, but this is difficult in the melting method because segregation of carbides is unavoidable. On the other hand, the powder metallurgy method of sintering copper powder in which alloy jll is supersaturated as a solid solution by rapid solidification provides a structure with less segregation of carbides than the melting method.
従来の粉末冶金による高速度鋼の製造は、１′、にガス
アトマイズ粉末をカプセル充填した後、熱間静水圧成形
（ＨＩＰ）Ｌ、鋼塊を製造して、加下成形する方法によ
ってル翫た。これはＡ、ＫａｓａｋらノＰｏｗｄｅｒ−
ｍｅｔａｌｌｕｒｇｙ 、ｔｏｏｌ ５ｔｅｅｌｓ （
ＰｏｗｄｅｒＭｅｔａｌｌｕｒｇｙ、 １９７８． ｖ
ｏ１２１．１１４）に示されるように、特性は良いが、
ニアネットシェイブが難しい方法である。The production of high-speed steel using conventional powder metallurgy involves 1' encapsulating gas atomized powder, followed by hot isostatic pressing (HIP) to produce a steel ingot, and then subjecting it to compression forming. . This is A, Kasak et al.'s Powder-
metalurgy, tool 5teels (
PowderMetalurgy, 1978. v
o121.114), the characteristics are good, but
Near net shave is the difficult method.
これに対し、通常の焼結による製造が考えられており、
特公昭５８−４７４４４号公報によると、水アトマイズ
粉末を仕上還元した後、液相焼結することにより製造可
能であることが示されている。しかしこの方法は焼結の
みで緻密化を行うため、空孔が充分除去できず、さらに
靭性の低下をもたらす。On the other hand, manufacturing by normal sintering is considered,
According to Japanese Patent Publication No. 58-47444, it is shown that it can be manufactured by carrying out liquid phase sintering after finishing reduction of water atomized powder. However, since this method performs densification only by sintering, pores cannot be sufficiently removed, further resulting in a decrease in toughness.
また焼結により閉気孔となりＨＩＰがかけられるように
焼結炉で焼結し、冷却後取り出して後ＨＩＰ炉でＨＩＰ
処理を行い空孔を除去し靭性の向上を図る方法が超硬合
金（ＷＣ−Ｃｏ）の製造に利用されているが、この方法
では、生産性が低くコスト高になるという問題がある。In addition, sintering is performed in a sintering furnace so that the pores become closed due to sintering, and HIP is applied. After cooling, it is taken out and then HIPed in a HIP furnace.
A method of processing to remove pores and improve toughness is used in the production of cemented carbide (WC-Co), but this method has the problem of low productivity and high cost.
そこで本発明は、硬さと靭性の両特性が優れた微細組織
を持ち、ニアネットシェイプが可能で、しかも低コスト
で高合金の高硬度焼結材料を製造する方法を提供するこ
とを目的とする。Therefore, an object of the present invention is to provide a method for manufacturing a high-alloy, high-hardness sintered material that has a microstructure with excellent properties of both hardness and toughness, is capable of near-net shaping, and is low-cost. .
本発明者らは、高合金材料について検討の結果、次の工
程によれば、ニアネットシエイプで、さらに硬さと靭性
の両特性が優れた微細組織を有し、高合金組成を持った
高硬度焼結材料を得られることを見出した。As a result of studies on high-alloy materials, the present inventors found that, according to the following process, a high-hardness material with a near-net shape, a microstructure with excellent properties of both hardness and toughness, and a high alloy composition. It has been found that a sintered material can be obtained.
すなわち、最終的な組成が
Ｃ：０．５〜４重量％
Ｃｒ：３〜６重量％
Ｗ ：６〜５０重量％
Ｖ：０．５〜２０重量％
を含み、かつ
Ｍｏ：２〜２２重量％
Ｃｏ２４〜２０重量％
のうち少なくとも一種を含み、残部が実質的にＦｅ組成
からなる合金鋼粉末、または上記組成に配合した合金鋼
の混合粉末を冷間成形した後焼結し、室温近くまでの冷
却を経ないで、直ちに同一炉内で熱間静水圧（ＨＩＰ）
処理を行う。これにより、従来のＨＩＰ法では困難なニ
アネットシェイプを低コストで容易に実現することがで
き、しかも高合金組成のため硬さが高く、靭性にも優れ
た微細組織を持つ高硬度材料が得られる。That is, the final composition contains C: 0.5 to 4% by weight, Cr: 3 to 6% by weight, W: 6 to 50% by weight, V: 0.5 to 20% by weight, and Mo: 2 to 22% by weight. Alloy steel powder containing at least one type of Co24 to 20% by weight and the remainder substantially consisting of Fe, or a mixed powder of alloy steel blended with the above composition, is cold-formed and then sintered, and then heated to near room temperature. Hot isostatic pressure (HIP) immediately in the same furnace without cooling
Perform processing. This makes it possible to easily achieve a near-net shape at low cost, which is difficult to achieve with the conventional HIP method.Moreover, a high-hardness material with a microstructure with high hardness and excellent toughness due to its high alloy composition can be obtained. It will be done.
以下、本発明法の構成を作用と共に詳細に説明する。 Hereinafter, the structure of the method of the present invention will be explained in detail along with its operation.
まず、基本成分範囲の限定理由について説明する。First, the reason for limiting the basic component range will be explained.
Ｃ：０．５〜４重量％
ＣはＦｅ基地中に固溶し、基地の硬さを高め、さらに合
金成分と炭化物を形成して硬さ向上に寄与する。その効
果を得るためには少なくとも０．５重量％以上のＣ量が
必要であり、また４重量％を超えると脆くなり靭性な劣
化させるので、０．５〜４重量％と定める。C: 0.5 to 4% by weight C is dissolved in the Fe base, increases the hardness of the base, and further forms carbides with alloy components to contribute to improving the hardness. In order to obtain this effect, an amount of C of at least 0.5% by weight is required, and if it exceeds 4% by weight, it becomes brittle and the toughness deteriorates, so it is set at 0.5 to 4% by weight.
Ｃｒ ： ３．０〜６．０重量％
ＣｒはＦｅ基地中に固溶して強度と焼入性を向上させる
一方、複合炭化物を形成して硬度を高め、耐摩耗性を向
上させる。その効果を得るには少なくとも３．０重量％
が必要であり、また６、０重量％を超えると靭性を劣化
させるので、３．０〜６．０重量％と定める。Cr: 3.0 to 6.0% by weight Cr forms a solid solution in the Fe base to improve strength and hardenability, and forms composite carbides to increase hardness and improve wear resistance. At least 3.0% by weight to achieve the effect
is required, and if it exceeds 6.0% by weight, the toughness deteriorates, so it is set at 3.0 to 6.0% by weight.
Ｗ ：６〜５０重量％
Ｗは特に微細な複合炭化物を形成して硬度を高め、耐摩
耗性を向上させる重要元素である。その効果は、６重量
％以上の含有によって顕著になり、硬さは上昇するが、
５０重量％を超えると、炭化物が急激に成長し易くなり
、その結果靭性が劣化するので、６〜５０重量％とした
。W: 6 to 50% by weight W is an important element that forms particularly fine composite carbides to increase hardness and improve wear resistance. The effect becomes remarkable when the content is 6% by weight or more, and the hardness increases, but
If it exceeds 50% by weight, carbides tend to grow rapidly and as a result, toughness deteriorates, so the content was set at 6 to 50% by weight.
Ｖ：０．５〜２０重量％
■は硬質炭化物を形成して硬度を高め、耐摩耗性と切削
性能を向上させるため、０．５重量％以」−が必要であ
る。しかし、２０重量％を超えると靭性を劣化させるの
で、０．５〜２０重量％を定める。V: 0.5 to 20% by weight ① is required to be 0.5% by weight or more in order to form hard carbides, increase hardness, and improve wear resistance and cutting performance. However, if it exceeds 20% by weight, the toughness deteriorates, so the range is determined to be 0.5 to 20% by weight.
Ｃｏ ： ４．０〜２０．０重量％
ＣＯは特に高温硬さを向上させるために有効な元素であ
り、ざらにＣＯ添加によってＭＯを省略することも可能
である。その効果は４．０重量％以」−の含有で顕著と
なるが、２０．０重量％を越えて含有させると靭性を劣
化させてしまうので、４．０〜２０．０重量％とすべき
である。Co: 4.0 to 20.0% by weight CO is an element particularly effective for improving high-temperature hardness, and it is also possible to omit MO by adding CO. The effect becomes noticeable when the content is 4.0% by weight or more, but since the content exceeds 20.0% by weight, the toughness deteriorates, so the content should be 4.0 to 20.0% by weight. It is.
Ｍ ｏ ： ２〜２２重量％
ＭｏはＷと同様の効果を持ち、その添加によって、一層
耐摩耗性を向」ニさせるとともに、Ｗの一部を置きかえ
るためにも使用される。Ｗが６重量％以」−含有されて
いる場合にＭＯの追加添加の効果が現れる最小ＭＯ量は
２重量％である。一方、通常用いられるＷ当ｉｌｌ、す
なわちＷ ＋ ２ Ｍ ｏ量が５０重量％を超えるとＷ
の場合と同様炭化物が粗大化して靭性を劣化させるから
、Ｍ ｏ ｆｉとして２２重量％が」−眼となる。Mo: 2 to 22% by weight Mo has the same effect as W, and its addition further improves the wear resistance, and is also used to partially replace W. When W is contained at 6% by weight or more, the minimum amount of MO at which the effect of additional addition of MO appears is 2% by weight. On the other hand, when the amount of W + 2 Mo that is commonly used exceeds 50% by weight, W
As in the case of , the carbide becomes coarse and deteriorates the toughness, so 22% by weight is the M o fi.
Ｉ−記に示した限定成分と残部Ｆｅからなる合金鋼粉ま
たはその組成に配合した混合粉末でもって高合金組成化
が可能で、硬さの優れた焼結体が製造できる。A high alloy composition can be obtained by using an alloy steel powder consisting of the limiting components shown in I- and the balance being Fe, or a mixed powder blended with that composition, and a sintered body with excellent hardness can be produced.
本発明方法は、」−記組成粉末な冷間で成形する。通常
の粉末冶金のように金型を用いて成形する場合は、潤滑
剤を添加するのが普通である。金型成形のほかに冷間静
水圧成形や射出成形でも成形可使である。In the method of the present invention, a powder having the following composition is cold-molded. When molding is performed using a mold as in ordinary powder metallurgy, a lubricant is usually added. In addition to molding, it can also be molded by cold isostatic pressing and injection molding.
次の工程は焼結ならびに熱間静水圧成形（ＨＩＰ）であ
る。焼結とＨＩＰ処理は同一炉内で行なう。この方法に
より、焼結炉とＨＩＦ炉を別々に運転しなくて済み、従
来のＨＩＰ処理を行う場合と比べて、低コスト化が可能
となる。The next steps are sintering and hot isostatic pressing (HIP). Sintering and HIP processing are performed in the same furnace. This method eliminates the need to operate the sintering furnace and the HIF furnace separately, making it possible to reduce costs compared to conventional HIP processing.
焼結は、真空中またはＨ２中で行う。加圧状態での焼結
も可能である。焼結温度を調整して、炭化物の微細な組
織を持つ緻密体を液相焼結によって得る。はぼ緻密化し
た後、直ちに、焼結体に直接ＨＩＰ処理を行う。焼結お
よびＨＩＰは１０００℃〜１３００℃、０．５ ｈ ｒ
−７ｈ ｒ（１）範囲で行われる。ＨＩＰ処理の温度は
液相焼結での炭化物の成長を防ぐために焼結時よりも少
し低目に選ぶことも可能である。ＨＩＰ処理の圧力は、
焼結体に僅かでも液相が存在すると、通常のＨＩＰ圧力
よりも低圧化が可能である。Sintering is performed in vacuum or in H2. Sintering under pressure is also possible. A dense body with a fine carbide structure is obtained by liquid phase sintering by adjusting the sintering temperature. Immediately after densification, the sintered body is directly subjected to HIP treatment. Sintering and HIP at 1000°C to 1300°C, 0.5 hr
Performed in the -7hr r(1) range. The temperature of the HIP process can be selected to be slightly lower than that during sintering in order to prevent the growth of carbides during liquid phase sintering. The pressure of HIP treatment is
If even a small amount of liquid phase exists in the sintered body, the pressure can be lowered than the normal HIP pressure.
従来の焼結炉で焼結後一旦冷却後取出し、ざらにＨＩＦ
炉で処理する場合、ＨＩＰの温度上昇時に炭化物の成長
が生じるため、靭性が著しく劣化する。靭性な著しく劣
化させないためには炭化物粒径５Ｊｉ、ｍ以下が望まし
い。この問題は焼結とＨＩＦを同一炉内で行うことによ
り、解決されることが解った。After sintering in a conventional sintering furnace, it is cooled and then taken out and processed into a rough HIF.
When processing in a furnace, carbide growth occurs when the HIP temperature increases, resulting in a significant deterioration of toughness. In order to avoid significant deterioration of toughness, it is desirable that the carbide particle size be 5 Ji, m or less. It has been found that this problem can be solved by performing sintering and HIF in the same furnace.
以上に述べた工程により炭化物の粗大化の無い、緻細な
組織をもつ、すなわち硬さと靭性に優れ、ニアネットシ
エイブが可能な高硬度合金材料の製造が可能となる。The process described above makes it possible to produce a high-hardness alloy material that has a fine structure without coarsening of carbides, that is, has excellent hardness and toughness, and is capable of near net shaving.
以下に本発明の実施例について述べる。 Examples of the present invention will be described below.
第１表に示す成分組成からなる予合金（プレアロイ）粉
あるいは混合粉を、平均粒径１１〜１３Ｂｍに粉砕して
焼鈍した後、ステアリン酸亜鉛を１重量％混合し、成形
圧力６ｔ／ｃｒｎ’でφ１１．３ｍｍＸｌｏｍｍの試験
片に成形した。これを脱ろう処理して、真空中（１０−
１０Ｔｏｒｒ）で１時間焼結させ、同一炉内で直ちにＡ
ｒガス中、１００気圧で２時間ＨＩＰ処理（焼結−ＨＩ
Ｐ法）を行った。その詩の焼結およびＨＩＰ処理の条件
と、特性値を第１表に示す。Pre-alloyed powder or mixed powder having the composition shown in Table 1 is pulverized to an average particle size of 11 to 13 Bm and annealed, then mixed with 1% by weight of zinc stearate, and the molding pressure is 6t/crn'. It was molded into a test piece with a diameter of 11.3 mm and a diameter of 11.3 mm. This was dewaxed and in vacuum (10-
10 Torr) for 1 hour, and immediately sintered in the same furnace.
HIP treatment (sintering-HI) in r gas at 100 atm for 2 hours
P method) was performed. Table 1 shows the sintering and HIP treatment conditions and characteristic values of the poem.
比較例のうち、Ｎｏ、１．３，５，７，９゜１１．１３
，１５，１７，１９．２１は別個に焼結炉とＨＩＰ装置
を用いて処理したもの（焼結−ＨＩＰ分離法）で、Ｎｏ
、２．２２は焼結−ＨＩＰ法で処理を行った。ＨＩＰ処
理温度は第１表の通りで行い空孔率は全て０．１％以下
であった。Among the comparative examples, No. 1.3, 5, 7, 9°11.13
, 15, 17, 19.21 were processed separately using a sintering furnace and HIP device (sintering-HIP separation method), and No.
, 2.22 was processed by the sintering-HIP method. The HIP treatment temperature was as shown in Table 1, and the porosity was all 0.1% or less.
第１図に炭化物平均粒径とＷ量の関係を焼結−ＨＩＰ法
と焼結−ＨＩＰ分離法に分けて示す。焼結−ＨＩＰ法は
Ｗ量の増加による炭化物成長が緩やかで、焼結−ＨＩＰ
分離法は炭化物成長が著しい。Ｗ量が６重量％以下では
、これらの差は見られないが、６重量％以」二では明ら
かである。Ｗ量が５０重量％を超えると、焼結−ＨＩＰ
法でも炭化物が成長（５ｇｍ以」二）シ過ぎる。このた
め靭性が劣化する。FIG. 1 shows the relationship between the average grain size of carbides and the amount of W for the sintering-HIP method and the sintering-HIP separation method. In the sintering-HIP method, carbide growth is gradual due to the increase in W content, and the sintering-HIP method
The separation method causes significant carbide growth. These differences are not observed when the amount of W is 6% by weight or less, but are obvious when the amount of W is 6% by weight or more. When the amount of W exceeds 50% by weight, sintering-HIP
Even with the method, the carbide grows too much (more than 5 gm). As a result, toughness deteriorates.
以］−示したように、本発明によれば微細な炭化物組織
を持つ高合金の高硬度合金材料をニアネットシエイプの
可能な方法で、低コストで製造することができる。As described above, according to the present invention, a high-alloy, high-hardness alloy material having a fine carbide structure can be manufactured at low cost by a method that allows near net shape.
第１図はＷ量と炭化物平均粒径との関係を焼結−ＨＩＰ
分離法と焼結−ＨＩＰ法に分けて示すグラフである。Figure 1 shows the relationship between the amount of W and the average grain size of carbides during sintering-HIP.
It is a graph showing the separation method and the sintering-HIP method separately.
Claims (1)
鋼組成に配合した合金鋼の混合粉末を冷間成形し、該成
形体を焼結した後直ちに熱間静水圧成形（ＨＩＰ）処理
を行うことを特徴とする高合金鋼焼結材料の製造方法。[Claims] 1 Contains C: 0.5-4% by weight, Cr: 3-6% by weight, W: 6-50% by weight, V: 0.5-20% by weight, and Mo: 2-22% by weight. An alloy steel powder containing at least one type of Co: 4 to 20% by weight or a mixed powder of an alloy steel blended with the above alloy steel composition is cold-formed, and immediately after sintering the compact, hot isostatic pressing ( 1. A method for producing a high-alloy steel sintered material, the method comprising performing HIP) treatment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61129228A JPS62287041A (en) | 1986-06-05 | 1986-06-05 | Production of high-alloy steel sintered material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61129228A JPS62287041A (en) | 1986-06-05 | 1986-06-05 | Production of high-alloy steel sintered material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62287041A true JPS62287041A (en) | 1987-12-12 |
Family
ID=15004326
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61129228A Pending JPS62287041A (en) | 1986-06-05 | 1986-06-05 | Production of high-alloy steel sintered material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62287041A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5811410A (en) * | 1989-09-21 | 1998-09-22 | Hyal Pharmaceutical Corporation | Method of administering of a hyaluronic acid and an NSAID to decrease side effects of the NSAID |
| US5817644A (en) * | 1991-07-03 | 1998-10-06 | Hyal Pharmaceutical Corporation | Targeting of dosages of medicine and therapeutic agents |
| US5990095A (en) * | 1991-07-03 | 1999-11-23 | Hyal Pharmaceutical Corporation | Use of hyaluronic acid and forms to prevent arterial restenosis |
| US6147059A (en) * | 1992-02-20 | 2000-11-14 | Hyal Pharmaceutical Corporation | Formulations containing hyaluronic acid |
| US8758819B2 (en) | 2006-09-13 | 2014-06-24 | Enhance Skin Products, Inc. | Cosmetic compositions for the treatment of skin and methods thereof |
| CN111378897A (en) * | 2020-04-20 | 2020-07-07 | 燕山大学 | Roll surface repairing material of wrapper roll and laser cladding remanufacturing method of wrapper roll |
-
1986
- 1986-06-05 JP JP61129228A patent/JPS62287041A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5811410A (en) * | 1989-09-21 | 1998-09-22 | Hyal Pharmaceutical Corporation | Method of administering of a hyaluronic acid and an NSAID to decrease side effects of the NSAID |
| US5827834A (en) * | 1989-09-21 | 1998-10-27 | Hyal Pharmaceutical Corporation | Method of using hyaluronic acid or its pharmaceutically acceptable salts for the treatment of disease |
| US5830882A (en) * | 1989-09-21 | 1998-11-03 | Hyal Pharmaceutical Corporation | Compositions containing a form of hyaluronic acid and a medicinal agent for treating acne in mammals and methods for administration of such composition |
| US5852002A (en) * | 1989-09-21 | 1998-12-22 | Hyal Pharmaceutical Corporation | Treatment of conditions and disease |
| US6194392B1 (en) | 1989-09-21 | 2001-02-27 | Hyal Pharmaceutical Corporation | Treatment of conditions and disease |
| US5817644A (en) * | 1991-07-03 | 1998-10-06 | Hyal Pharmaceutical Corporation | Targeting of dosages of medicine and therapeutic agents |
| US5990095A (en) * | 1991-07-03 | 1999-11-23 | Hyal Pharmaceutical Corporation | Use of hyaluronic acid and forms to prevent arterial restenosis |
| US6147059A (en) * | 1992-02-20 | 2000-11-14 | Hyal Pharmaceutical Corporation | Formulations containing hyaluronic acid |
| US8758819B2 (en) | 2006-09-13 | 2014-06-24 | Enhance Skin Products, Inc. | Cosmetic compositions for the treatment of skin and methods thereof |
| CN111378897A (en) * | 2020-04-20 | 2020-07-07 | 燕山大学 | Roll surface repairing material of wrapper roll and laser cladding remanufacturing method of wrapper roll |
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