CN105239160B - Nano crystal zirconium diboride and its alloy and the application in bearing ball surface treatment - Google Patents
Nano crystal zirconium diboride and its alloy and the application in bearing ball surface treatment Download PDFInfo
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Abstract
The present invention relates to high-abrasive material field, it is desirable to provide a kind of nano crystal zirconium diboride and its alloy and the application in bearing ball surface treatment.This method includes：Zirconium compounds and alkali metal boronhydride powder are taken, ball grinder ball milling is added in the lump with zirconia balls, obtains mechanical impurity；It is placed in reactor, is incubated 2 hours after being heated to 300~600 DEG C from room temperature with 2 DEG C/min heating rate, discharges gas；Room temperature is subsequently cooled to, is dried in vacuo after washing at 80 DEG C, obtains nano crystal zirconium diboride.This invention greatly reduces zirconium diboride or the synthesis temperature of zirconium diboride alloy, lifts the homogeneity of ingredients and monocrystalline granularity uniformity of zirconium diboride alloy, is advantageous to the qualitative control of large-scale production.When handling ball surface, it is avoided that high temperature causes the change of ball size or roundness, beneficial to the qualitative control of ball industrialized production.Technique is simple, and energy consumption is low, is easy to quality control, has wide industrialization prospect.
Description
Technical field
The present invention is to be related to the preparation method of nano crystal zirconium diboride and alloy on high-abrasive material field, is especially related to
And one kind surface treatment temperature is low, deformation is small, forms nano crystal zirconium diboride or zirconium diboride alloy wear-resisting on ball surface
The bearing ball surface treatment method of layer, the abrasive resistance and service life of bearing ball can be effectively improved.
Background technology
Zirconium boride includes a zirconium boride, zirconium diboride and three zirconium borides, wherein, only zirconium diboride is in very wide temperature model
It is stable to enclose.Zirconium diboride is hexahedron crystal formation, gray crystals or powder, and relative density 5.8, fusing point is 3040 DEG C, resistance to height
Temperature.Normal temperature and high temperature strength are very high.Resistance to heat shocks is good, and resistance is small, anti-oxidant under high temperature.
The preparation of metal boride has hot pressed sintering, mechanical alloying, SHS process, electrolysis fused salt, solvent heat
The synthetic methods such as method, discharge plasma sintering.Such as boron powder is mixed by a certain percentage with tungsten powder, synthesizes boronation tungsten powder at high temperature
Body, then tungsten boride ceramics are prepared for using cold pressing and high temperature sintering as raw material；With ZrB2As adulterating agent, burnt by hot pressing
Knot is prepared for TiB2-ZrB2Composite ceramics is dissolved, is that process and equipment are complicated the shortcomings that hot pressed sintering, production control requires strict,
Mold materials require high, and energy resource consumption is big, and production efficiency is relatively low, and production cost is high；Mechanical alloying is non-under a normal temperature
Solid-state reaction process is balanced, the reaction is also referred to as mechanico-chemical reaction, and its thermodynamics, dynamics are anti-different from common solid-state
Should, easily cause composition uneven, equally exist the shortcomings that energy resource consumption is big, and production efficiency is relatively low, and production cost is high.
Self-propagating high-temperature synthesis (SHS), also referred to as combustion synthesis method, it is the heat for utilizing the chemical reaction between material to release
Amount, synthetic reaction is set voluntarily persistently to carry out until reaction terminates, so as to synthesize one kind of material requested in a short period of time
New method.SHS technologies are because the characteristics of aggregate velocity is fast, temperature is high, cooling velocity is fast, equipment is simple, small investment, less energy consumption
A kind of new material technology of preparing paid attention to extensively as modern science and industrial technical field.But SHS methods can generate
Compound in introduce " external " material (impurity), and make inert boron participate in reaction required for high temperature can cause to come it is reflexive
Answer the dirt of container (crucible), reactant (carbon, the metallic additionses added as reducing agent) and reaction atmosphere (water and oxygen) etc.
Dye.Except by the inertia and height temperate zone of boron Lai difficulty in addition to, the boride rich in metal is in atmosphere or in wet environment
Instability problem also can not be ignored.
Diboron trioxide (or borax) and metal oxide are dissolved in a kind of appropriate fused salt (such as alkali metal or alkali together
The halide or borofluoride of earth metal) in, make anode with graphite at 700~1000 DEG C, graphite or steel make negative electrode, carry out electricity
The easy control of reaction conditions of the fused salt electrolysis process of solution, environment is relatively friendly, is to prepare the up-and-coming method of metal boride
One of.But the shortcomings that existing is also that can not be ignored: (1) may generate the thing phase of several borides；(2) prepared by fused salt electrolysis process
Boride is not easy serialization, because electrolysate is mostly insulator, is attached near negative electrode, prevents electrolysis from continuing.(3) melt
The shortcomings that salt electrolysis generally existing current efficiency is low, current efficiency are not higher than 50%.The insulating property (properties) of boride, which turns into, to be improved
The serious hindrance of current efficiency.
Discharge plasma sintering (SPS), also referred to as pulse electric current sintering (pulsed electric current
Sintering, PECS) and field assisted sintering (field assisted sintering technique, FAST), it is a kind of
Quickly, low temperature, the material of energy-saving and environmental protection prepare New Machining Technology, can not only enter the sintering of row metal and ceramic material, also may be used
To realize that reaction in-situ sinters, thermograde sintering, material connection can be also used for.The technology is between the powder granule that pressurizes
DC pulse electric energy is passed directly into, the Joule heat as caused by inside particle causes to produce hundreds of to thousands of degree with surface inside particle
The temperature difference, so as to realize sintering neck formation, extension and densification, its consume electric energy only have conventional sintering technique (it is no pressure burn
Tie PLS, hot pressed sintering HP, high temperature insostatic pressing (HIP) HIP) 1/5~1/3.SPS technologies are with sintering is quick, sintering temperature is low, operation is simple
The advantages that folk prescription is just, occupation area of equipment is small, automaticity is high, technological process is short, be widely used in recent years metal and
In the research and development of alloy material, ceramic material, composite, functionally gradient material (FGM), nano material etc..By rare earth hydride powder
Sinter and synthesize with boron powder reaction in-situ, it is 80~100nm successfully to prepare grain size, consistency reach 99.2% it is nanocrystalline
Rare-earth boride block materials, show excellent mechanical property and electron emission capability.But pulse electric current sintering there is also,
Discharge uneven, control of product quality is difficult, can not the disadvantage such as mass industrialized production.
Zirconium diboride is heated to 2000 DEG C in argon gas stream and is made after generally being mixed by metal zirconium with boron carbide, boron nitride.
It can be used as aerospace exotic material, the solid material of wear resistant smooth, cutting element, temperature difference heat galvanic couple protection pipe and electrolyzing fused
The electrode material of compound.It is suitable for use as the surface of rolling bearing ball.Using hot pressed sintering, mechanical alloying, self- propagating
High―temperature nuclei, electrolysis fused salt, solvent-thermal method, discharge plasma sintering are readily obtained its polycrystalline material when preparing zirconium diboride.This
The usual energy consumption of a little methods is larger, and control of product quality is difficult.
Ball bearing is one kind of rolling bearing, and spherical alloy steel ball is arranged on to the centre of interior steel ring and outer rim, with
Roll mode come reduce the frictional force in power transmission process and improve machine power transmission efficiency.Because ball bearing is held
Section product is small, easily occurs serious mechanical injuries in the case where running at high speed, and reduces the mechanicalness damage on ball surface
Wound is to improve the key factor in ball bearing life-span.Therefore, the anti-wear performance for improving ball is most important.
Bearing steel wire rod is cut into certain length generally in sphere forming machine, by the hemispherical ball seat in both sides
Female, male dies compress, spheroid shaping；Between the ball of compression molding is clipped in two mills, rotates and apply pressure, remove
Burr；The intensity and wearability of steel ball are improved through Overheating Treatment.Technology for Heating Processing and method, pole is influenceed on the wearability of ball
Greatly.
The content of the invention
The technical problem to be solved in the present invention is to overcome deficiency of the prior art, there is provided a kind of reaction temperature is low, reaction
The condition nano crystal zirconium diboride small compared with gentle, energy consumption, the preparation method of nano crystal zirconium diboride alloy and right using its
Bearing ball surface carries out processing method.
In order to solve the above technical problems, the solution of the present invention is：
The invention provides a kind of method for preparing nano crystal zirconium diboride, comprise the following steps：
Zirconium compounds and alkali metal boronhydride powder are weighed for 1: 2 or 1: 4 by Zr: B mol ratio, with zirconium dioxide
Ball adds ball grinder in the lump, the ball milling after 16 hours under 200rpm rotating speeds, obtains zirconium compounds and alkali metal boronhydride
Mechanical impurity；Mechanical impurity is placed in reactor, 300~600 DEG C are heated to from room temperature with 2 DEG C/min heating rate
2 hours are incubated afterwards, discharges gas；Room temperature is subsequently cooled to, is dried in vacuo after washing at 80 DEG C, obtains the boron of nano crystal two
Change zirconium.
Further, the invention provides a kind of method for preparing nano crystal zirconium diboride alloy, comprise the following steps:
Alkali metal boronhydride, zirconium compounds, the second metal compound powders are placed in ball grinder, zr element and
Two metal molar number sums and the mol ratio of boron are 1: 2；Second metallic compound is the oxide of transition metal M, hydroxide
Or inorganic salts, transition metal M refer to Cr, Mn, Fe, Co, Ni, Cu or Zn, Zr: M in zirconium compounds and the second metallic compound
Mol ratio is 1: 0.11~1；
Mixture after ball milling 16 hours, is obtained into zirconium compounds, the second metallic compound and alkali gold under 200rpm rotating speeds
Belong to the mechanical impurity of hydroboron；Mechanical impurity is placed in reactor, added with 2 DEG C/min heating rate from room temperature
2 hours are incubated after hot to 300~600 DEG C, discharges gas；Room temperature is subsequently cooled to, is dried in vacuo, obtains at 80 DEG C after washing
To nano crystal zirconium diboride alloy.
Further, closed the invention provides one kind using foregoing nano crystal zirconium diboride or nano crystal zirconium diboride
Gold prepares the method that surface possesses the bearing ball of wearing layer, comprises the following steps：
The polyvinyl alcohol for being 3wt% with 10mL concentration (PVA) aqueous solution, mixed with 0.1g nano crystal zirconium diboride alloys
It is formed uniformly suspension；Dried after suspension is coated on into bearing ball surface, make the coated weight on bearing ball surface for 0.1~
0.3mg/cm2；Then it is placed in reactor, is heated to 600~900 DEG C with 2 DEG C/min heating rate, is incubated 2 hours,
Obtaining surface has the bearing ball of wearing layer.
Further, the invention provides a kind of bearing ball for preparing surface and possessing nano crystal zirconium diboride wearing layer
Method, comprise the following steps：
Zirconium compounds and alkali metal boronhydride powder are weighed for 1: 2 or 1: 4 by Zr: B mol ratio, with bearing ball
Blank adds ball grinder in the lump, and ball milling makes to attach zirconium chemical combination on bearing ball blank surface after 16 hours under 200rpm rotating speeds
The mechanical impurity of thing and alkali metal boronhydride；Take out bearing ball blank to be placed in reactor, with 2 DEG C/min heating
Speed is incubated 2 hours after being heated to 600~900 DEG C from room temperature, discharges gas；Room temperature is subsequently cooled to, at 80 DEG C after washing
Lower vacuum drying, obtains the bearing ball for possessing nano crystal zirconium diboride wearing layer to surface.
Further, the invention provides a kind of bearing ball for preparing and possessing nano crystal zirconium diboride alloy wear-resisting layer
Method, comprise the following steps：
In ball grinder, alkali metal boronhydride is dissolved in tetrahydrofuran, then adds zirconium compounds, the second metallization
Compound and bearing ball blank；Wherein, every liter of 0.1~0.4 mole of tetrahydrofuran alkali metal containing hydroboron；Second metallization
Compound is the oxide, hydroxide or inorganic salts of transition metal M, and transition metal M refers to Cr, Mn, Fe, Co, Ni, Cu or Zn；
In zirconium compounds and the second metallic compound Zr: M mol ratio be 1: 0.11~1 zr element and the second metal molar number sum and
The mol ratio of boron is 1: 2；
By said mixture under 400rpm rotating speeds ball milling 2 hours, bearing ball blank surface is attached pastel；Take out
Bearing ball blank is placed in reactor, and solvent THF is evaporated at 120 DEG C, pastel is turned into zirconium compounds and alkali metal boron
The mechanical impurity of hydrogen compound；2 hours are incubated after being heated to 600~900 DEG C again with 2 DEG C/min of heating rate, discharges gas
Body；Room temperature is subsequently cooled to, is dried in vacuo after washing at 80 DEG C, obtains to surface and possesses nano crystal zirconium diboride alloy wear-resisting
The bearing ball of layer.
In the present invention, the alkali metal boronhydride is lithium borohydride, sodium borohydride or potassium borohydride.
In the present invention, the zirconium compounds refers to the oxide, hydroxide or inorganic salts of zirconium.
In the present invention, the inorganic salts of the transition metal M refer to：Chloride, sulfate, nitrate or the phosphorus of transition metal
Hydrochlorate.
Inventive principle describes：
At 600~900 DEG C, alkali metal boronhydride dehydrogenation forms the boride intermediate of high activity, in boride
Mesosome generates zirconium diboride or zirconium diboride alloy with zirconium compounds, or the reaction of the second metallic compound again, so as to relatively low
At a temperature of reaction obtain nano crystal zirconium diboride or zirconium diboride alloy；The molecular formula of zirconium diboride alloy is Zr1-xMxB2, M
For Cr, Mn, Fe, Co, Ni, Cu or Zn.In the present invention, the release gas is hydrogen, or the hydrogen containing diborane.
Compared with prior art, the beneficial effects of the invention are as follows：
1st, the present invention is raw material using alkali metal boronhydride, significantly reduces zirconium diboride or zirconium diboride alloy
Synthesis temperature, lifted zirconium diboride alloy homogeneity of ingredients and monocrystalline granularity uniformity, be advantageous to large-scale production product
Matter management.
2nd, the present invention avoids high temperature from causing ball when carrying out zirconium diboride or zirconium diboride alloy treatment to ball surface
The change of size or roundness, beneficial to the qualitative control of ball industrialized production.
3rd, technique is simple, and energy consumption is low, is easy to quality control.The present invention has wide industrialization prospect.
Embodiment
The present invention is described in further detail with reference to embodiment：
Embodiment 1：Nano crystal zirconium diboride synthesizes
It is that 1: 4 (Zr: B=1: 4) weigh ZrO by the mol ratio of zirconium and boron2(0.123g) and lithium borohydride (0.088g) powder
End adds ball grinder, and ball milling obtains the mechanical impurity of zirconium oxide and lithium borohydride under 200rpm rotating speeds after 16 hours, is placed in
In reactor, 2 DEG C/min of heating rate is incubated 2 hours after being heated to 300 DEG C from room temperature.
ZrO2+4LiBH4→ZrB2+2Li2O+B2H6+5H2
When discharging gas, because diborane be toxic and harmful gas, it is impossible to directly discharge, therefore by the hydrogen containing diborane
Gas is passed through in water, and diborane hydrolyzes to obtain harmless hydrogen and boric acid.Washed after being cooled to room temperature, lithia is dissolved in during washing
Water, centrifuge, be dried in vacuo at 80 DEG C and obtain nano crystal zirconium diboride.
Embodiment 2：Zirconium diboride using zirconium hydroxide and sodium borohydride as raw material synthesizes
When replacement zirconium oxide uses zirconium hydroxide as metal zirconium source, zirconium diboride does not produce poisonous and hazardous second when synthesizing
Borine, therefore, zirconium hydroxide and sodium borohydride are more green for the zirconium diboride synthesis technique of raw material.
It is that 1: 4 (Zr: B=1: 4) weigh Zr (OH) by the mol ratio of zirconium and boron4(0.159g) and sodium borohydride (0.152g)
Powder adds ball grinder, and ball milling obtains the mechanical impurity of zirconium hydroxide and sodium borohydride under 200rpm rotating speeds after 16 hours,
It is placed in reactor, 2 DEG C/min of heating rate is incubated 2 hours after being heated to 400 DEG C from room temperature.
Zr(OH)4+4NaBH4→ZrB2+2NaBO2+2NaH+9H2
Hydrogen is discharged, is washed after being cooled to room temperature, NaH and water reaction generation hydrogen and sodium hydroxide, hydrogen-oxygen during washing
Change sodium and NaBO2Water is dissolved in, is centrifuged, is dried in vacuo at 80 DEG C and obtains nano crystal zirconium diboride.
Embodiment 3：Zirconium chloride is Material synthesis monocrystalline zirconium diboride
By zirconium, the mol ratio of copper and boron weighs ZrCl for 1: 2 (Zr: B=1: 2)2(0.162g) and potassium borohydride
(0.215g) powder adds ball grinder, and ball milling obtains mechanical impurity after 16 hours under 200rpm rotating speeds, is placed on reaction
In device, 2 DEG C/min of heating rate is incubated 2 hours after being heated to 600 DEG C from room temperature.
ZrCl2+2KBH4→ZrB2+2KCl+4H2
Hydrogen is discharged, is washed after being cooled to room temperature, potassium chloride is dissolved in water during washing, centrifuges, and vacuum is done at 80 DEG C
It is dry to obtain nano crystal zirconium diboride alloy.
Embodiment 4：The synthesis of monocrystalline zirconium diboride copper alloy
By zirconium, the mol ratio of copper and boron is 0.5: 0.5: 2 (Zr: Cu: B=0.5: 0.5: 2), wherein zr element and copper mole
Number sum and the mol ratio of boron are 1: 2；Weigh ZrCl2(0.081g)、CuCl2(0.067g) and potassium borohydride (0.215g) powder
Ball grinder is added, ball milling obtains mechanical impurity after 16 hours under 200rpm rotating speeds, is placed in reactor, heating rate
2 DEG C/min is incubated 2 hours after being heated to 600 DEG C from room temperature.
0.5ZrCl2+0.5CuCl2+2KBH4→Zr0.5Cu0.5B2+2KCl+4H2
Hydrogen is discharged, is washed after being cooled to room temperature, potassium chloride is dissolved in water during washing, centrifuges, and vacuum is done at 80 DEG C
It is dry to obtain nano crystal zirconium diboride copper alloy.
When copper chloride is substituted by the copper nitrate, copper sulphate or cupric phosphate of the copper containing equimolar, corresponding ZrCl is added2And boron
Hydrofining, ball milling obtains mechanical impurity after 16 hours under 400rpm rotating speeds, is placed in reactor, and 2 DEG C of heating rate/
Min is incubated 2 hours after being heated to 500 DEG C from room temperature.Hydrogen is discharged, is washed after being cooled to room temperature, is centrifuged, it is true at 80 DEG C
Sky drying can equally obtain nano crystal zirconium diboride copper alloy.
Embodiment 5：Synthesized using the nano crystal zirconium diboride alloy of sulfate
By zirconium, the mol ratio of the second metal and boron weighs ZrSO for 0.6: 0.4: 2 (Zr: M: B=0.6: 0.4: 2)4
(0.113g)、MSO4(0.4 mM) and lithium borohydride (0.044g) powder is placed in ball grinder, and wherein zirconium rubs with the second metal
That number sum and the mol ratio of boron are 1: 2；Ball milling obtains mechanical impurity after 16 hours under 200rpm rotating speeds, is placed on anti-
Answer in device, 2 DEG C/min of heating rate is incubated 2 hours after being heated to 600 DEG C from room temperature.
0.6ZrSO4+0.4MSO4+2LiBH4→Zr0.6M0.4B2+Li2SO4+4H2
M is Cr, Mn, Fe, Co, Ni, Cu, Zn.Discharge hydrogen.Wash after being cooled to room temperature, be dried in vacuo at 80 DEG C
To the alloy of zirconium diboride containing nano crystal: zirconium diboride chromium, zirconium diboride manganese, zirconium diboride iron, zirconium diboride cobalt, zirconium diboride
Nickel, zirconium diboride copper and zirconium diboride zinc.
Embodiment 6：Synthesized using the nano crystal zirconium diboride nickel of nickel nitrate
By zirconium, the mol ratio of nickel and boron weighs Zr (NO for 0.8: 0.2: 2 (Zr: Ni: B=0.8: 0.2: 2)3)2
(0.172g)、Ni(NO3)2(0.042g) and lithium borohydride (0.044g) powder is placed in ball grinder, wherein zr element and nickel mole
Number sum and the mol ratio of boron are 1: 2；Ball milling obtains mechanical impurity after 16 hours under 200rpm rotating speeds, is placed on reaction
In device, 2 DEG C/min of heating rate is incubated 2 hours after being heated to 600 DEG C from room temperature.
0.8Zr(NO3)2+0.2Ni(NO3)2+2LiBH4→Zr0.8Ni0.2B2+2LiNO3+4H2
M is Cr, Mn, Fe, Co, Ni, Cu, Zn.Discharge hydrogen.Wash after being cooled to room temperature, be dried in vacuo at 80 DEG C
To the nickel of zirconium diboride containing nano crystal.
Embodiment 7：Synthesized using the nano crystal zirconium diboride iron of ferrous hydroxide
By zirconium, the mol ratio of iron and boron is 0.9: 0.1: 2 (Zr: Fe=1: 0.11, Zr: Fe: B=0.9: 0.1: 2) weigh
Zr3(PO4)2(0.139g)、Fe(OH)2(0.072g) and lithium borohydride (0.044g) powder is placed in ball grinder, wherein zr element
It is 1: 2 with iron molal quantity sum and the mol ratio of boron；Ball milling obtains mechanical impurity after 16 hours under 200rpm rotating speeds, by it
It is placed in reactor, 2 DEG C/min of heating rate is incubated 2 hours after being heated to 300 DEG C from room temperature.
0.3Zr3(PO4)2+0.1Fe(OH)2+2LiBH4→Zr0.9Fe0.1B2+0.6Li3PO4+0.2LiOH+4H2
Discharge hydrogen.Lithium phosphate and lithium hydroxide are water-washed away after being cooled to room temperature, is dried in vacuo to obtain containing at 80 DEG C and receives
Meter Dan Jing zirconium diboride iron.
Embodiment 8：Zirconium oxide is the application that the nano crystal zirconium diboride that raw material obtains is surface-treated in ball
Mixed with the 0.1g nano crystal zirconium diborides obtained in embodiment 1 with the 3wt% PVA aqueous solution (10mL)
It is even, form suspension；Suspension is coated on ball surface, is placed in after drying in reactor, zirconium diboride coated weight reaches
0.1mg/cm2, 2 DEG C/min of heating rate, which is incubated 2 hours after being heated to 600 DEG C and obtains surface, has nano crystal zirconium diboride resistance to
Grind the ball of layer.
Embodiment 9：Zirconium hydroxide is the application that the nano crystal zirconium diboride that raw material obtains is surface-treated in ball
Mixed with the 0.1g nano crystal zirconium diborides obtained in embodiment 2 with the 3wt% PVA aqueous solution (10mL)
It is even, form suspension；Suspension is coated on ball surface, is placed in after drying in reactor, zirconium diboride coated weight reaches
0.2mg/cm2, 2 DEG C/min of heating rate, which is incubated 2 hours after being heated to 700 DEG C and obtains surface, has nano crystal zirconium diboride resistance to
Grind the ball of layer.
Embodiment 10：Zirconium chloride is the application that the nano crystal zirconium diboride that raw material obtains is surface-treated in ball
Mixed with the 0.1g nano crystal zirconium diborides obtained in embodiment 3 with the 3wt% PVA aqueous solution (10mL)
It is even, form suspension；Suspension is coated on ball surface, is placed in after drying in reactor, zirconium diboride coated weight reaches
0.3mg/cm2, 2 DEG C/min of heating rate, which is incubated 2 hours after being heated to 900 DEG C and obtains surface, has nano crystal zirconium diboride resistance to
Grind the ball of layer.
Embodiment 11：The nano crystal zirconium diboride copper alloy processing on ball surface
Mixed with the 0.1g nano crystal zirconium diboride copper obtained in embodiment 4 with the 3wt% PVA aqueous solution (10mL)
It is even, form suspension；Suspension is coated on ball surface, is placed in after drying in reactor, zirconium diboride copper coated weight reaches
0.2mg/cm2, 2 DEG C/min of heating rate, which is incubated 2 hours after being heated to 900 DEG C and obtains surface, has nano crystal zirconium diboride copper
The ball of wearing layer.
Embodiment 12：The nano crystal zirconium diboride nickel alloy processing on ball surface
Mixed with the 0.1g nano crystal zirconium diboride nickel obtained in embodiment 5 with the 3wt% PVA aqueous solution (10mL)
It is even, form suspension；Suspension is coated on ball surface, is placed in after drying in reactor, zirconium diboride nickel coated weight reaches
0.3mg/cm2, 2 DEG C/min of heating rate, which is incubated 2 hours after being heated to 800 DEG C and obtains surface, has nano crystal zirconium diboride nickel
The ball of wearing layer.
Embodiment 13：The nano crystal zirconium diboride kirsite processing on ball surface
Mixed with the 0.1g nano crystal zirconium diboride zinc obtained in embodiment 5 with the 3wt% PVA aqueous solution (10mL)
It is even, form suspension；Suspension is coated on ball surface, is placed in after drying in reactor, zirconium diboride zinc coated weight reaches
0.1mg/cm2, 2 DEG C/min of heating rate, which is incubated 2 hours after being heated to 600 DEG C and obtains surface, has nano crystal zirconium diboride zinc
The ball of wearing layer.
Embodiment 14：Zirconium oxide is surface-treated for the ball of raw material
It is that 1: 4 (Zr: B=1: 4) weigh ZrO by the mol ratio of zirconium and boron2(0.123g) and lithium borohydride (0.088g) with
And a diameter of 1 centimetre of ball blank 7 adds ball grinders, ball grinder internal diameter is 3.5 centimetres, high 4 centimetres, in 200rpm rotating speeds
Lower ball milling attaches the mechanical impurity of zirconium oxide and lithium borohydride after 16 hours on ball blank surface, take out ball blank
It is placed in reactor, 2 DEG C/min of heating rate is incubated 2 hours after being heated to 600 DEG C from room temperature.When discharging gas, due to second boron
Alkane is toxic and harmful gas, it is impossible to directly discharges, therefore the hydrogen containing diborane is passed through in water, diborane hydrolyzes to obtain nothing
Harmful hydrogen and boric acid.Washed after being cooled to room temperature, be dried in vacuo at 80 DEG C and obtain the wearing layer of zirconium diboride containing nano crystal
Ball, surface zirconium diboride content are 0.1mg/cm2。
Embodiment 15：Zirconium hydroxide is surface-treated for the ball of raw material
It is that 1: 4 (Zr: B=1: 4) weigh Zr (OH) by the mol ratio of zirconium and boron4(0.159g) and sodium borohydride (0.152g)
Powder and a diameter of 1 centimetre 7 addition ball grinders of ball blank, ball grinder internal diameter is 3.5 centimetres, high 4 centimetres,
Ball milling attaches the mechanical impurity of zirconium hydroxide and lithium borohydride after 16 hours under 200rpm rotating speeds on ball blank surface,
Take out ball blank to be placed in reactor, 2 DEG C/min of heating rate is incubated 2 hours after being heated to 800 DEG C from room temperature.Discharge hydrogen
Gas.Washed after being cooled to room temperature, be dried in vacuo at 80 DEG C and obtain the ball of the wearing layer of zirconium diboride containing nano crystal, the boron of surface two
Change zirconium content is 0.2mg/cm2。
Embodiment 16：Zirconium sulfate is surface-treated for the ball of raw material
It is that 1: 2 (Zr: B=1: 2) weigh ZrSO by the mol ratio of zirconium and boron4With sodium borohydride (0.076g) and a diameter of
1 centimetre 7 addition ball grinders of ball blank, ball grinder internal diameter is 3.5 centimetres, high 4 centimetres, the ball milling 16 under 200rpm rotating speeds
After hour, ball blank has attached ZrSO on surface4With the mechanical impurity of sodium borohydride, take out ball blank and be placed in reactor
In, 2 DEG C/min of heating rate is incubated 2 hours after being heated to 900 DEG C from room temperature,
ZrSO4+2NaBH4→ZrB2+Na2SO4+4H2
Discharge hydrogen.Washed after being cooled to room temperature, to obtain zirconium diboride containing nano crystal wear-resisting for vacuum drying at 80 DEG C
The ball of layer, surface zirconium diboride content is 0.3mg/cm2。
Wear-resisting test experiment shows that the ball of the ferroalloy wearing layer of zirconium diboride containing nano crystal is more wear-resisting than original ball
Life-span is doubled.
Embodiment 17：Zirconium sulfate and ferric phosphate for the ball surface of raw material Alloying Treatment
Lithium borohydride (0.044g) is dissolved in tetrahydrofuran (THF) in ball grinder, by zirconium, the mol ratio of iron and boron is
0.8: 0.2: 2 (Zr: M=1: 0.25, Zr: Fe: B=0.8: 0.2: 2) weigh ZrSO4(0.15g)、FePO4(0.03g) and powder
And a diameter of 1 centimetre of ball blank 7 adds ball grinders, ball grinder internal diameter is 3.5 centimetres, high 4 centimetres, wherein, every liter
0.1 mole of tetrahydrofuran alkali metal containing hydroboron；Ball milling forms pastel under 400rpm rotating speeds after 2 hours, and ball is former
Pastel has been attached on base surface, ball blank has been taken out and is placed in reactor, solvent THF is evaporated at 120 DEG C and obtains mechanical mixture
Thing, 2 DEG C/min of heating rate are incubated 2 hours after being heated to 900 DEG C,
Discharge hydrogen.Washed after being cooled to room temperature, be dried in vacuo at 80 DEG C and obtain the conjunction of the iron of zirconium diboride containing nano crystal
The ball of golden wearing layer.Surface zirconium diboride iron content is 0.3mg/cm2。
Wear-resisting test experiment shows that the ball of the ferroalloy wearing layer of zirconium diboride containing nano crystal is more wear-resisting than original ball
Life-span improves 1.5 times.
Embodiment 18：Handled using the ball surface alloying of sulfate
Lithium borohydride (0.044g) is dissolved in tetrahydrofuran (THF) in ball grinder, by zirconium, mole of the second metal and boron
Than for 0.6: 0.4: 2 (Zr: M=1: 0.667, Zr: M: B=0.6: 0.4: 2) weigh ZrSO4(0.113g)、MSO4(0.4 mmoles
You) and a diameter of 1 centimetre of addition ball grinders of ball blank 7, ball grinder internal diameter is 3.5 centimetres, high 4 centimetres, wherein, often
Rise 0.3 mole of tetrahydrofuran alkali metal containing hydroboron；Ball milling forms pastel, ball under 400rpm rotating speeds after 2 hours
Pastel has been attached on blank surface, ball blank has been taken out and is placed in reactor, solvent THF is evaporated at 120 DEG C and obtains mechanical mix
Compound, 2 DEG C/min of heating rate are incubated 2 hours after being heated to 800 DEG C,
0.6ZrSO4+0.4MSO4+2LiBH4→Zr0.6M0.4B2+Li2SO4+4H2
Discharge hydrogen.Washed after being cooled to room temperature, be dried in vacuo at 80 DEG C and obtain the alloy of zirconium diboride containing nano crystal
The ball of wearing layer.M is Cr, Mn, Fe, Co, Ni, Cu, Zn
Embodiment 19：Handled using the ball surface alloying of basic zirconium phosphate and ferrous hydroxide
Lithium borohydride (0.044g) powder is dissolved in tetrahydrofuran (THF), by zirconium, the mol ratio of iron and boron in ball grinder
For 0.9: 0.1: 2 (Zr: M=1: 0.11, Zr: Fe: B=0.9: 0.1: 2) weigh Zr3(PO4)2(0.139g)、Fe(OH)2
(0.072g) and a diameter of 1 centimetre 7 addition ball grinders of ball blank, ball grinder internal diameter is 3.5 centimetres, high 4 centimetres, its
In, zr element is 1: 2 with iron sum and the mol ratio of boron；Every liter of 0.4 mole of tetrahydrofuran alkali metal containing hydroboron；
Ball milling forms pastel under 400rpm rotating speeds after 2 hours, and pastel has been attached on ball blank surface, takes out ball blank and is placed in
In reactor, solvent THF is evaporated at 120 DEG C and obtains mechanical impurity, insulation 2 is small after 2 DEG C/min of heating rate is heated to 600 DEG C
When,
0.3Zr3(PO4)2+0.1Fe(OH)2+2LiBH4→Zr0.9Fe0.1B2+0.6Li3PO4+0.2LiOH+4H2
Discharge hydrogen.Lithium phosphate and lithium hydroxide are water-washed away after being cooled to room temperature, is dried in vacuo to obtain containing at 80 DEG C and receives
The ball of meter Dan Jing zirconium diboride ferroalloy wearing layers.Surface zirconium diboride iron content is 0.1mg/cm2。
Embodiment 20：Zirconium chloride and copper chloride are surface-treated for the ball of raw material
By zirconium, the mol ratio of copper and boron weighs ZrCl for 0.5: 0.5: 2 (Zr: Cu: B=0.5: 0.5: 2)2(0.081g)、
CuCl2(0.067g) and potassium borohydride (0.215g) powder and a diameter of 1 centimetre 7 addition ball grinders of ball blank, ball
Grinding jar internal diameter is 3.5 centimetres, high 4 centimetres, wherein, zirconium is 1: 2 with copper molal quantity sum and the mol ratio of boron；Every liter of tetrahydrofuran
0.2 mole of alkali metal containing hydroboron；Ball milling forms pastel under 400rpm rotating speeds after 2 hours, on ball blank surface
Pastel has been attached, ball blank has been taken out and is placed in reactor, solvent THF is evaporated at 120 DEG C and obtains mechanical impurity, heating speed
2 DEG C/min of rate is incubated 2 hours after being heated to 600 DEG C,
0.5ZrCl2+0.5CuCl2+2KBH4→Zr0.5Cu0.5B2+2KCl+4H2
Discharge hydrogen.Washed after being cooled to room temperature, to obtain zirconium diboride containing nano crystal wear-resisting for vacuum drying at 80 DEG C
The ball of layer, surface zirconium diboride copper content is 0.2mg/cm2。
Claims (3)
- A kind of 1. method for preparing surface and possessing the bearing ball of wearing layer, it is characterised in that comprise the following steps：The polyvinyl alcohol water solution for being 3wt% with 10mL concentration, with 0.1g nano crystals zirconium diboride or the boronation of nano crystal two Zircaloy is well mixed to form suspension；Dried after suspension is coated on into bearing ball surface, make the painting on bearing ball surface The amount of covering is 0.1~0.3mg/cm2；Then it is placed in reactor, 600~900 is heated to 2 DEG C/min heating rate DEG C, 2 hours are incubated, obtaining surface has the bearing ball of wearing layer；The preparation method of the nano crystal zirconium diboride comprises the following steps：Zirconium compounds and alkali metal boronhydride powder are weighed for 1: 2 or 1: 4 by Zr: B mol ratio, with zirconia balls one And ball grinder is added, ball milling obtains the machinery of zirconium compounds and alkali metal boronhydride after 16 hours under 200rpm rotating speeds Mixture；Mechanical impurity is placed in reactor, protected after being heated to 300~600 DEG C from room temperature with 2 DEG C/min heating rate Temperature 2 hours, discharges gas；Room temperature is subsequently cooled to, is dried in vacuo after washing at 80 DEG C, obtains the boronation of nano crystal two Zirconium；The preparation method of the nano crystal zirconium diboride alloy comprises the following steps：Alkali metal boronhydride, zirconium compounds, the second metal compound powders are placed in ball grinder, zr element and the second gold medal The mol ratio for belonging to molal quantity sum and boron is 1: 2；Second metallic compound is the oxide, hydroxide or nothing of transition metal M Machine salt, transition metal M refer to Cr, Mn, Fe, Co, Ni, Cu or Zn, Zr: M mole in zirconium compounds and the second metallic compound Than for 1: 0.11~1；Mixture after ball milling 16 hours, is obtained into zirconium compounds, the second metallic compound and alkali metal boron under 200rpm rotating speeds The mechanical impurity of hydrogen compound；Mechanical impurity is placed in reactor, is heated to 2 DEG C/min heating rate from room temperature 2 hours are incubated after 300~600 DEG C, discharges gas；Room temperature is subsequently cooled to, is dried in vacuo, is received at 80 DEG C after washing Meter Dan Jing zirconium diboride alloys；The alkali metal boronhydride is lithium borohydride, sodium borohydride or potassium borohydride, and the zirconium compounds refers to the oxygen of zirconium Compound, hydroxide or inorganic salts；The inorganic salts of the transition metal M refer to：Chloride, sulfate, the nitric acid of transition metal Salt or phosphate.
- A kind of 2. method for preparing surface and possessing the bearing ball of nano crystal zirconium diboride wearing layer, it is characterised in that including Following steps：Zirconium compounds and alkali metal boronhydride powder are weighed for 1: 2 or 1: 4 by Zr: B mol ratio, with bearing ball blank Add ball grinder in the lump, the ball milling after 16 hours under 200rpm rotating speeds, make to attach on bearing ball blank surface zirconium compounds with The mechanical impurity of alkali metal boronhydride；Take out bearing ball blank to be placed in reactor, with 2 DEG C/min heating rate 2 hours are incubated after being heated to 600~900 DEG C from room temperature, discharges gas；Room temperature is subsequently cooled to, it is true at 80 DEG C after washing Sky is dried, and obtains the bearing ball for possessing nano crystal zirconium diboride wearing layer to surface；The alkali metal boronhydride is lithium borohydride, sodium borohydride or potassium borohydride, and the zirconium compounds refers to the oxygen of zirconium Compound, hydroxide or inorganic salts.
- A kind of 3. method for preparing the bearing ball for possessing nano crystal zirconium diboride alloy wear-resisting layer, it is characterised in that including Following steps：In ball grinder, alkali metal boronhydride is dissolved in tetrahydrofuran, then adds zirconium compounds, the second metallic compound With bearing ball blank；Wherein, every liter of 0.1~0.4 mole of tetrahydrofuran alkali metal containing hydroboron；Second metallic compound It is the oxide, hydroxide or inorganic salts of transition metal M, transition metal M refers to Cr, Mn, Fe, Co, Ni, Cu or Zn；Zirconium Zr: M mol ratio is 1: 0.11~1 in compound and the second metallic compound, zr element and the second metal molar number sum and boron Mol ratio be 1: 2；By said mixture under 400rpm rotating speeds ball milling 2 hours, bearing ball blank surface is attached pastel；Take out bearing Ball blank is placed in reactor, and solvent THF is evaporated at 120 DEG C, pastel is turned into zirconium compounds and alkali metal hydroboration The mechanical impurity of compound；2 hours are incubated after being heated to 600~900 DEG C again with 2 DEG C/min of heating rate, discharges gas；So After be cooled to room temperature, be dried in vacuo after washing at 80 DEG C, obtain to surface and possess nano crystal zirconium diboride alloy wear-resisting layer Bearing ball；The alkali metal boronhydride is lithium borohydride, sodium borohydride or potassium borohydride, and the zirconium compounds refers to the oxygen of zirconium Compound, hydroxide or inorganic salts；The inorganic salts of the transition metal M refer to：Chloride, sulfate, the nitric acid of transition metal Salt or phosphate.
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|---|---|---|---|---|
| EP0826790A1 (en) * | 1996-08-28 | 1998-03-04 | Premark RWP Holdings, Inc. | Diboride coated pressing surface |
| CN1846006A (en) * | 2003-05-20 | 2006-10-11 | 埃克森美孚研究工程公司 | Advanced erosion-corrosion resistant boride cermets |
| CN102344149A (en) * | 2011-06-16 | 2012-02-08 | 兰州理工大学 | Preparation method of ZrB2 powder material |
| CN103757603A (en) * | 2014-01-07 | 2014-04-30 | 哈尔滨工业大学 | Method for preparing zirconium diboride coating |
| CN104045093A (en) * | 2014-06-18 | 2014-09-17 | 陕西科技大学 | Method for preparing nanometer ZrB2 powder through assistance of microwave-hydrothermal treatment |
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Patent Citations (5)
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|---|---|---|---|---|
| EP0826790A1 (en) * | 1996-08-28 | 1998-03-04 | Premark RWP Holdings, Inc. | Diboride coated pressing surface |
| CN1846006A (en) * | 2003-05-20 | 2006-10-11 | 埃克森美孚研究工程公司 | Advanced erosion-corrosion resistant boride cermets |
| CN102344149A (en) * | 2011-06-16 | 2012-02-08 | 兰州理工大学 | Preparation method of ZrB2 powder material |
| CN103757603A (en) * | 2014-01-07 | 2014-04-30 | 哈尔滨工业大学 | Method for preparing zirconium diboride coating |
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