JPS6022060B2 - Chromium iron alloy composite material and its manufacturing method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a chromium-iron alloy composite material and a method for producing the same.

In particular, the present invention provides a chromium-iron alloy composite material that has excellent heat resistance, corrosion resistance, oxidation resistance, abrasion resistance, hardness, and strength, and is made of a chromium-iron alloy, carbides and silicides of the alloy, and SIC that are firmly connected to each other. and its manufacturing method. Fe--Cr alloys have excellent oxidation resistance and corrosion resistance, and are conventionally used in, for example, salt pots, retorts, feed pipes, boiler parts, cement kiln parts, and the like.

Among these, those with a low Cr content are generally used as corrosion-resistant materials, and those with a high Cr content are used as oxidation-resistant materials. However, those with a low Cr content are still insufficient in terms of corrosion resistance and oxidation resistance, and
Those with a high content have excellent corrosion resistance and oxidation resistance to some extent, but have drawbacks such as being relatively difficult to manufacture, high in manufacturing cost, and lacking in processability. Therefore, for alloys with a high Cr content, materials have been developed that are made by powdering and heat-forming in a hot press.The material is then made into a powder and heat-forming in a hot press. However, the hot-pressed products have the disadvantage that they do not have sufficient hardness and wear resistance like cast products, and the corrosion resistance and heat resistance of hot-pressed products are almost the same or inferior to those of cast products. The present invention eliminates the various drawbacks of conventional casting or forging materials made of chromium iron alloys or materials manufactured by powder casting method, and improves heat resistance, corrosion resistance, oxidation resistance, abrasion resistance, hardness and strength. The purpose of the present invention is to provide an excellent chromium-iron alloy composite material and a method for manufacturing the same.

The present invention is an organosilicon polymer compound containing 30 to 9% by weight of chromium iron alloy powder and carbon and silicon as main skeleton components.
The mixture with ~70% by weight was pressure molded and exposed to N2 in vacuo.
A chromium-iron alloy composite material that is heated and solidified at a temperature range of 700 to 1400 qo in an atmosphere consisting of at least one selected from gas, inert gas, CO gas, CQ gas, N ratio gas, and hydrogen gas. Fe-Cr alloy 10-99.5%, chromium carbide 0.05-80%,
Chromium silicide 0.05~20%, iron carbide 0.01~
40%, iron silicide 0.01-10%, SICO. 01
At least one carbide selected from Fe, Cr, and Si and at least one silicide selected from Fe and Cr are present between the chromium-iron alloy powder particles having a composition of ~30%. A chromium-iron alloy composite material having a composition in which the chromium-iron alloy, carbide, and silicide are uniformly dispersed, and the interface of the dispersed particles is formed from a new phase of binding of the chromium-iron alloy, carbide, and silicide. The present invention is a chromium-iron alloy composite material having excellent heat resistance, corrosion resistance, oxidation resistance, abrasion resistance, hardness, and strength, and having a structure in which the carbides and silicides have a size of 1 cape or less.

Another object of the present invention is chromium iron alloy powder 30~
A step of pressure molding a mixture of 9 $ wt % and 1 to 7 wt % of an organosilicon polymer compound whose main skeleton components are carbon and silicon, and N2 gas, inert gas, CO gas, C in vacuum.
700 to 140 in an atmosphere consisting of at least one selected from 02 gas, NH3 gas, and hydrogen gas.
Heating light stripes in the temperature range of 0o○, Fe-Cr alloy 10 ~
99.5%, chromium carbide 0.05-80%, chromium silicide 0.05-20%, iron carbide 0.01-40%,
Iron silicide 0.01-10%, SICO. 01-30%
The composition is as follows: Fe, Fe,
It has a composition in which at least one type of carbide selected from C, Si and at least one type of silicide selected from Fe and Cr are present, and the chromium iron alloy, carbide, and silicide are uniform. and the interface of the dispersed particles is formed by a fastening phase shift of the chromium iron alloy, carbide, and silicide, and the size of the carbide and silicide is 1.
A chromium-iron alloy with good heat resistance, corrosion resistance, oxidation resistance, wear resistance, hardness, and strength, characterized by comprising a step of obtaining a chromium-iron alloy composite material having a structure of 0 μm or less. In the manufacturing method of composite materials.

Next, the present invention will be explained in detail.

The composite material of the present invention has at least one selected from iron carbide, chromium carbide, and silicon carbide and at least one selected from iron silicide and chromium silicide between the chromium-iron alloy powder particles. It is a structure in which particles are finely and uniformly dispersed and strongly connected to each other, and the interface of the particles constituting this structure is formed by the fastening phase shift of the chromium-iron alloy, carbide, and silicide. The present invention is a composite material having a novel composition characterized in that the size of the silicide is less than or equal to low.

In the present invention, the carbides and silicides are very fine particles with a size of 10 mm or less because the carbides and silicides have carbon and silicon as their main skeleton components, as will be described in detail later. The highly active free carbon produced when the organosilicon polymer compound thermally decomposes, the carbides and silicides of iron and chromium produced when the free silicon combines with the base matrix Fe-Cr alloy, and the free carbon and free carbon. Amorphous and/or a-type SIC produced by combining with silicon
Since these carbides and silicides are finely intermixed and bonded, even when the composite material of the present invention is manufactured by high temperature heating, the growth of the crystal grains of each carbide and silicide is affected by the presence of different particles. This is thought to result in ultra-fine grain sizes of less than 1 mm. It should be noted that general metal materials cannot avoid the drawback that when heated to high temperatures for a long time, crystal grain size grows and strength and other mechanical qualities deteriorate, but the composite material of the present invention has the disadvantage of One of the major features of the composite material of the present invention is that grain size growth does not occur and therefore mechanical properties do not deteriorate.

In the composite material of the present invention, the particle interfaces of the chromium-iron alloy, carbide, and silicide are formed by their fastening gradual phase shift. For example, Cr in the chromium-iron alloy undergoes a contact reaction with the free carbon at high temperatures. The interface of the particles is formed from a fastening gradual phase in which the molar ratio of Cr and C in the contact layer gradually changes, and the carbide and silicide particles forming a tidal phase shift are Because it is ultra-fine, measuring less than one cape, it is an extremely strong connection.

Even when hot-pressing a mixture of chromium-iron alloy powder and SIC powder, which is conventionally done, the fastening force is extremely small compared to that of the composite material of the present invention, because of the contact interface between the chromium-iron alloy particles and SIC particles. This is thought to be because the fastening in the composite material of the present invention is not fastened by ultra-fine carbide or silicide particles as in the gradual phase shift of the composite material of the present invention, and the composite material of the present invention has a new structure not previously known. In addition to this, a strong connection has been realized.

The composite material of the present invention has a Fe-Cr alloy of 10 to 99.5%.
, chromium carbide 0.05-80%, chromium silicide 0.
05-20%, iron carbide 0.01-40%, iron silicide 0.01-10%, BjCO. It consists of a component composition of 01 to 30%.

The above component composition is the result of a quantitative method using X-ray powder diffraction using a standard material, point/line/area analysis using a scanning electron microscope/X-ray microanalyzer using a standard material, crab light analysis, and chemical analysis using a wet method. This is the value determined by

Figure 1A is a micrograph of a composite material of the present invention using 13% Cr-Fe chromium iron alloy powder as a base matrix, and Figure 1B is a micrograph of a polished corrosion sample of a conventional material made by hot pressing only the chromium iron powder. (magnification: 100 needle sounds), and it can be seen that A is finely and firmly fastened compared to B.

Among the strengths of the composite material of the present invention, its pile breaking strength is 90 to 15
0k9/light compressive strength is 300-700k9/boiled,
One major feature of the composite material of the present invention is that the strength is much higher than that of conventional hot-pressed composite materials.

Further, the composite material of the present invention has carbides as its constituent components,
It is true that silicides, SIC, etc. each have a high micro-Pickus hardness value of 1500 or more, and because they are bonded extremely homogeneously, the overall Micro-Picks hardness is extremely high at 1500-3000. This is another feature of the composite material of the invention. In Table 1,
The micro-Vickers hardness values of a conventional hot-pressed sintered body of 28% CF-Fe powder and a composite material of the present invention obtained by hot-pressing the powder with 3% by weight of polycarbosilane added are shown.

As can be seen from the X-ray microanalysis shown in Figures 1A and 2, the composite material of the present invention has excellent mechanical properties. There is a continuous interfacial change at the contact surface, that is, a gradual phase shift is formed, which increases adhesion, continuously reduces and averages out the difference in thermal expansion coefficient, and is firmly connected. It's for a reason.

The composite material of the present invention not only has chromium iron, which is a base matrix, having relatively high oxidation resistance, but also carbides, silicides, etc. are compounds that are extremely stable both thermally and chemically. Another feature of the composite material of the present invention is that it has high oxidation resistance and corrosion resistance because it is tightly bonded.

Next, the method for manufacturing the composite material of the present invention will be explained. The chromium-iron alloy powder that is the raw material for the composite material of the present invention is preferably fine particles, and those having a particle size of usually 350 mesh or less can be advantageously used.

The composition of the chromium iron alloy is Cro. 5-99
．． A chromium-iron alloy consisting mainly of Fe with a 5% balance can advantageously be used. It is advantageous to change the content of Cr depending on the purpose and use of the composite material of the present invention. For example, when the purpose is corrosion resistance, Crl
It is desirable that the Cr content be 0% or more, and on the other hand, in the case of applications that require rice grain properties, it is desirable that the Cr content be relatively low or considerably high. One of the raw materials used to manufacture the cermet of the present invention is an organosilicon polymer compound whose skeleton components are mainly carbon and silicon. Kosho 57-2
No. 6527, Tokuko Showa 57-Gi-mura No. 91, Tokuko Sho-Baraichi 38
No. 534, Special Publication No. 892, General Publication No. 892, Special Publication No. 51-14.
No. 992, JP-A-51-149926, JP-A-57-
5-Masa No. 93, JP-A-51-14762, JP-A-57-
No. 56566, Samurai Public Sho-Mura No. 535, Tokuko Sho 57-5
Madaraban number, Tokko Sho 52-59724, Tokko Sho 59-33
No. 681, Special Publication No. 59-33682 and Special Publication No. 1983
The method for producing this compound is described in detail in the specification of No. 34012, and the method for producing this compound is described below. The organosilicon compound that can be used as a starting material is one or more selected from the following types m to (2).

[11 R4Si, a compound called silahydromarbon, containing only Si-C bonds
, R3Sj (RSIR2) 'SIR3' and its carbon-functional derivatives belong to this category.

Example (CH3)4Si, (CH2=CH)4Si, (C
H3) 3SIC=OSi(CH3)3, (C ratio)5Si
(CH2) 4, (C2 is) 3SIC day 2C ratio CI, (C
6th 5) 3SIC02nd,■ In addition to Sj-C bond, S
Compounds including mono-, di-, and triorganosilanes, including j-day compound, belong to this category.

Example (C2 is) 2Si4, (CH2) 5SiQ, (C place) 3SIC day 2Si (CH3) 2 day, CICHbuiH3
, '3'Si is a compound organohalogensilane having an Al bond.

Example C ratio=CHSiF3, C2day5SiHC12, (C
H3)2(CICH2)SiSi(CH3)2CI, (
This includes C6&)3SiBr, silylamine, a compound having a [41 Si--N bond, and the like.

Example aside: Si-CR organoalkoxy (or alkoxysilane).

Example (CH3)2Si(OC2day5)2,C2day5
SIC12 (〇C2 days 5), p-CIC6 days OSi (C
H3) 3, [6}Example of organosilanol compounds having Si-CH bond (C2 is)3SiOH, (CH3)bui(OH
)2, C6&Si(OH)3, (HO)(CH3)2S
IC day 2Si(C&)2, (〇H),'7} Si-S
Examples of compounds containing i-bonds (CH3)3SiSi(C ratio)2CI, (CH3)
BuiSi(Cmelon)3,(C64)3SiSi(C6&)
? (C6 day 5) 2CI, {81 It is an organosiloxane compound containing a Si-○-Si bond.

Example (C ratio) 3SiSj (CH3) 3, day 0 (CH3) buiSi (CQ) 20 days, CI2 (C&
)SiOSi(CH3)CI2, [(C6 ratio)2Si0
]4, CH2 = C (CH3) C02C payment Si
・(C horse) 2CH2QC(CH3)=C ratio '9} Organosilicon compound ester: An ester thought to be formed from silanol and acid, (C ratio) 2Si(OCO
C horse) 2 etc. belong to this category.

■ Organosilicon compound peroxide: (CH3)3SiOC
C・(CH3)3,(CH3)3Si00Si (C ratio)
Such.

In the molecular structures of {1} to (2) above, R represents an alkyl group or an alizole group.

In the present invention, an organosilicon polymer compound having silicon and carbon as main skeleton components, for example, a compound having the following molecular structure, is produced from the raw materials.

〇 Those containing the skeletal components described in (a) to (c) above as at least one partial structure of a chain or three-dimensional structure, or a combination of (a), (b), and (c).

Examples of compounds having the above molecular structure include the following.

n=1, poly(silmethylene siloxane) n=2, poly(silethylene siloxane) n=6, poly(silphenylene siloxane) n=1, poly(methyleneoxysiloxane) n=2, poly(ethyleneoxysiloxane) )n=
6, Poly(phenyleneoxysiloxane) n=12, Poly(diphenyleneoxysiloxane) n=
1, polysylmethylene n = 2, polysylethylene n = 3, polysyltrimethylene n = 6, polysylphenylene n = 12, polysyldiphenylene 8 The skeleton components described in (a) to (c) above One containing as a partial structure at least one of chain, cyclic, and three-dimensional structures, or a mixture of (a), (b), and (c).

Furthermore, examples of organosilicon polymer compounds containing different elements other than silicon, carbon, hydrogen, and oxygen that can be used in the present invention include the following (e) to (g).

Polymer having a carbon nucleus The organosilicon polymer compound containing the above-mentioned foreign element can be synthesized by a known method.

In addition to the organosilicon compounds containing different elements synthesized by the above-mentioned known methods, there are
It can also be manufactured by the manufacturing method described in the specification of No. 134012. That is, the above '11-00
At least one or more organometallic compounds selected from the following organometallic compounds (11) to (20) are added to the organosilicon compound of 200 to 15% in a non-oxidizing atmosphere.
An organosilicon polymer compound containing different elements other than silicon, carbon, hydrogen, and oxygen can be synthesized by heating to a temperature range of 00°C. (11) Examples of organosilicon compounds containing nitrogen (C2day5) BuiN ratio, (C is) 3SI
NHSi(CH3)3, (CH3)3Si(CN), (
CH3)3SINC0, (Cmelon)SINCS (12) Examples of organometallic compounds (coordination compounds) containing Group 1 metals
CH3Li, C2 day 5Na, C6 day 5Li, Na [(C
)2Li], KCH3, Ayahi3, AuCH3Hg(
13) Examples of organometallic compounds (coordination-containing compounds) containing Group 0 metals: BeC2 melon, MgCH2, CaC2HB, BeC2
ratio, ZnC 4 days.

, CdC 2 days 6, HgCH3Br, Sn0 2 days 6 (1 core Organometallic compound (coordination compound) containing group m metal example BCH502, BC 3 days 9, NC 2 days 7, GaCH30
, Inc2&N, Inc3 is TIC34, Sc (
CH3COCH COH3)3, La(C ratio C
OCHCOCH3)3, Cc(CH3CO
CHCOCH3)4, Pr(C ratio COC
HCOC ratio )3 Nd( CH3COCH
COCH3)3, Sm(CH3COC
HCOC ratio )3 Eu( CH3COC
HCOCH3 )3 Gd( CQCOCH
CCCH3)3, Tb(CH3COCHC
OCH3)3Py(C ratio COCHCO
C ratio )3Ho(CH3C.

C.H.C. CH3)3, Er(CH3C
OCHCOCH3)3, Tm(CH3
COCHOCH3)3, Yb(C ratio C
OCHCOCH3 )3 Ln( CH3C
OCHCOC ratio )3, (15) Examples of organometallic compounds (coordination-containing compounds) containing Group W metals mC, oH, o
C12, GaC 2 days 8, SnC2, pbC 2 days 8 (1
6) Organometallic compounds containing Group V metals (coordination compounds)
Example VC606, NbC606, TaC606, C4 day 4N, PC2 is 05, PC2 day 7, AgC ratio S, AsC
2 days 7, SOC 2 days 7, BiC 3 days 9 (17) Examples of organometallic compounds (coordination-containing compounds) containing town group metals WC8 is 03, C2 days 5SH, SeC days 2, TeC2 is PoC
2 is (1) Examples of organometallic compounds (coordination compounds) containing group metals NhC, 2 days, o, TeC, oH, o, R
eC6 day 3Q (19D Examples of organometallic compounds (coordination compounds) containing Group W metals FeC, Yama, o, CoC6&0
3, NiC 6 days. o, R mountain C,.

Day,. , RhC 9 days, 3, PdC 8 days. , PdC 5 days 5CI, 0sC,. Day,. , lrC303, PtC 4 days, 2 Organosilicon polymer compounds whose main skeleton components are mainly silicon and carbon as shown in (i) to (d) synthesized in this way, and g) and (1
) to (19) At least one or more organosilicon polymers selected from organosilicon polymer compounds containing different elements other than silicon, carbon, hydrogen, and oxygen, which are produced from two or more compounds shown in (19). The compounds can be used as raw materials for the composite materials of the present invention. The organosilicon polymer compound described above, which has carbon and silicon as its main skeleton components and optionally contains metal elements in its skeleton, can be obtained as a solid or a viscous liquid at room temperature by a relatively simple and inexpensive manufacturing method. Therefore, in the present invention, these solids or viscous liquids can be used as they are.

In other words, it becomes a slightly viscous liquid by heating at a relatively low temperature of around 300q0, so it is not necessary to heat the compact at an early stage when it is heated and fired. It becomes a low viscosity fluid and the base Fe-Cr
This generally covers the alloy powder and facilitates the necessary reactions and diffusion that occur during the subsequent heating to high temperatures, which ultimately results in a strongly bonded fired compact. The effect is extremely large. The chemical changes that occur during the heating process in the compacted compact formed from the starting material mentioned by Muyama will be explained below.

As described above, the organosilicon polymer compound becomes a low viscosity fluid at the initial stage of heating and uniformly and generally covers the metal powder.
When the heating temperature further increases, the organosilicon polymer compound thermally decomposes, some organic substances containing carbon, hydrogen, and silicon are dispersed as volatile components, and the remaining highly active carbon and silicon are heated to about 700℃ or Fe, Starts to react with Cr, 10-100
Carbides and silicides with diameter A begin to form. Furthermore, 140
If heated to a temperature higher than 0°C, the Cr-Fe alloy will soften or melt and the carbides and silicides once formed will decompose, so it is necessary to heat within the temperature range of 700 to 1400°C.

If the initial amount of the organosilicon polymer compound is large, an SIC phase is further formed in the composite material. The morphology of the SIC phase is approximately 1000 qo when heated from 700 qo to 1400 qo.
When the temperature is below 0.degree. C., it becomes amorphous, and when it is above 1000 qo, it becomes a B-type crystal phase. Finally, the Fe-Cr-based alloy, carbides, silicides, and SIC phases of Fe and C are mutually uniformly dispersed and firmly bonded to each other to form a composite material. In the present invention, Fe-Cr alloy of 99-3% by weight and 1-3% by weight of Fe-Cr alloy and
7% by weight of an organosilicon polymer compound.

The amount of this organosilicon polymer compound can be changed depending on the firing method, but if it is less than 1%, the addition effect is poor and it is difficult to obtain a molded product with strong bonding and high strength.If it is more than 70%, most of the base Fe-Cr alloy is is converted into carbides and silicides, thereby impairing the high-temperature plowability and other advantageous properties inherent in the Fe-Cr alloy, so it is necessary to add it within the range of 1 to 7% by weight.

The reason why the amount of Fe-Cr alloy powder is set to 30 to 9% by weight is that if it is less than 3% by weight, carbides and silicides will increase and the balling properties will be poor, whereas if it is more than 9% by weight, strong bonding and high strength will occur. Therefore, it is necessary to keep it within the range of 30 to 9% by weight. Furthermore, the organosilicon polymer compound is thermally decomposed during the firing process, and a portion of it is removed in the form of hydrocarbons, hydrogen, etc., and about 60% of the added weight remains and participates in the reaction. The above blending amount can be set depending on the purpose of use of the composite material, but if you want to add more rut resistance, use a large amount of metal powder, and if high strength or hardness is required, use a large amount of metal powder. It is preferable to use a relatively small amount.

However, when using the organosilicon polymer compound containing the metal element described above, good results can be obtained even if the amount of metal powder added is 5% or less. Also, if necessary, Mg0 or M
Customary setting accelerators such as gO-Si02 can be added.

Next, the Fe--Cr and organosilicon polymer compounds described above are mixed to form a mixture. Two methods can be used for the mixing method: dry mixing and wet mixing. In the dry mixing method, the metal powder and the solid powder of the organosilicon polymer compound are mixed in a powder mixer such as a ball mill, mortar, mixer, or rotating drum. It is mixed using In addition, intense mixing can be carried out by heating and melting the organosilicon polymer compound to form a solution, or by adding it to a solvent that can dissolve the organosilicon polymer compound, such as benzene, toluene, xylene, ethylbenzene, styrene, cumene, bentane, etc. Xane, octane, cyclobentadiene, cyclohexane, cyclohexene, methylene chloride, chloroform, carbon tetrachloride, 1,1-dichloroethane, 1,2-dichloroethane,
Methyl chloroform, 1,1,2-trichloroethane,
A metal powder is added to the solution as a solution dissolved in hexachloroethane, chlorobenzene, dioxybenzene, ethyl ether, dioxane, tetrahydrofuran, methyl acetate, ethyl acetate, acetonitrile, carbon disulfide, etc., and a mixer (e.g., ball mill, Mix using a mixer, rotating drum, mortar). The mixing is preferably carried out so that the powder and the organosilicon polymer compound are mixed sufficiently and uniformly. Next, the method of pressurization and coagulation can be roughly divided into two: pressurizing and coagulating the mixed powder grains of the starting raw material at a pressure of 100 to 8000 k9/base using a powder compaction method such as die press, isostatic press, or extrusion. Press,
After forming the powder into a predetermined shape, the powder is compacted by a heating method using, for example, a resistance heating furnace or a high frequency furnace. Add mixed powder grains and add 100~800
It is possible to use a hot press method in which sintering is performed while pressurizing the powder at a rate of 0 kg/powder and sintering is performed at the same time.

Although the hot pressing method is advantageous in order to obtain a material with higher performance, depending on the properties required of the cermet, the powder pressing method may also be sufficient to achieve the objective. As the atmosphere in the above-mentioned deposition, an atmosphere consisting of at least one type suitably selected from the group consisting of vacuum, N2 gas, inert gas, NH3 gas, CO gas, and hydrogen gas is used.

It is necessary to select and set the above-mentioned firing conditions such that the base metal powder and the organosilicon polymer compound are not adversely altered.

The Fe-Cr alloy used in the present invention includes Cr, F
In addition to e, it is possible to use a Fe-Cr metal material containing alloying elements that are normally added to Fe-Cr materials. Next, examples of the present invention will be described.

Example 1 Fe-Cr alloy powder (under 350 mesh) containing 13% by weight of Cr and polycarbosilane with an average molecular weight of 1000 were weighed at a weight ratio of 9:1, normal hexane was added thereto, mixed thoroughly and then dried. Dry in air.

After the above treatment, the powder is hot pressed to make it oxidation resistant.
A molded article with excellent corrosion resistance was obtained. A hot press jig was made of carbon, and hot pressing was performed at a press pressure of 200 k9/ground under an argon stream. The heating method is high frequency induction heating, the heating rate is 300oo/hr, and the maximum temperature is 110℃.
0.0 at 00C. After holding for a certain period of time, the pressure was released, the high frequency power was turned off, and the sample was left to cool. As a result of comparing the case where only Fe-Cr alloy was hot-pressed and the case where 1% by weight of polycarbosilane was added and then hot-pressed, it was found that polycarbosilane greatly contributed to improving oxidation resistance and acid resistance. It turned out that. Figure 3 shows Fe-13%Cr and Fe-13%
It is a figure which shows the result of the oxidation weight increase when two samples with Cr+1 broad weight% polycarbosilane were heated at 1000 qo in air.

From the same figure, it can be seen that oxidation progresses fairly rapidly over time in the hot-pressed product containing only Fe-13%Cr, but the oxidation weight gain of the product of the present invention, which was hot-pressed with the addition of polycarbosilane, was 20%. There wasn't much time until Kajima. The reference figure shows a photograph of the appearance of a sample after the test of product A of the present invention and conventional hot-pressed product B of chromium-iron alloy powder, which were subjected to an oxidation test by heating in air for 100 mm and 20 hours. Inventive product A showed no spalling at all. As shown in Figure 1A, the grain size was extremely small and the appearance did not change much from before the test, but in conventional product B, spalling was clearly observed, and grain growth was observed as shown in Figure 1B. was also recognized. In addition, transmission electron micrographs of a hot-pressed product of Fe-1+10% polycarposilane (product of the present invention) and a hot-pressed product of Fe-1*r (conventional product) are shown in Figures 1C and 1, respectively. Shown in D.

Comparing the two figures above, the product of the present invention containing 1% by weight of polycarbosilane differs from the conventional product in that the product has 0.0% polycarbosilane content along the grain boundaries.
Circular or oval CrSi2 or Cr7 of 34k or less
It is understood that C3 is generated and suppresses the growth of crystal grains, resulting in improved mechanical strength, wear resistance, and hardness. In addition, when the above-mentioned polycarposilane-added sample was piled up for 20 hours in the MPCI solution, there was no change in appearance and no increase in weight due to corrosion was observed.

It was also found that the same sample was stable up to 1150°C even in an atmosphere containing sulfur. On the other hand, those that were hot-pressed without the addition of polycarbosilane suffered significant corrosion under these corrosion conditions, resulting in material deterioration. As described above, the composite material obtained by the present invention has excellent acid resistance and corrosion resistance.
Example 2 Fe-Cr alloy powder containing 28% by weight of Cr (
350 mesh under) and polycarbosilane with an average molecular weight of 1000 were weighed at a weight ratio of 70:30, normal hexane was added, the mixture was mixed well, dried in dry air, and cold pressed at 0.5 ton/press. 50q in vacuum
The mixture was preheated to 60,000 ℃ at a rising/lowering temperature of o/hr, cooled, taken out, and pulverized in a ball mill.

This was further molded at 2bn/cm and heated to 120,000 at a heating rate of 10,000/hr in an argon stream, held at the same temperature for 1 hour, and then cooled to achieve heat resistance, high hardness,
A fired composite material with high ballistic properties was obtained. The results of the oxidation test of the obtained fired bodies (B without addition of polycarbosilane and A with addition of 3% by weight) are shown in FIG. As can be seen from FIG. 4, the effect of adding polycarbosilane is remarkable. 1000q0 in air
The appearance in the 20 feeding time oxidation test corresponded to the orientation shown in Figures 1A and B, but the oxidation resistance improved in proportion to the amount of polycarbosilane added. Next, the hardness of the obtained fired body is the same as that of the first
It was as shown in the table.

The hardness values are micro-Vickers hardness values. The indenter used during the measurement was a diamond, the load was 500 mm, and the holding time was 3.
For each sample of sand, one measurement point was taken as one needle point, and the average value was determined. As can be seen from the table, the addition of polycarbosilane dramatically increased the hardness of the fired product. Furthermore, the measured values of hardness had extremely small deviations.

This is because the carbides, silicides, etc. that make up this composite material are formed from reactively active ultrafine carbon and silicon, which are the decomposition products of organosilicon polymers, so they are extremely uniformly dispersed and the material itself is homogeneous. It is shown that. An increase in hardness usually means a drastic decrease in transverse rupture strength, but the transverse rupture strength of the highly hard fired product with polycarbosilane added was only 5% lower than that of one without polycarbosilane, indicating high strength. This material can be said to be sufficiently superior in terms of the development of high-hardness materials. Example 3 Fe-Cr alloy powder (under 350 mesh) containing 30% by weight of Cr and polycarposilane with an average molecular weight of 1500 were weighed at a weight ratio of 45:55, normal hexane was added, and the mixture was thoroughly mixed and mixed. The product was cold pressed at a temperature of .5k9/base, pre-calcined in vacuum to 600°C at an overflow rate of 25°C/hr, cooled, taken out and pulverized in a pole mill.

This was hot-pressed under conditions similar to Example 1 (pressing at 200k9/m and holding at 1100q○ for 0.5 hours) to obtain a composite material molded body. The micro Vickers hardness value of this material was 2200, and the resistance was 82k9/m. The composite material molded body obtained in this example fully satisfies the requirements for a cutting tool. As described above, the present invention provides a composite material with particularly excellent corrosion resistance, oxidation resistance, high hardness, and strength, and a method for manufacturing the same.The composite material according to the present invention can be used for cutting tools, press tools, Dice materials, various nozzles, engine parts, turbine blades, wear-resistant parts, heating element materials, heat-resistant materials, other mechanical parts, rubbo materials, or structural materials, durable materials with heat resistance, high temperature strength, oxidation resistance, and corrosion resistance. It is thought that it can exhibit sufficiently excellent performance in various fields where thermal shock resistance is required.

[Brief explanation of the drawing]

Figure 1A is a polishing corrosion micrograph of a composite material of the present invention prepared by adding and mixing 1% by weight of polycarbosilane to 13%Cr-Fe alloy powder and firing under pressure. Figure 1B is a 13%Cr-Fe alloy powder.
Fig. 1C is a transmission electron micrograph of the conventional composite material of the present invention, and Fig. 1D is a transmission electron micrograph of the conventional composite material made by hot-pressing e-alloy powder. The photograph, Figure 2 is a diagram showing the results of scanning X-ray analysis of the polished surface of the composite material of the present invention, and Figure 3 is 13%C.
Adding 1% by weight of polycarbosilane to r-Fe powder;
Composite material A of the present invention mixed, pressed and fired with 13% Cr
-Conventional material B made by pressurizing and firing Fe powder 10 in air
Figure 4 shows the results of the oxidation test at 0 pi 0.
2 instead of 13% Cr-Fe for each material shown in the figure.
It is a figure which shows the result of the oxidation test in the air at 1000 degreeC when 8%Cr-Fe was used. Fig. 1 Fig. 1 Fig. 1 Fig. 21 Fig. 3 Fig. 4

Claims (1)

[Claims] 1. Iron-chromium alloy 10-99.5%, 0 chromium carbide
．． 05-80%, chromium silicide 0.05-20%, iron oxide 0.01-40%, iron silicide 0.01-10%
, SiC0.01 to 30%, and at least one carbide selected from Fe, Cr, and Si and at least one selected from Fe and Cr between the chromium-iron alloy powder particles. A chromium-iron alloy composite material having a composition in which one type of silicide is present, wherein the chromium-iron alloy, carbide, and silicide are uniformly dispersed, and the interface of the dispersed particles is the chromium-iron alloy, carbide, and silicide. A chromium-iron alloy composite material having excellent heat resistance, corrosion resistance, oxidation resistance, abrasion resistance, hardness, and strength, and having a composition in which the carbides and silicides have a size of 10 μm or less and is formed from a fastening gradual phase shift. 2 Organosilicon polymer compound 1-70 containing 30-99% by weight of chromium-iron alloy powder and carbon and silicon as main skeleton components
The process of pressure molding the mixture with weight% and in vacuum, N_2
Gas, inert gas, CO gas, CO_2 gas, NH_3
At least one selected from gas and hydrogen gas
Heat and sinter in an atmosphere consisting of seeds at a temperature range of 700 to 1400°C to produce 10 to 99.5% iron/chromium alloy, 0.05 to 80% chromium carbide, and 0.05 to chromium silicide.
20%, iron carbide 0.01-40%, iron silicide 0.0
1 to 10% SiC, 0.01 to 30% SiC, and at least one carbide selected from Fe, Cr, and Si and Fe, C between the chromium iron alloy powder particles.
It has a composition in which at least one type of silicide selected from r is present, the chromium iron alloy, carbide, and silicide are uniformly dispersed, and the interface of the dispersed particles is the chromium iron alloy, carbide, and silicide. heat resistance, corrosion resistance, oxidation resistance, characterized by the step of obtaining a chromium-iron alloy composite material formed from fastening gradual phase shift and having a composition in which the size of the carbide and silicide is 10μ or less; wear resistance,
A method for producing a chromium-iron alloy composite material with excellent hardness and strength.