JPH0249362B2 - - Google Patents
Info
- Publication number
- JPH0249362B2 JPH0249362B2 JP59034041A JP3404184A JPH0249362B2 JP H0249362 B2 JPH0249362 B2 JP H0249362B2 JP 59034041 A JP59034041 A JP 59034041A JP 3404184 A JP3404184 A JP 3404184A JP H0249362 B2 JPH0249362 B2 JP H0249362B2
- Authority
- JP
- Japan
- Prior art keywords
- melting point
- powder
- sheet
- adhesive
- laminate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000000843 powder Substances 0.000 claims description 113
- 238000002844 melting Methods 0.000 claims description 68
- 239000000853 adhesive Substances 0.000 claims description 67
- 230000001070 adhesive effect Effects 0.000 claims description 66
- 230000008018 melting Effects 0.000 claims description 64
- 239000002184 metal Substances 0.000 claims description 46
- 229910052751 metal Inorganic materials 0.000 claims description 46
- 238000005245 sintering Methods 0.000 claims description 33
- 239000000956 alloy Substances 0.000 claims description 30
- 229910045601 alloy Inorganic materials 0.000 claims description 30
- 239000000758 substrate Substances 0.000 claims description 26
- 239000004925 Acrylic resin Substances 0.000 claims description 24
- 229920000178 Acrylic resin Polymers 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 21
- 239000007791 liquid phase Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 14
- 238000004898 kneading Methods 0.000 claims description 9
- 230000001590 oxidative effect Effects 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 2
- 239000007789 gas Substances 0.000 description 37
- 239000000463 material Substances 0.000 description 14
- 239000000126 substance Substances 0.000 description 14
- 239000011269 tar Substances 0.000 description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- 238000009835 boiling Methods 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 230000007547 defect Effects 0.000 description 6
- 229910001873 dinitrogen Inorganic materials 0.000 description 6
- 239000006023 eutectic alloy Substances 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 230000035939 shock Effects 0.000 description 4
- 239000007790 solid phase Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000005979 thermal decomposition reaction Methods 0.000 description 4
- 230000007423 decrease Effects 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 230000008961 swelling Effects 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000007872 degassing Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 238000003754 machining Methods 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000000994 depressogenic effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011295 pitch Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 239000011271 tar pitch Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Landscapes
- Powder Metallurgy (AREA)
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、金属基体表面に焼結層を形成する方
法に関するものである。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a method for forming a sintered layer on the surface of a metal substrate.
（従来技術）
従来より、金属基体に対し、耐摩耗性が要求さ
れる表面に粉末合金シートを接着した後、この粉
末合金シートを加熱焼結して耐摩耗性焼結層を得
るようにした技術は、特公昭53−19540号に見ら
れるように公知である。(Prior art) Conventionally, a powder alloy sheet is adhered to the surface of a metal substrate where wear resistance is required, and then this powder alloy sheet is heated and sintered to obtain a wear-resistant sintered layer. The technique is known as seen in Japanese Patent Publication No. 53-19540.
しかるに、この粉末合金シートの焼結方法にお
いては、金属基体の下面、傾斜面、曲面等に対し
粉末合金シートを接着した際に、焼結温度である
1000℃程度の高温状態に加熱する過程においても
上記シートが確実に金属基体表面に接着している
だけの密着強度が得られない恐れがある。 However, in this method of sintering a powder alloy sheet, when the powder alloy sheet is adhered to the lower surface, inclined surface, curved surface, etc. of a metal substrate, the sintering temperature is
Even in the process of heating to a high temperature state of about 1000° C., there is a possibility that the adhesive strength sufficient to ensure that the sheet adheres to the surface of the metal substrate cannot be obtained.
一方、本件出願人が先に提案した特願昭57−
1931125号明細書に開示されている粉末合金シー
トは、加熱焼結時に粉末合金シートに混入されて
いる粘着剤もしくは粉末合金シートを金属基体に
接着するための接着剤の焼失に伴つて発生するガ
スによつて、焼結層に凹みまたは脹れ等の欠陥が
生起する恐れがある。 On the other hand, the applicant had previously proposed a patent application filed in 1983.
The powder alloy sheet disclosed in the specification of No. 1931125 does not contain the gas generated when the adhesive mixed in the powder alloy sheet or the adhesive for bonding the powder alloy sheet to the metal substrate is burned out during heating and sintering. This may cause defects such as dents or bulges in the sintered layer.
すなわち、第５図Ａ〜Ｄに焼結工程を順に示す
ように、金属基体Ｍ表面に、合金粉末と合成樹脂
粘着剤とを混練してある粉末合金シートＳを接着
剤Ｐを使用して接着（第５図Ａ参照）した後、約
1100℃程度の焼結温度に加熱処理する。この焼結
温度への昇温過程において、1050℃位の温度で第
５図Ｂの如く粉末合金シートＳの表面が溶融して
液相ｅを示し、この状態からのガスの発生に伴つ
て第５図Ｃに示すように粉末合金シートＳの一部
に脹れｆを形成し、この閉じ込められたガスが液
相ｅを破つて噴出したときには、焼結完了後の焼
結層表面に第５図Ｄに示すように当該部分が液相
の移動により逆に凹みｄとして欠陥が残るもので
ある。また、上記脹れｆが破れずにそのまま焼結
が完了すると、表面に突部が残つて、焼結層と金
属基体Ｍとの接合が不十分となる問題を有する。 That is, as the sintering process is sequentially shown in FIGS. 5A to 5D, a powder alloy sheet S prepared by kneading alloy powder and a synthetic resin adhesive is adhered to the surface of a metal base M using an adhesive P. (See Figure 5A) After that, approx.
Heat treatment to a sintering temperature of approximately 1100℃. In the process of raising the temperature to this sintering temperature, the surface of the powder alloy sheet S melts at a temperature of about 1050°C and exhibits a liquid phase e as shown in Figure 5B, and as gas is generated from this state, a liquid phase e occurs. As shown in Figure 5C, a bulge f is formed in a part of the powder alloy sheet S, and when this trapped gas breaks the liquid phase e and blows out, a fifth layer is formed on the surface of the sintered layer after sintering is completed. As shown in Figure D, the defect remains in this area as a concave d due to the movement of the liquid phase. Further, if the sintering is completed without tearing the bulge f, a protrusion remains on the surface, resulting in a problem that the bonding between the sintered layer and the metal base M becomes insufficient.
上記現象の発生原因を研究したところ、粘着剤
および接着剤の樹脂成分の熱分解によるガス発生
が焼結温度近傍の高温状態においても生じている
ことによると判明した。つまり、上記のように金
属基体に粉末合金シートを接着して加熱し焼結を
行う際に、300℃付近から粘着剤および接着剤の
低沸点成分がガス化して揮散し、600℃付近では
高沸点成分ガスの発生が始まり、900℃程度に上
昇するとガスの発生は殆どなく、さらに温度が
1050℃程度に上昇すると、前述のように液相が生
成されるとともに、再びガスの発生があり、この
ガスは液相の存在によつて粉末合金シートを通つ
て抜けるのが阻害され、金属基体とシートとの間
に閉じこめられ、さらに発生したガスで内圧が上
昇して粉末合金シートを持ち上げて脹らますもの
である。 When the cause of the above phenomenon was investigated, it was found that it was caused by gas generation due to thermal decomposition of the adhesive and the resin component of the adhesive, even at high temperatures near the sintering temperature. In other words, when a powder alloy sheet is bonded to a metal substrate and heated and sintered as described above, the adhesive and low boiling point components of the adhesive gasify and volatilize from around 300°C, and at around 600°C, the low boiling point components of the adhesive gasify and evaporate. The generation of boiling point component gases begins, and when the temperature rises to around 900℃, there is almost no gas generation, and the temperature continues to rise.
When the temperature rises to about 1050°C, a liquid phase is generated as described above, and gas is generated again.The presence of the liquid phase prevents this gas from passing through the powder alloy sheet, and the metal substrate The generated gas increases the internal pressure, lifting the powder alloy sheet and causing it to swell.
上記現象は粘着剤の焼結温度までの加熱に伴う
ガスの発生状況をガスクロマトグラフによつて測
定した結果から判明したものである。この測定結
果を第６図に示し、分析方法は装置として熱分解
装置を備えたガスクロマトグラフを用い、ステン
レスカラムに所定量の試料（アクリル系樹脂粘着
剤、試料量24.11mg）を入れて300℃、600℃、900
℃、1050℃と順に各温度で５分間加熱を繰り返
し、発生したガスをN2ガスをキヤリアガスとし
て収集し、分析測定したものである。 The above phenomenon was discovered from the results of gas chromatograph measurements of the gas generated as the adhesive was heated to the sintering temperature. The measurement results are shown in Figure 6, and the analysis method was to use a gas chromatograph equipped with a pyrolysis device, put a predetermined amount of sample (acrylic resin adhesive, sample amount 24.11 mg) into a stainless steel column, and heat it at 300°C. , 600℃, 900
℃ and 1050℃ for 5 minutes at each temperature, the generated gas was collected using N 2 gas as a carrier gas, and analyzed and measured.
第６図の結果に見られる如く、300℃で低沸点
成分のガスが発生し、600℃では高沸点成分のガ
スが発生し、900℃ではガスの発生は殆ど見られ
なかつたのに対し、1050℃ではタールピツチ化し
て残存する有機成分のガスが発生している。この
1050℃の温度近傍では、粉末合金シートは液相の
出現が始まつて焼結が表面から生起して接着剤お
よび粉末合金シートの粘着剤から発生するガスの
逃げ場を塞ぎ、粉末合金シートと金属基体との間
にガスが溜るためシートが脹れる。そして、この
脹れた部分のガスが膨張し、シートを破り、次い
でシート部は凹み状態となる。表面に凹みができ
ると均一な焼結層の厚さにならないため、加工代
も多く、粉末合金シート材料を必要以上に要し、
焼結層は硬質層であるため加工工程にも時間を要
する不具合を有している。 As seen in the results in Figure 6, low boiling point component gas was generated at 300℃, high boiling point component gas was generated at 600℃, and almost no gas generation was observed at 900℃. At 1050°C, it turns into tarp and generates residual organic gas. this
At a temperature around 1050℃, the powder alloy sheet begins to exhibit a liquid phase and sintering occurs from the surface, blocking the escape of gases generated from the adhesive and the adhesive of the powder alloy sheet, and causing the powder alloy sheet and the metal to sinter. The sheet swells because gas accumulates between it and the substrate. Then, the gas in this swollen portion expands and tears the sheet, and then the sheet portion becomes depressed. If depressions are formed on the surface, the thickness of the sintered layer will not be uniform, resulting in a large processing cost and the need for more powder alloy sheet material.
Since the sintered layer is a hard layer, it also has the disadvantage that the processing process requires time.
（発明の目的）
本発明は上記事情に鑑み、合成樹脂の焼失温度
を越えて金属同志の焼結温度に至るまでの高温に
おいても粉末シートと母材との間に必要な接着力
を有するとともに、粉末シートの粘着剤または接
着剤の焼失に伴つて発生するガスを良好に逃がし
てやり、ガス抜けを容易にして焼結層に脹らみも
しくは凹み等の欠陥が発生しないようにした金属
基体表面に焼結層を形成する方法を提供すること
を目的とするものである。(Object of the Invention) In view of the above circumstances, the present invention provides the necessary adhesive force between the powder sheet and the base material even at high temperatures exceeding the burnout temperature of synthetic resin and reaching the sintering temperature of metals. , a metal substrate that allows the gas generated when the adhesive or adhesive of the powder sheet burns out to escape easily, thereby preventing defects such as swelling or dents from occurring in the sintered layer. The object of the present invention is to provide a method for forming a sintered layer on a surface.
（発明の構成）
本発明の焼結層形成方法は、耐摩耗性を有する
低融点の合金粉末にアクリル系樹脂からなる粘着
剤を混練して形成した低融点粉末シートと、高融
点の金属粉末にアクリル系樹脂からなる粘着剤を
混練して形成し、かつ液相焼結時に該粘着剤の焼
失による気孔率が20〜60％となる高融点粉末シー
トとを設け、高融点粉末シートと低融点粉末シー
トを交互に複数層重ね合わせてロール圧着して積
層体を形成し、該積層体を所定の厚さに切断し、
該積層体を、高融点粉末シートと低融点粉末シー
トとが金属基体の接合面とほぼ直角な方向に積層
された状態で金属基体表面に接着し、次に積層体
を非酸化性雰囲気下で150〜380℃の温度で５分以
上加熱保持した後、少なくとも高融点粉末シート
が固相状態で低融点粉末シートの液相焼結（半液
相状態も含む）して金属基体表面に焼結層を形成
することを特徴とするものである。(Structure of the Invention) The sintered layer forming method of the present invention comprises a low melting point powder sheet formed by kneading a wear-resistant, low melting point alloy powder with an adhesive made of acrylic resin, and a high melting point metal powder sheet. A high melting point powder sheet is formed by kneading an adhesive made of acrylic resin, and has a porosity of 20 to 60% due to burnout of the adhesive during liquid phase sintering. Multiple layers of melting point powder sheets are alternately stacked and roll-pressed to form a laminate, and the laminate is cut to a predetermined thickness,
The laminate is adhered to the surface of the metal substrate in a state in which the high melting point powder sheet and the low melting point powder sheet are laminated in a direction substantially perpendicular to the bonding surface of the metal substrate, and then the laminate is placed in a non-oxidizing atmosphere. After heating and holding at a temperature of 150 to 380°C for 5 minutes or more, at least the high melting point powder sheet is in a solid state, and the low melting point powder sheet is liquid phase sintered (including a semi-liquid state) and sintered on the surface of the metal substrate. It is characterized by forming a layer.
（発明の効果）
本発明によれば、金属基体表面に低融点粉末シ
ートと高融点粉末シートとを重ね合せた積層体を
接着することにより、粉末シートの粘着剤または
接着剤が焼失する際に発生するガスの抜けを容易
にし、温度が上昇して低融点粉末シート表面に液
相が生成されてもガスは高融点粉末シートを通つ
て放出され、金属基体と積層体との接合部にガス
が溜ることがなく、焼結層に脹れもしくは凹み等
の欠陥が発生するのを未然に防止することがで
き、加工代も少なくして材料費および加工コスト
の低減化が図れる。(Effects of the Invention) According to the present invention, by adhering a laminate in which a low melting point powder sheet and a high melting point powder sheet are stacked on the surface of a metal substrate, when the adhesive or adhesive of the powder sheet is burned out, This makes it easy for the generated gas to escape, and even if the temperature rises and a liquid phase is generated on the surface of the low melting point powder sheet, the gas is released through the high melting point powder sheet, and the gas is released at the joint between the metal substrate and the laminate. This prevents the accumulation of defects such as swelling or dents in the sintered layer, and reduces machining costs, thereby reducing material costs and machining costs.
また、積層体を焼結する際、金属基体に積層体
を接着した後、液相焼結する前に150〜380℃の温
度に５分以上加熱保持することにより、焼結温度
に至るまで良好な積層体の接着性を有し、積層体
による焼結層と金属基体とが良好に密着接合して
品質の優れた焼結層を得ることができるものであ
る。 In addition, when sintering the laminate, after bonding the laminate to the metal substrate, heat and hold at a temperature of 150 to 380°C for 5 minutes or more before liquid phase sintering will ensure a good temperature up to the sintering temperature. The sintered layer of the laminate has excellent adhesion, and the sintered layer of the laminate and the metal base can be bonded well to each other, and a sintered layer of excellent quality can be obtained.
（実施例）
第１図は本発明の一実施態様における金属基体
に積層体を接着した状態を示す断面図である。(Example) FIG. 1 is a sectional view showing a state in which a laminate is adhered to a metal base in one embodiment of the present invention.
鉄系の金属基体１表面に、焼結層を形成するた
めの低融点粉末シート２と高融点粉末シート３と
を重ね合せた積層体５を接着してなる。 A laminate 5 in which a low melting point powder sheet 2 and a high melting point powder sheet 3 for forming a sintered layer are laminated is adhered to the surface of an iron-based metal base 1.
上記低融点粉末シート２は融点が例えば950〜
1150℃程度の低温で耐摩耗性を有する合金粉末に
アクリル系樹脂からなる粘着剤を混練して形成し
てなる。また、高融点粉末シート３は上記低融点
粉末シート２の合金粉末より高い融点（例えば
1050℃以上）を有する金属粉末にアクリル系樹脂
からなる粘着剤を混練して形成してなる。金属基
体１に接着する積層体５は、金属基体１の接合面
と直角な方向に、低融点粉末シート２と高融点粉
末シート３を交互に複数層接着し積層してなり、
上記積層体５を接着した後、上記積層体５を非酸
化性雰囲気（真空もしくは水素ガス雰囲気）下
で、150〜380℃の温度で５分以上加熱保持した
後、さらに、上記非酸化性雰囲気（真空もしくは
水素ガス雰囲気）下で、950〜1150℃の温度で高
融点粉末シート３が固相状態で低融点粉末シート
２を液相焼結して、金属基体１に耐摩耗性の焼結
層を接合形成するものである。 The low melting point powder sheet 2 has a melting point of, for example, 950~
It is formed by kneading an adhesive made of acrylic resin with an alloy powder that has wear resistance at a low temperature of about 1150°C. Further, the high melting point powder sheet 3 has a melting point higher than that of the alloy powder of the low melting point powder sheet 2 (for example,
It is formed by kneading an adhesive made of acrylic resin with metal powder having a temperature of 1050°C or higher). The laminate 5 to be adhered to the metal substrate 1 is made by laminating a plurality of low melting point powder sheets 2 and high melting point powder sheets 3 alternately bonded and laminated in a direction perpendicular to the bonding surface of the metal substrate 1,
After bonding the laminate 5, the laminate 5 is heated and held at a temperature of 150 to 380°C for 5 minutes or more in a non-oxidizing atmosphere (vacuum or hydrogen gas atmosphere), and then further heated in the non-oxidizing atmosphere (vacuum or hydrogen gas atmosphere). Under (vacuum or hydrogen gas atmosphere), the low melting point powder sheet 2 is liquid-phase sintered at a temperature of 950 to 1150°C with the high melting point powder sheet 3 in a solid phase state, and the metal base 1 is sintered with wear resistance. It is used to bond and form layers.
上記金属基体１に積層体５を接着した状態にお
いては、高融点粉末シート３は低融点粉末シート
２との接合面（両側面）と大気開放面（上端面）
とを有し、低融点粉末シート２から発生したガス
を導いて大気開放面から放出するように設けてい
る。 When the laminate 5 is adhered to the metal base 1, the high melting point powder sheet 3 has a joint surface (both sides) with the low melting point powder sheet 2 and a surface open to the atmosphere (upper end surface).
It is provided so that the gas generated from the low melting point powder sheet 2 is guided and released from the atmosphere open surface.
また、上記積層体５は、第２図に示すように広
い面積を有する帯状の低融点粉末シート２と高融
点粉末シート３とを交互に多数枚積層し、圧着ロ
ール６で圧着した後、所定の厚さに切断して形成
するものである。なお、低融点粉末シート２と高
融点粉末シート３との接着は、自己粘着性による
圧着もしくは接着剤を使用して行う。 As shown in FIG. 2, the laminate 5 is made by alternately laminating a large number of belt-shaped low-melting point powder sheets 2 and high-melting point powder sheets 3 having a wide area, and pressing them together with a pressure roll 6. It is formed by cutting to a thickness of . Note that the low-melting point powder sheet 2 and the high-melting point powder sheet 3 are bonded together using self-adhesive pressure bonding or an adhesive.
上記の実施態様においては、金属基体１に積層
体５の接着後、150〜380℃の温度に５分以上保持
する熱処理（例えば300℃×60分）の時に、低融
点粉末シート２および高融点粉末シート３のアク
リル系樹脂の低沸点成分のガスは比較的自由に放
出されるとともに、その一部は重縮合反応により
タール状となつて高温時の金属基体１と両粉末シ
ート２，３との接着を確保する。次に焼結工程に
おいて、1050℃程度に加熱されると高沸点成分ガ
スが発生するが、この時点では低融点粉末シート
２は表面（大気開放面）部分から液相が出始めて
おり、一方、高融点粉末シート３は融点が高いた
めまだ固相の状態で有機成分の焼失によつて気孔
が形成されていることから、発生したガスは高融
点粉末シート３を通つて大気開放面から放出され
る。さらに加熱されると、高沸点成分のガス発生
も終り、低融点粉末シート２と高融点粉末シート
３と金属基体１とは互いに拡散して焼結結合を終
了する。 In the embodiment described above, after bonding the laminate 5 to the metal substrate 1, during heat treatment (for example, 300°C x 60 minutes) held at a temperature of 150 to 380°C for 5 minutes or more, the low melting point powder sheet 2 and the high melting point The gas of the low boiling point component of the acrylic resin in the powder sheet 3 is released relatively freely, and a part of it becomes tar-like due to a polycondensation reaction, and is transferred to the metal substrate 1 and both powder sheets 2 and 3 at high temperatures. to ensure adhesion. Next, in the sintering process, when heated to about 1050°C, high boiling point component gas is generated, but at this point, the low melting point powder sheet 2 has begun to produce a liquid phase from the surface (the surface open to the atmosphere), and on the other hand, Since the high melting point powder sheet 3 has a high melting point and is still in a solid phase, pores are formed by burning off the organic components, so the generated gas passes through the high melting point powder sheet 3 and is released from the surface open to the atmosphere. Ru. When heated further, the gas generation of the high boiling point components ends, and the low melting point powder sheet 2, the high melting point powder sheet 3, and the metal base 1 diffuse into each other to complete the sintering bond.
上記低融点粉末シートは、P0.5〜2.5重量％，
C1.5〜4.5重量％，Mo2.5〜10.5重量％，Cr≦10重
量％，残部Feで、粉末粒度150メツシユ以下より
なる耐摩耗性共晶合金粉末85〜97容量％と溶剤で
溶いたアクリル系樹脂粘着剤15〜３容量％とを混
練した後、圧延したものを所定形状に切断してな
るものである。 The above low melting point powder sheet contains P0.5~2.5% by weight,
Dissolved in a solvent with 85-97 volume% wear-resistant eutectic alloy powder consisting of 1.5-4.5% by weight of C, 2.5-10.5% by weight of Mo, Cr≦10% by weight, balance Fe, and a powder particle size of 150 mesh or less. It is prepared by kneading 15 to 3% by volume of an acrylic resin adhesive, rolling it, and cutting it into a predetermined shape.
さらに、低融点粉末シートの具体的な実施例を
示して説明すれば、P1.2重量％，Mo4.9重量％，
Cr6.2重量％，C1.9重量％，Si0.4重量％，残部Fe
の組成を有し、粒度200メツシユ以下の耐摩耗性
共晶合金粉末97重量％（91容量％）と、アクリル
系樹脂粘着剤３重量％（９容量％）とにトルエン
を加えて湿式混練し、ロール圧延によつて密度が
4.6ｇ／cm3、厚さが1.5mmになるようにシート化
し、これを15mm×18mmの大きさに切断し、低融点
粉末シートの試料を作製した。 Furthermore, to explain specific examples of low melting point powder sheets, P1.2% by weight, Mo4.9% by weight,
Cr6.2wt%, C1.9wt%, Si0.4wt%, balance Fe
97% by weight (91% by volume) of wear-resistant eutectic alloy powder with a particle size of 200 mesh or less and 3% by weight (9% by volume) of an acrylic resin adhesive are wet-kneaded by adding toluene. , the density is increased by roll rolling.
A sheet having a weight of 4.6 g/cm 3 and a thickness of 1.5 mm was formed, and this was cut into a size of 15 mm x 18 mm to prepare a sample of a low melting point powder sheet.
また、高融点粉末シートの具体的実施例を示せ
ば、Cr12.0重量％，Si0.6重量％，Mn0.2重量％，
P0.002重量％，残部Feの組成を有し、粘度80メ
ツシユ以下（200メツシユ以下を50重量％以下含
む）の合金粉末96重量％（88容量％）と、アクリ
ル系樹脂粘着剤４重量％（12容量％）とにトルエ
ンを加えて湿式混練し、ロール圧延によつて密度
が4.8ｇ／cm3、厚さが0.5mmになるようにシート化
し、これを15mm×18mmの大きさに切断し、高融点
粉末シートの試料を作製した。この高融点粉末シ
ートは粘着剤の含有量が比較的多いので自己粘着
性を有しているとともに、この粘着剤の焼失によ
つて形成される気孔が多くなりガス流通性が大き
くなる。 In addition, specific examples of high melting point powder sheets include Cr12.0% by weight, Si0.6% by weight, Mn0.2% by weight,
96% by weight (88% by volume) of alloy powder with a composition of P0.002% by weight, balance Fe, and a viscosity of 80 mesh or less (including 50% by weight or less of 200 mesh or less), and 4% by weight of acrylic resin adhesive. (12% by volume) and wet-kneaded with toluene, rolled into a sheet with a density of 4.8g/cm 3 and a thickness of 0.5mm, and cut into a size of 15mm x 18mm. Then, a sample of a high melting point powder sheet was prepared. This high melting point powder sheet has a relatively large adhesive content, so it has self-adhesive properties, and the number of pores formed by burning out the adhesive increases, resulting in increased gas flowability.
上記低融点粉末シートと高融点粉末シートとを
ロールで圧着接合して積層体を形成し、この積層
体を鋼製の金属基体表面に接着し、下記の熱処理
を行つた。 The above-mentioned low melting point powder sheet and high melting point powder sheet were pressure-bonded with a roll to form a laminate, and this laminate was adhered to the surface of a steel metal substrate and subjected to the following heat treatment.
熱処理（H2ガス雰囲気下）→→
昇温速度10℃／分→300℃×60分
昇温速度15℃／分→1060℃×15分
昇温速度５℃／分→1090℃×20分
上記熱処理後、徐冷（冷却速度６℃／分）して
金属基体表面に接合した耐摩耗性焼結層が得られ
た。また、この焼結層には、脹らみもしくは凹み
等の欠陥は発生していなかつた。 Heat treatment (under H2 gas atmosphere) →→ Temperature increase rate 10℃/min → 300℃×60 minutes Temperature increase rate 15℃/min → 1060℃×15 minutes Temperature increase rate 5℃/min → 1090℃×20 minutes Above After the heat treatment, it was slowly cooled (cooling rate: 6° C./min) to obtain a wear-resistant sintered layer bonded to the surface of the metal substrate. Furthermore, no defects such as swelling or depressions were observed in this sintered layer.
さらに、焼結時に低融点粉末シートの液相は高
融点粉末シートの気孔に１mm程度浸入するので、
高融点粉末シート気孔は完全に塞がれている。 Furthermore, during sintering, the liquid phase of the low melting point powder sheet penetrates about 1 mm into the pores of the high melting point powder sheet, so
The high melting point powder sheet pores are completely blocked.
なお、上記熱処理において、の1060℃の温度
で15分保持するのは、焼結炉に収容された積層体
の昇温が各部において不均一となるため、その均
一化を図ることから行つているものであり、収容
量が少なく温度が均一化している場合には不要で
ある。 In addition, in the above heat treatment, holding at a temperature of 1060°C for 15 minutes was done to ensure uniformity since the temperature rise of the laminate housed in the sintering furnace would be uneven in each part. This is not necessary if the storage capacity is small and the temperature is uniform.
上記高融点粉末シートは、金属粉末の組成は実
施例に示したもののほかに、純Fe粉でもよく、
また、Ｃを少量含有するFe粉でもよい。その厚
さは、ガス抜きが有効に行なわれるのに積層体の
全厚みの1/3以上に設けるのが好ましく、具体的
には0.5mm以上が好ましく、第１図の場合には例
えば高融点粉末シートが１mmで低融点粉末シート
３mmとし、両者の面積比１：３となるようにする
ものである。また、ガス抜きを有効に行うには、
粘着剤の焼失によつて生じる気孔の割合が関連
し、その値は20〜60％の気孔率の範囲が設定し、
20％未満ではガス抜きが困難となり、60％を越え
ると焼結される金属粉末の量が少なく焼結強度が
低下するものである。 In the above-mentioned high melting point powder sheet, the composition of the metal powder may be pure Fe powder in addition to those shown in the examples.
Alternatively, Fe powder containing a small amount of C may be used. The thickness is preferably 1/3 or more of the total thickness of the laminate for effective degassing, specifically 0.5 mm or more, and in the case of Fig. 1, for example, The powder sheet is 1 mm long and the low melting point powder sheet is 3 mm wide, so that the area ratio of the two is 1:3. In addition, in order to effectively remove gas,
The percentage of pores caused by burnout of the adhesive is related, and its value is set in the porosity range of 20 to 60%.
If it is less than 20%, degassing becomes difficult, and if it exceeds 60%, the amount of metal powder to be sintered is small and the sintering strength is reduced.
ここで、低融点粉末シートおよび高融点粉末シ
ートからなる積層体についてさらに詳しく説明す
る。通常、樹脂による粘着剤は200〜300℃までは
母材との接着が可能であるが、温度がさらに上昇
すると、接着剤が焼失、揮散してしまい、粘着剤
としての機能を失つて母材との接着性が消失して
しまう。従つて、母材の斜面や湾曲面さらには下
向きの面等の積層体の重量が母材との接着面に作
用する場合には、積層体の重量を支えることがで
きなくなつて、母材から剥離もしくは脱落する恐
れがある。特に、振動や衝撃がワークに作用しな
い設備においては、母材との接着力はそれほど要
求されないが、メツシユベルト式あるいはプツシ
ヤー式連続焼結炉や真空焼結炉等では、搬送中の
振動や衝撃は避けがたい。これに対し粘着剤の接
着力が強い常温から200℃の間は問題はないが、
それ以上の温度と金属粉末の焼結が始まる700℃
付近の温度までの間に、強振動や衝撃が加わる
と、粘着剤が炭化した炭素による接合力が弱い場
合には、積層体が剥離してしまうことになる。 Here, the laminate consisting of the low melting point powder sheet and the high melting point powder sheet will be explained in more detail. Normally, resin adhesives can bond to the base material at temperatures of 200 to 300°C, but as the temperature rises further, the adhesive burns out and evaporates, losing its adhesive function and causing the base material to deteriorate. The adhesion with the product will be lost. Therefore, if the weight of the laminate, such as the sloped or curved surface of the base material or the downward facing surface, acts on the adhesive surface with the base material, the base material will no longer be able to support the weight of the laminate, and the base material will There is a risk of it peeling off or falling off. In particular, in equipment where vibrations and shocks do not act on the workpiece, adhesive strength with the base material is not required so much, but in mesh belt type or pusher type continuous sintering furnaces, vacuum sintering furnaces, etc., vibrations and shocks during transportation are not required. Unavoidable. On the other hand, there is no problem between room temperature and 200℃, where the adhesive has strong adhesive strength.
Temperatures above 700℃ and sintering of metal powder begins
If strong vibrations or shocks are applied until the adhesive reaches a temperature close to that temperature, the laminate will peel off if the bonding force due to the carbonized adhesive is weak.
上記点につき、前記したように合金粉末（金属
粉末）85〜97容量％とアクリル系樹脂粘着剤15〜
３容量％とを混練した後、圧延形成したシート
を、粘着性を持たせたアクリル系樹脂によつて鉄
系基材に接着し、非酸化性雰囲気中で150〜380℃
好ましくは200〜350℃の間の処理温度まで、40
℃／分以下の昇温速度で加熱し、この温度に５分
以上保持するようにしたものでは、120℃付近よ
り低沸点成分が揮発し、200℃付近より熱分解重
縮合反応が起こり、タールピツチ状物質が生成さ
れる。このタールピツチ状物質は粘着性があるた
め300℃以上での搬送による振動や衝撃に耐える
接着力を得ることができるものである。 Regarding the above points, as mentioned above, alloy powder (metal powder) 85-97% by volume and acrylic resin adhesive 15-97%
After kneading 3% by volume, the rolled sheet was adhered to an iron base material using an acrylic resin with adhesive properties, and heated at 150 to 380°C in a non-oxidizing atmosphere.
40 to a processing temperature preferably between 200 and 350 °C
If the temperature is heated at a temperature increase rate of less than ℃/min and held at this temperature for 5 minutes or more, low boiling point components will volatilize from around 120℃, and thermal decomposition polycondensation reactions will occur from around 200℃, resulting in tar pitch. A substance is produced. Since this tar pitch-like substance is sticky, it can provide adhesive strength that can withstand vibrations and shocks caused by transportation at temperatures of 300°C or higher.
上記現象を第３図の試験結果に沿つて説明す
る。この試験は、Mo10.5重量％，Cr2.5重量％，
P2.4重量％，C3.6重量％，残部Feの化学組成を
有し、粒度150メツシユ以下の三元共晶合金粉末
48.5重量％、SUS410の粒度150メツシユ以下の粉
末48.5重量％とアクリル系樹脂３重量％（９容量
％）とをアセトンを加えて湿式混練し、ロール圧
延によつて密度4.8ｇ／cm3，厚さ２mmにシート化
し、１cm×１cmに切断したシートを、同上のアク
リル系樹脂接着シート（厚さ10μ）で１cm×１cm
の接着面になるように、鋼製基材の垂直面に接着
した。この時の、粉末合金シートの重量は約0.96
ｇであるから、接着面には0.96ｇ／cm2のせん断力
が作用しており、この値以上の接着強度があれば
シートは脱落しない。 The above phenomenon will be explained along with the test results shown in FIG. This test consisted of Mo10.5wt%, Cr2.5wt%,
Ternary eutectic alloy powder with a chemical composition of 2.4% by weight of P, 3.6% by weight of C, and the balance Fe, with a particle size of 150 mesh or less
48.5% by weight of SUS410 powder with a particle size of 150 mesh or less and 3% by weight (9% by volume) of acrylic resin were wet-kneaded with acetone and rolled to a density of 4.8g/cm 3 and thickness. Cut the sheet into 2mm wide sheets and cut them into 1cm x 1cm pieces, then use the same acrylic resin adhesive sheet (thickness 10μ) as above to 1cm x 1cm.
It was adhered to the vertical surface of the steel base material so that the adhesive surface was as follows. At this time, the weight of the powder alloy sheet is approximately 0.96
g, a shearing force of 0.96 g/cm 2 is acting on the adhesive surface, and if the adhesive strength is greater than this value, the sheet will not fall off.
第３図で試料は、無処理の試料を窒素ガス雰
囲気中で加熱し、各温度での高温せん断試験を行
つたもので、常温では約5000ｇ／cm2であつたせん
断強度が、100℃では粘着剤が軟化することによ
つて3000ｇ／cm2以下になる。さらに、約200℃よ
りアクリル系樹脂の熱分解が始まり、分解に従つ
て強度が低下し、約400℃では急激な分解によつ
て強度が著しく低下するため、シートが脱落して
しまう。ここでは、シートの重力によるせん断力
に耐えられなかつたものと考えられるので、約１
ｇ／cm2以下のせん断強度になつていると推測でき
る。 In Figure 3, the untreated sample was heated in a nitrogen gas atmosphere and subjected to high-temperature shear tests at various temperatures. By softening the adhesive, it becomes less than 3000g/cm 2 . Furthermore, thermal decomposition of the acrylic resin begins at about 200°C, and its strength decreases as it decomposes, and at about 400°C, the strength drops significantly due to rapid decomposition, causing the sheet to fall off. Here, it is thought that the sheet could not withstand the shearing force due to gravity, so approximately 1
It can be assumed that the shear strength is less than g/cm 2 .
これに対し、試料，，は、予め水素ガス
雰囲気中で昇温速度10℃／分で加熱し、それぞれ
300℃×60分，250℃×60分，380℃×60分の熱処
理を行つて、常温まで徐冷した試料を再度加熱
し、各温度での高温せん断試験を行つたものであ
り、400℃までは未反応の樹脂が存在するために、
徐々に強度が低下している。400℃以上になると
未反応の樹脂は揮発してしまい、加熱とともにタ
ールピツチ状物質の炭素化が進んで、接着力が低
下する。しかし、700℃を越えると合金粉末の固
相焼結が進行するに従つて強度が逆に上昇し、さ
らに、1000℃近くになると共晶成分により液相が
晶出して、その液相成分が基材へ拡散することに
よつて再び凝固するため、せん断強度が著しく上
昇する。なお、第３図の右側の縦軸に示す目盛り
は、焼結層のせん断強度上昇に対応させたせん断
強度の値を示す。 On the other hand, samples , , were heated in advance at a heating rate of 10°C/min in a hydrogen gas atmosphere, and
The samples were heat treated at 300℃ x 60 minutes, 250℃ x 60 minutes, and 380℃ x 60 minutes, then slowly cooled to room temperature, then heated again, and a high-temperature shear test was conducted at each temperature. Due to the presence of unreacted resin,
The strength is gradually decreasing. At temperatures above 400°C, the unreacted resin evaporates, and the carbonization of the tar pit-like substance progresses with heating, reducing adhesive strength. However, when the temperature exceeds 700℃, the strength increases as the solid phase sintering of the alloy powder progresses, and furthermore, when the temperature approaches 1000℃, the liquid phase crystallizes due to the eutectic component, and the liquid phase component It solidifies again by diffusing into the base material, resulting in a significant increase in shear strength. Note that the scale shown on the vertical axis on the right side of FIG. 3 indicates the value of shear strength corresponding to the increase in shear strength of the sintered layer.
よつて、試料のように連続的に昇温した場合
には380℃を越える温度で脱落する可能性がある
が、試料，，のように予め熱処理を施した
ものは脱落せずに接着しているものである。 Therefore, if the temperature is raised continuously like a sample, there is a possibility that it will fall off at a temperature exceeding 380℃, but if the sample has been heat-treated in advance, it will not fall off and will adhere. It is something that exists.
さらに、上記現象を解明するために第５図に示
す実験を行つた。この実験は、アクリル系樹脂粘
着剤［（メタ）アクリル酸アルキルエステル−ア
クリル酸共重合体］を窒素ガス雰囲気中で加熱し
たときの重量減少を示す。なお、後述する各温度
までの昇温速度は15℃／分である。アクリル系樹
脂粘着剤は300℃で約10％が分解し、さらに加熱
すると約400℃付近で急激に分解し、約90％が分
解してしまう。 Furthermore, in order to elucidate the above phenomenon, an experiment shown in FIG. 5 was conducted. This experiment shows the weight loss when an acrylic resin adhesive [(meth)acrylic acid alkyl ester-acrylic acid copolymer] is heated in a nitrogen gas atmosphere. Note that the rate of temperature increase to each temperature described later is 15° C./min. Approximately 10% of acrylic resin adhesives decompose at 300°C, and when heated further, they rapidly decompose at around 400°C, resulting in approximately 90% decomposition.
一方、窒素ガス雰囲気中で加熱特性ａに沿つて
300℃×60分加熱した試料Ａでは、予め非酸化性
雰囲気で昇温し加熱したことによつて、約40％分
解し残りの約60％が熱分解重縮合反応を起こし
て、タールピツチ状物質に変化している。このタ
ールピツチ状物質によつて、400〜700℃までの接
着力すなわち保持力を備えているものと考えられ
る。 On the other hand, along the heating characteristic a in a nitrogen gas atmosphere
Sample A, which was heated at 300°C for 60 minutes, was heated in a non-oxidizing atmosphere beforehand, so about 40% decomposed and the remaining 60% underwent a thermal decomposition polycondensation reaction, resulting in a tar pit-like substance. is changing. It is thought that this tar pitch-like substance provides adhesive strength, that is, holding power up to 400 to 700°C.
また、加熱特性ｂに沿つて400℃×60分加熱し
た試料Ｂでは、約90％が分解しており、400℃以
上での接着力を有するためのタールピツチ状物質
の生成が少なくなるために、シートの脱落等を生
じている。さらに、加熱特性ｃに沿つて500℃×
60分加熱した試料Ｃでも、上記試料Ｂ（400℃×60
分）と同様のことが言える。以上のように、急激
な樹脂の分解が起こる400℃以上の高温では、生
成するタールピツチ状物質の寄与が支配的とな
り、合金粉末の固相焼結が始まる700℃付近まで
続くと考えられる。 In addition, in sample B, which was heated at 400°C for 60 minutes according to heating characteristic b, about 90% of the sample B was decomposed, and the generation of tar pit-like substances required to maintain adhesive strength at temperatures above 400°C was reduced. Sheets are falling off, etc. Furthermore, according to the heating characteristic c, 500℃×
Even if sample C was heated for 60 minutes, sample B (400℃ x 60℃) was heated for 60 minutes.
The same thing can be said for (minutes). As described above, at high temperatures of 400°C or higher, where rapid resin decomposition occurs, the contribution of the generated tar pit-like substances becomes dominant, and it is thought that this continues until around 700°C, when solid phase sintering of the alloy powder begins.
上記タールピツチ状物質の生成を確認するた
め、アクリル系樹脂粘着剤を窒素ガス雰囲気で
300℃×60分保持後、500℃および700℃で加熱し
たものについて元素分析を行つた結果につき、炭
素と水素についての元素の重量％と、Ｈ／Ｃ原子
比を次に示す。試料１は500℃加熱物、試料２は
700℃加熱物である。 In order to confirm the formation of the above-mentioned tar pitch-like substance, the acrylic resin adhesive was placed in a nitrogen gas atmosphere.
After holding at 300°C for 60 minutes, the samples heated at 500°C and 700°C were subjected to elemental analysis. The weight percent of carbon and hydrogen elements and the H/C atomic ratio are shown below. Sample 1 is heated to 500℃, sample 2 is
It is heated to 700℃.
Ｃ Ｈ Ｈ／Ｃ
試料１ 91.7％ 5.9％ 0.77
試料２ 95.2％ 1.4％ 0.18
ここで、ピツチ類と総称されるものは、Ｈ／Ｃ
原子比をみると、アスフアルト類の1.0以上から
コールタールピツチ類の0.5〜0.6までである。よ
つて、試料１の場合、Ｈ／Ｃが0.77であり、ター
ルピツチ状物質が残存しているのが確認された。
試料２は、Ｈ／Ｃが0.18であり、炭素化が進むこ
とにより、タールピツチ状物質が減少している
が、この温度近辺からは金属焼結が始まり、強固
な金属結合に移行するものである。 C H H/C Sample 1 91.7% 5.9% 0.77 Sample 2 95.2% 1.4% 0.18 Here, those collectively referred to as Pits are H/C
Looking at the atomic ratio, it ranges from over 1.0 for asphalts to 0.5 to 0.6 for coal tar pitches. Therefore, in the case of sample 1, H/C was 0.77, and it was confirmed that tar pitch-like substances remained.
Sample 2 has an H/C of 0.18, and as carbonization progresses, the tar pit-like substance decreases, but metal sintering begins around this temperature and transitions to a strong metal bond. .
なお、上記焼結前の積層体の加熱処理におい
て、その加熱雰囲気は、合金粉末、金属粉末およ
びアクリル系樹脂粘着剤の酸化を防ぐため、窒素
ガス、アルゴンガス等の不活性ガス中、水素ガス
等の還元性ガス中、真空中等の非酸化性雰囲気で
行う必要がある。また、昇温速度が40℃／分以下
とするのは、この昇温速度が40℃／分を越えると
アクリル樹脂粘着剤中の低沸点分が急激に揮発す
るため、積層体を破損したり、接着面に気泡が発
生して脱落するので、これを防止するためであ
る。そして、加熱温度を150〜380℃好ましくは
200〜350℃とするのは、150℃未満では粘着剤の
未分解量が多くなり、400℃以上に加熱したとき
に急激な分解を起こすことと、タールピツチ状物
質の生成量が少ないため、高温における接着強度
が低くなつて積層体が脱落する可能性がある一
方、380℃を越えると粘着剤が急激な分解を生起
し、接着に寄与するタールピツチ状物質の生成量
が少なく積層体が脱落する可能性があるからであ
る。さらに、保持時間を５分以上とするのは、上
記加熱温度によつて最適な時間が異なるが、５分
未満ではタールピツチ状物質の生成量が少なく接
着が不十分になり、また、120分以上の加熱は経
済的でないものであり、上記各条件はかかる範囲
に設定するのが良好な処理が行える点で好まし
い。 In addition, in the heat treatment of the laminate before sintering, the heating atmosphere is hydrogen gas in an inert gas such as nitrogen gas or argon gas to prevent oxidation of the alloy powder, metal powder, and acrylic resin adhesive. It is necessary to carry out the process in a non-oxidizing atmosphere such as a vacuum or in a reducing gas such as. Also, the temperature increase rate should be 40℃/minute or less because if the temperature increase rate exceeds 40℃/minute, the low boiling point content in the acrylic resin adhesive will rapidly volatilize, which may damage the laminate. This is to prevent air bubbles from forming on the adhesive surface and falling off. And the heating temperature is preferably 150~380℃
The reason why the temperature is set at 200 to 350℃ is that if the adhesive is lower than 150℃, there will be a large amount of undecomposed adhesive, which will cause rapid decomposition when heated to 400℃ or higher, and the amount of tar pit-like substance produced will be small. On the other hand, if the temperature exceeds 380℃, the adhesive will rapidly decompose, and the amount of tar pitch-like substances that contribute to adhesion will be small, causing the laminate to fall off. This is because there is a possibility. Furthermore, the optimal holding time is 5 minutes or more, which varies depending on the heating temperature mentioned above, but if it is less than 5 minutes, the amount of tar pitch-like substances produced is small and the adhesion is insufficient, and if the holding time is 120 minutes or more, Heating is not economical, and it is preferable to set the above conditions within such ranges in order to perform a good treatment.
また、積層体における低融点粉末シートの合金
粉末は、加熱焼結したときに耐摩耗性を有する必
要があることは当然であるが、アクリル系樹脂粘
着剤の接着性には温度的に限界があるため、焼結
温度はできるだけ低いことが好ましい。このこと
は、高融点粉末シートにも言えることである。 In addition, it goes without saying that the alloy powder of the low melting point powder sheet in the laminate needs to have wear resistance when heated and sintered, but there is a temperature limit to the adhesion of the acrylic resin adhesive. Therefore, it is preferable that the sintering temperature is as low as possible. This also applies to high melting point powder sheets.
かかる観点から、耐摩耗性合金粉末としては、
耐摩耗性共晶合金粉末、特に、Fe−Ｍ−Ｃ系の
三元共晶合金粉末を用いることが好ましく、Ｍと
しては、Mo，ＢおよびＰのうちいずれか一種ま
たはそれらの複合であることが好ましい。特に、
Ｐを用いることはＣと同様に母材への拡散性が強
いので好ましい。 From this point of view, as wear-resistant alloy powder,
It is preferable to use wear-resistant eutectic alloy powder, especially Fe-MC-based ternary eutectic alloy powder, where M is any one of Mo, B, and P, or a combination thereof. is preferred. especially,
It is preferable to use P because, like C, it has strong diffusibility into the base material.
また、Fe−Ｍ−Ｃの三元共晶合金の強度、耐
摩耗性を改善する副次的な元素としてはCr，Ｖ，
Ｗ，Nb，Ta，Tiが有効であり、さらに、その他
の元素として、Si，Ni，Mnを各種の性能を改善
するのに役立つ元素であり、添加するのが好まし
い。 In addition, Cr, V,
W, Nb, Ta, and Ti are effective, and it is preferable to add Si, Ni, and Mn as other elements that are useful for improving various performances.
第１図は本発明の一実施態様における金属基体
の積層体を接着した状態を示す断面図、第２図は
第１図における積層体の形成例を示す斜視図、第
３図は積層体の焼結前の加熱温度に対するせん断
強度と温度の関係を示す特性図、第４図はアクリ
ル系樹脂粘着剤を300〜500℃の範囲で加熱処理し
た後、窒素ガス雰囲気中で加熱したときの重量減
少を示す特性図、第５図Ａ〜Ｄは焼結工程を順に
示し欠陥の発生状況を示す説明図、第６図はアク
リル系樹脂粘着剤の焼結温度までの加熱に伴うガ
スの発生状況をガスクロマトグラフによつて測定
した結果を示すグラフである。
１……金属基体、２……低融点粉末シート、３
……高融点粉末シート、５……積層体。
FIG. 1 is a sectional view showing a state in which a laminate of metal substrates is bonded together in an embodiment of the present invention, FIG. 2 is a perspective view showing an example of forming the laminate in FIG. 1, and FIG. A characteristic diagram showing the relationship between shear strength and temperature with respect to the heating temperature before sintering. Figure 4 shows the weight when heated in a nitrogen gas atmosphere after heat treating the acrylic resin adhesive in the range of 300 to 500°C. A characteristic diagram showing the decrease, Figures 5A to 5D are explanatory diagrams showing the sintering process in order and the occurrence of defects, and Figure 6 is a diagram showing the generation of gas as the acrylic resin adhesive is heated to the sintering temperature. This is a graph showing the results of measurement using a gas chromatograph. 1... Metal base, 2... Low melting point powder sheet, 3
...High melting point powder sheet, 5...Laminated body.
Claims (1)
方法であつて、耐磨耗性を有する低融点の合金粉
末にアクリル系樹脂からなる粘着剤を混練して形
成した低融点粉末シートと、高融点の金属粉末に
アクリル系樹脂からなる粘着剤を混練して形成し
かつ液相焼結時に該粘着剤の焼失による気孔率が
20〜60％となる高融点粉末シートとを設け、該高
融点粉末シートと低融点粉末シートを交互に複数
層重ね合わせてロール圧着して積層体を形成し、
該積層体を所定の厚さに切断し、該積層体を、高
融点粉末シートと低融点粉末シートとが金属基体
の接合面とほぼ直角な方向に積層された状態で上
記金属基体表面に接着し、次に上記積層体を非酸
化性雰囲気下で150〜380℃の温度で５分以上加熱
保持した後、少なくとも高融点粉末シートが固相
状態で低融点粉末シートを液相焼結することを特
徴とする金属基体表面に接合された焼結層を形成
する方法。1. A method for forming a sintered layer bonded to the surface of a metal substrate, comprising: a low melting point powder sheet formed by kneading a wear-resistant, low melting point alloy powder with an adhesive made of acrylic resin; It is formed by kneading an adhesive made of acrylic resin into a metal powder with a high melting point, and the porosity is reduced due to burnout of the adhesive during liquid phase sintering.
20 to 60% high melting point powder sheets are provided, and a plurality of layers of the high melting point powder sheets and low melting point powder sheets are alternately stacked and roll pressure bonded to form a laminate,
The laminate is cut to a predetermined thickness, and the laminate is adhered to the surface of the metal substrate in a state where the high melting point powder sheet and the low melting point powder sheet are laminated in a direction substantially perpendicular to the bonding surface of the metal substrate. Then, after heating and holding the laminate at a temperature of 150 to 380°C for 5 minutes or more in a non-oxidizing atmosphere, the low melting point powder sheet is liquid phase sintered with at least the high melting point powder sheet in a solid state. A method for forming a sintered layer bonded to the surface of a metal substrate, characterized by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3404184A JPS60181206A (en) | 1984-02-24 | 1984-02-24 | Method for forming sintered layer on surface of metallic base body |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3404184A JPS60181206A (en) | 1984-02-24 | 1984-02-24 | Method for forming sintered layer on surface of metallic base body |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60181206A JPS60181206A (en) | 1985-09-14 |
| JPH0249362B2 true JPH0249362B2 (en) | 1990-10-30 |
Family
ID=12403232
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3404184A Granted JPS60181206A (en) | 1984-02-24 | 1984-02-24 | Method for forming sintered layer on surface of metallic base body |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60181206A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60181203A (en) * | 1984-02-24 | 1985-09-14 | Mazda Motor Corp | Method for forming sintered layer on surface of metallic base body |
| JPS6196012A (en) * | 1984-10-15 | 1986-05-14 | Mazda Motor Corp | Method for joining powder alloy sheet to ferrous member by sintering |
| US6386127B1 (en) * | 2000-02-07 | 2002-05-14 | Case Corporation | Disc opener assembly for a seed planter |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60181203A (en) * | 1984-02-24 | 1985-09-14 | Mazda Motor Corp | Method for forming sintered layer on surface of metallic base body |
-
1984
- 1984-02-24 JP JP3404184A patent/JPS60181206A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60181203A (en) * | 1984-02-24 | 1985-09-14 | Mazda Motor Corp | Method for forming sintered layer on surface of metallic base body |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60181206A (en) | 1985-09-14 |
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