CN103906723B

CN103906723B - The zircon particle of sintering

Info

Publication number: CN103906723B
Application number: CN201280045448.4A
Authority: CN
Inventors: 伊曼纽尔·诺妮特; 伊夫·布散特-卢
Original assignee: Saint Gobain Centre de Recherche et dEtudes Europeen SAS
Current assignee: Saint Gobain Centre de Recherche et dEtudes Europeen SAS
Priority date: 2011-07-20
Filing date: 2012-07-13
Publication date: 2016-10-12
Anticipated expiration: 2032-07-13
Also published as: WO2013011436A1; CN103906723A

Abstract

The present invention relates to a kind of sintered particles, be in terms of 100% by percentage by weight based on oxide and total amount, this granule has following chemical composition: 22%≤ZrO₂+HfO₂≤ 55%, wherein HfO₂≤2%；14%≤SiO₂≤35%；6%≤Al₂O₃≤60%；0.5%≤MgO≤6%；B₂O₃≤5%；Other oxides < 9.0%, and, being in terms of 100% based on the percentage by weight of crystallization phase existed and total amount, described granule has a following crystallization phase: 32%≤zircon≤80%；3%≤mullite≤15%；Zirconium oxide+hafnium oxide :≤9%, zirconium oxide and hafnium oxide are the most stabilized；4%≤corundum≤57%；Other crystallization phases < 10%, and total porosity is not higher than 6%.

Description

The zircon particle of sintering

Technical field

The present invention relates to the zircon particle of the zircon particle of novel sintering, especially bead form, relate to And the method manufacturing these beadlet, and relate to these granules as abrasive material, dispersant in humid medium Or the purposes processed for surface.

Background technology

Mining industry uses granule for the material being dried pre-grinding optionally with traditional method Carry out fine gtinding, be particularly useful for the essence of calcium carbonate, titanium dioxide, Gypsum Fibrosum, Kaolin and iron ore Fine lapping.

Additionally, coating industry, ink industry, dye industry, magnetic paint industry and pesticide industry make With granule for dispersion and homogenization liquid component and solid constituent.

Finally, Surface Processing Industry utilizes granule, (such as, uses in particular for cleaning metal die In manufacturing bottle), the chamfering of parts, eliminate rust, prepare for scheming the base material of layer, shot peening or shot-peening The operation of shaping etc..

Routinely, all these granules substantially have the spherical of the particle diameter from 0.005mm to 10mm, To meet above-mentioned all of market.In order to use in this three classes purposes, they especially must have There is good wearability.

Especially in the field of micro-grinding, following different types of granule (the especially form of beadlet) It is commercially available:

_■Rounded sand grain, such as, OTTAWA sand is cheap natural prodcuts, but it is unsuitable for modernization Pressurization, the grinder of high yield.It is true that sand is low intensive, low-density, quality change Change indefinite and wear equipment.

_■Widely used glass beads, it has higher intensity, relatively low abrasiveness and can be wider Use in diameter range.

_■Metal beadlet, especially steel ball grain, demonstrate low dark decay relative to handled product, especially cause The pollution of mineral filler and coating graying, and its density is too high, needs special grinder.They are especially Cause the high energy consumption of equipment, substantial amounts of heating and be subject to higher mechanical stress.

It is known that ceramic beads.These ceramic beads have than glass beads more preferably intensity, higher Density and excellent chemical inertness.

Ceramic beads is following classes:

_■The ceramic beads of consolidation, it generally passes through molten ceramic component, from the material shape globulate melted Drop, then solidify described drop and obtain, and

_■The ceramic beads of sintering, it generally passes through cold forming ceramic powders, then by high temperature roasting Burn into capable consolidation to obtain.

Compared with sintered particles, consolidation granule generally includes the substantial amounts of intergranular of the network by filling crystal grain Glass phase.Therefore, sintered particles and consolidation granule the problem met with in the application of each of which And solve the technical scheme that these problems are used and be typically different.Additionally, due to manufacturer Essence between method is different, and therefore, the compositions developed to prepare consolidation granule can not be used as Preparing the priori of sintered particles, vice versa.

Japan Patent JP6106087 discloses sintered beads based on zircon, and this sintered beads has height In 4.46g/cm³Density.Sintered beads based on zircon also can be from Chinese patent CN101786867 Know with in Korean Patent KR20070096131.

In order to increase the efficiency of grinding operation, i.e. for the amount of the abrasive product of specification cost, grind Granule must be more and more wear-resisting, especially more and more wear-resisting in alkaline medium.

It is an object of the invention to meet this needs at least in part.

Summary of the invention

The present invention relates to a kind of novel sintered particles, the preferably form of beadlet, this granule has:

-it is in terms of 100% by percentage by weight based on oxide and total amount, described granule has followingization Learn and form:

22%≤ZrO₂+HfO₂≤ 55%, and HfO₂≤ 2%；

14%≤SiO₂≤ 35%；

6%≤Al₂O₃≤ 60%；

0.5%≤MgO≤6%；

B₂O₃≤ 5%；

Other oxides < 9.0%, and

-to be in terms of 100% based on the percentage by weight of crystallization phase existed and total amount, described granule has Following crystallization phase:

32%≤zircon≤80%；

3%≤mullite≤15%；

Zirconium oxide+hafnium oxide :≤9%, zirconium oxide and hafnium oxide are the most stabilized；

4%≤corundum≤57%；

Other crystallization phases < 10%, and

-total porosity is less than or equal to 6%.

Preferably, the form of described sintered particles, preferably beadlet, described granule has:

30%≤ZrO₂+HfO₂≤ 55%, and HfO₂≤ 2%；

18%≤SiO₂≤ 35%；

6%≤Al₂O₃≤ 40%；

0.5%≤MgO≤6%；

B₂O₃≤ 5%；

Other oxides < 9.0%, and

32%≤zircon≤80%；

3%≤mullite≤15%；

4%≤corundum≤37%；

Other crystallization phases < 10%, and

-total porosity is less than or equal to 6%.

Will be seen in greater detail from description, inventor is it was surprisingly found that the group of these features Conjunction significantly improves wearability, especially improves the wearability in alkaline medium.

Therefore, according to the granule of the present invention, especially beadlet, be particularly well-suited in humid medium dispersion, The application that micro-grinding and surface process.

Additionally, they demonstrate the chemical corrosivity of good media-resistant, in the medium, especially exist When strongly basic medium (that is, pH > 8) performing grind.Such as, the granule according to the present invention is the most special Be not suitable to the suspended substance of grinding calcium carbonate.

Sintered particles according to the present invention can also have the one or more spies in following optional characteristics Levy:

-percentage by weight meter based on oxide, ZrO₂+HfO₂Content more than 25%, preferably more than or Equal to 30%, preferably more than 33%, preferably more than 35%, preferably more than 40% or very To more than 42% and/or less than 50%；

-percentage by weight meter based on oxide, SiO₂Content more than 16%, preferably larger or equal than 18%, it is preferably more than 20%, preferably more than 23% or even greater than 26% and/or is less than 33% or even less than 31%；

-percentage by weight meter based on oxide, Al₂O₃Content more than 10%, preferably more than 14%, Preferably more than 18% or even greater than 20% and/or less than 55%, preferably less than 50%, Preferably less than 45%, preferably less or equal to 40%, preferably less than 36%, preferably less than 31% or even less than 26%；

-percentage by weight meter based on oxide, the content of MgO more than 0.6% or even greater than 0.7%, Or even greater than 0.8% or even greater than 0.9% or even greater than 1.0% and/or be less than 5.0% or even less than 4.5% or even less than 4.0% or even less than 3.5% or Person is even less than 3.0% or even less than 2.5% or even less than 2.0%；

-percentage by weight meter based on oxide, B₂O₃Content less than 0.2%, preferably about equal to zero； In another embodiment, B₂O₃Content more than 1.0% and less than 3.0%；

-in one embodiment, percentage by weight meter based on oxide, " other oxides " includes greatly In 0.1% selected from Y₂O₃, oxide in lanthanide oxide and its mixture, be preferably selected from Y₂O₃ And La₂O₃Oxide, preferably Y₂O₃Oxide；Preferably, Y₂O₃And/or group of the lanthanides oxidation Thing, preferred Y₂O₃And/or La₂O₃, preferred Y₂O₃Content more than 0.7%, preferably greater than 0.9%, And/or less than 3.0% or even less than 2.5%；

-in one embodiment, percentage by weight meter based on oxide, " other oxides " includes greatly In the CaO of 0.1%, especially when obtaining based on the method including the step d) shaped by gelation During granule.Be preferably based on the percentage by weight meter of oxide, the content of CaO more than 0.3%, Preferably greater than 0.4%, preferably greater than 0.5%, and/or less than 4.0%, preferably less than 3.0% or It is even less than 2.0% or even less than 1.0%；

-in one embodiment, " other oxides " includes Y₂O₃And/or lanthanide oxide and CaO, Preferably include Y₂O₃And CaO；

-percentage by weight meter based on oxide, except CaO, Y₂O₃With " other outside lanthanide oxide Oxide " it is less than 3.0%, preferably smaller than 2.0%, preferably smaller than 1.5% or even less than 1.0%；

-except CaO, Y₂O₃It is impurity with " other oxides " outside lanthanide oxide；

-preferably, the gross weight of described granule is being accounted for according to the content of the oxide in the granule of the present invention More than 99.5%, preferably greater than 99.9% and, more preferably from about 100%；

-based on crystallizing the total amount of phase by weight percentage, zircon content (phase ZrSiO₄) more than 45%, Preferably greater than 50%, preferably greater than 60%, preferably greater than 65%；

-based on crystallizing the total amount of phase by weight percentage, mullite content (phase 3Al₂O₃-2SiO₂) More than 5%, preferably greater than 7%, preferably greater than 8% and/or less than 14%, preferably smaller than 12%, Preferably smaller than 11%；

-during sintering, generate at least some of or even all of mullite, i.e. fabricated in situ Mullite；

-based on crystallizing the total amount of phase by weight percentage, the most stabilized zirconium oxide (phase ZrO₂) + hafnium oxide (phase HfO₂) content less than 5% or even less than 4% or be even less than 3% or even less than 2%；

-weight based on zirconium oxide+hafnium oxide by weight percentage, more than 90%, is preferably more than Zirconium oxide+the hafnium oxide of 95% is monocline crystalline phase；

-based on crystallizing the total amount of phase by weight percentage, corundum content (phase Al₂O₃) more than 8%, excellent Choosing more than 12%, preferably greater than 15% and/or less than 50%, preferably smaller than 45%, preferably smaller than 40%, Preferably lower than or equal to 37%, preferably smaller than 35%, preferably smaller than 30%, preferably smaller than 25% or Person is even less than 20%；

-based on crystallization phase gross weight by weight percentage, the content of " other crystallizes phase " be less than 8%, excellent Selection of land less than 6% or even less than 5% or even less than 4% or even less than 3%, Or even less than 2%；

-preferably, " other crystallize phase " is spinelle MgAl₂O₄And/or cordierite and/or anorthite and/or Quartz and/or cristobalite and/or tridymite；

-relative to described granule weight by weight percentage, containing of noncrystalline phase (that is, glass phase) Amount is less than 20%, less than 15% or even less than 14% or even less than 12% and/or be more than 5% or even greater than 7%；

-the amorphous phase that represents in the form of an oxide includes MgO and SiO₂, and/or B₂O₃And/or Y₂O₃And/or Lanthanide oxide and/or Al₂O₃And/or CaO and/or Na₂O and/or K₂O and/or P₂O₅；

-the amorphous phase that represents in the form of an oxide includes MgO and SiO₂And Y₂O₃And Al₂O₃And Na₂O and K₂O and P₂O₅；

-total porosity less than 5.5%, preferably less than 5%, preferably less than 4.5% or even less than 4%, Or even less than 3% or even less than 2%；

The particle diameter that-sintered particles has is less than 10mm and/or more than 0.005mm；

-sintered particles is beadlet；

The sphericity that-sintered particles has more than 0.7, preferably greater than 0.8, preferably greater than 0.85 or the biggest In 0.9；

The density of-sintered particles is more than 3.6g/cm³, or even greater than 3.7g/cm³, or even greater than 3.80g/cm³, or even greater than 3.85g/cm³, or even greater than 3.93g/cm³, or very To more than 4.00g/cm³, or even greater than 4.05g/cm³, or even greater than 4.10g/cm³With/ Or less than 4.40g/cm³, or even less than 4.30g/cm³, or even less than 4.20g/cm³。

According to the sintered particles of the present invention, preferably beadlet, this beadlet has precedence over every other material, Have:

42%≤ZrO₂+HfO₂≤ 50%, and HfO₂≤ 2%；

23%≤SiO₂≤ 31%；

20%≤Al₂O₃≤ 26%；

0.6%≤MgO≤2%；

B₂O₃≤ 3%；

0.9%≤Y₂O₃≤ 2.5%；

0.4%≤CaO≤1%；

Less than 3% except ZrO₂、HfO₂、SiO₂、Al₂O₃、MgO、B₂O₃、Y₂O₃With

Oxide outside CaO, and

65%≤zircon≤80%；

8%≤mullite≤11%；

Zirconium oxide+hafnium oxide :≤3%, zirconium oxide and hafnium oxide are the most stabilized；

15%≤corundum≤20%；

Other crystallization phases less than 2%, and

-weight based on granule, the amorphous phase less than 14%, and

-total porosity is less than or equal to 6%.

The invention still further relates to the powder of a kind of granule, including by weight percentage more than 90%, preferably More than 95%, the granule according to the present invention of preferably from about 100%.

The method that the invention still further relates to manufacture the sintered particles according to the present invention, the beadlet especially sintered, The method includes the following step carried out successively:

A) if necessary, then one or more raw-material powder are ground, preferably by being co-mulled and made into Grind so that in step c), their mixing produces the grain with the median particle diameter less than 0.6 μm Shape mixture,

B) alternatively, it is dried described particulate mixtures,

C) prepare starting material from described particulate mixtures, be dried alternatively, the group of described starting material Becoming to be adjusted to obtain sintered particles at the end of step g), it forms to have and meets according to the present invention The composition of sintered particles, described starting material has the glass particle containing magnesium oxide and/or containing aerobic Change the granule of the glass ceramics of magnesium and/or include MgO and SiO₂The granule of compound,

D) starting material with rough particle form is formed,

E) alternatively, washing,

F) alternatively, it is dried,

G) sinter to obtain sintering under more than 1330 DEG C with less than the sintering temperature between 1410 DEG C Grain.

Present invention finally relates to particularly by manufactured by the method according to the invention according to the present invention The powder of grain (especially beadlet) (is especially used as abrasive material, the dispersant in humid medium, carrier In preventing the carrier of the deep geologic crack closure of generation in the well extracting well, it is particularly useful for oil) Or the purposes that heat exchanging agent (such as, for fluid bed) or surface process.

Definition

-" granule " refers to single solid product in the powder.

-" sintering " is that rough granule (granular aggregation) is by higher than the heat treatment at 1100 DEG C Solidification, wherein, some compositions (but not every composition) part or complete of the most rough granule Portion's consolidation.

-" beadlet " refers to the granule that sphericity is more than 0.6, how to realize regardless of this sphericity, wherein, Sphericity is the minimum diameter ratio with its maximum gauge of granule.Preferably, have according to the beadlet of the present invention There is the sphericity more than 0.7.

What " size " of-beadlet (or granule) was its full-size dM with its minimum dimension dm is average Value: (dM+dm)/2.

-generally use D₅₀" median particle diameter of powder " that represent is such particle diameter: by the granule of this powder Being divided into etc. first group and second group of weight, described first group and second group includes having being more than the most respectively Or the granule of the particle diameter less than median particle diameter.Such as, laser granulometer is used can to assess median particle diameter.

-" beadlet of sintering ", or broader for " sintered particles " refer to by sinter rough granule gained The solid bead (or granule) arrived.

-" impurity " should be understood to the unavoidable component referring to must be introduced by raw material.Specifically, one In individual embodiment, belong to by oxide, nitride, oxynitride, carbide, oxycarbide, The compounds that the metallics of carbonitride, sodium and other alkali metal, ferrum, vanadium and chromium is formed is Impurity.As example, it may be mentioned that impurity be Fe₂O₃、TiO₂Or Na₂O.The carbon of residual is basis A part for impurity in the composition of the granule of the present invention.

-when mentioning ZrO₂Or (ZrO₂+HfO₂) time it should be understood that ZrO₂HfO with trace₂。 It is true that based on ZrO₂+HfO₂Percentage by weight meter, it is impossible to from ZrO₂Middle Chemical Decomposition and having A small amount of HfO of similar performance₂Always naturally occur in zirconium oxide with the content of usually less than 3% In source.Hafnium oxide is not qualified as impurity.

" precursor " of-oxide refers to provide described during the manufacture according to the granule of the present invention The component of oxide.

-" group of the lanthanides " is atomic number chemical element between 57 (lanthanums) and 71 (lutecium), lanthanum and lutecium It is included in described group of the lanthanides.

For the sake of clarity, term " ZrO₂”、“HfO₂" and " Al₂O₃" it is used to refer to these oxides in group Content in compound, " zirconium dioxide ", " hafnium oxide " and " corundum " is used to refer to respectively by ZrO₂、HfO₂ And Al₂O₃The crystallization phase of these oxides constituted.But, these oxides can also be as other phases Exist, especially with zircon (ZrSiO₄) form or mullite (3Al₂O₃-2SiO₂) Form.

Unless otherwise indicated, all percentage ratios the most in this specification are weight based on oxide Percentage ratio.

Unless otherwise indicated, otherwise " comprise one ", " including one " or " having one " refers to " at least one ".

Specifically describe

In order to manufacture the sintered particles according to the present invention, can follow above-described and hereafter incite somebody to action in detail The technique of the step a) presented to step g).

In step a), raw-material powder can be ground individually, or is preferably co-mulled and made into, as Fruit be suitable for prepare initial charge ratio by they mix, then will not produce in step c) have little Particulate mixtures in the median particle diameter of 0.6 μm.This grinding can be wet grinding.

Preferably, grind or be co-mulled and made into and be done so that the median particle diameter of described particulate mixtures is less than 0.5 μm, preferably less than 0.4 μm.

Preferably, powder used, especially zircon ZrSiO₄Powder, aluminium oxide Al₂O₃Powder, Y₂O₃Powder, lanthanide oxide powder, the glass powder containing magnesium oxide, the glass containing magnesium oxide Ceramic powders, comprise MgO and SiO₂The powder of compound and the powder of mullite, Its median particle diameter having be respectively smaller than 5 μm or even less than 3 μm, less than 1 μm, be less than 0.7 μm, preferably smaller than 0.6 μm, preferably smaller than 0.5 μm or even less than 0.4 μm.Favorably Ground, the median particle diameter having when every kind of powder in these powder is less than 0.6 μm, preferably smaller than 0.5 μm Or even less than during 0.4 μm, then step a) is optional.

Preferably, the ratio that zircon powder used is calculated by BET method (specific surface area method) Surface area is more than 5m²/ g, preferably greater than 8m²/ g, preferably greater than 10m²/ g and/or less than 30m²/g。 Advantageously, convenient generally with the grinding in the step a) of form of suspension by this point.Additionally, can To reduce the sintering temperature in step f).

Preferably, the median particle diameter that alumina powder used has is less than 7 μm, is preferably less than 6 μm or even less than 3 μm or even less than 2 μm or even less than 1 μm or Person is even less than 0.5 μm.Advantageously, by this point convenient from present in particulate mixtures or Person forms mullite in alumina powder and the silicon dioxide of step g) period generation.

In step b), alternatively, if obtaining raw-material abrasive flour, then example by wet lapping As in an oven or being dried raw-material abrasive flour by spray drying.Preferably, temperature is adjusted Degree and/or persistent period of drying steps make the content of residual water of raw-material powder less than 2% or It is even less than 1.5%.

In step c), at room temperature preparing initial charge, this initial charge includes zircon ZrSiO₄ Powder, Al₂O₃Powder and optional Y₂O₃And/or lanthanide oxide and/or containing magnesium oxide Glass and/or containing the glass ceramics of magnesium oxide and/or include MgO and SiO₂Compound and/or many aluminum The powder of andalusite.

These powder can also use the powder of the precursor of these oxides that equivalent introduces at least in part Replace.

Specifically, a part of or even all of zircon according to the present invention and/or mullite Granule may be from these crystallization phases present in the initial charge.

The powder of the glass powder containing magnesium oxide and/or the glass ceramics containing magnesium oxide preferably contains More than 40%, preferably more than 50% or even greater than 60% or even greater than 70% or Person is even greater than the silicon dioxide of 80 weight %.They can also not contain silicon dioxide.

Including MgO and SiO₂Compound, further preferably include Al₂O₃.Preferably, described compound Selected from Talcum, cordierite and its mixture.Preferably, described compound is cordierite.Specifically, Weight based on initial charge, the amount of the cordierite that initial charge can contain is preferably greater than 3.8%, excellent Choosing more than 4%, preferably greater than 5% and/or less than 30%, preferably smaller than 25%, preferably smaller than 20%, Or even less than 15 weight %.

The powder providing oxide or precursor is preferably selected so that based on oxide percentage by weight Than meter, " other oxides " is (except ZrO₂、HfO₂、SiO₂、Al₂O₃, MgO and B₂O₃Outside Oxide) total content less than 3%.

Weight based on initial charge, zircon powder (that is, the ZrSiO that initial charge contains₄Granule) Amount by weight more than 32%, preferably greater than 45%, preferably greater than 50%, preferably greater than 60%, It is preferably greater than 65% and/or less than 80%.

Weight based on initial charge, alumina powder (that is, the Al that initial charge contains₂O₃Granule) Amount more than 4%, preferably greater than 8%, preferably greater than 12%, preferably greater than 15% and/or less than 55%, Preferably smaller than 50%, preferably smaller than 45%, preferably smaller than 40%, preferably smaller than 35%, preferably smaller than 30%, it is preferably smaller than 25 weight %.Preferably, described alumina powder be active alumina powder and/ Or calcined oxide aluminium powder and/or transition state of alumina powder.The most described alumina powder is activity Alumina powder.

In one embodiment, based on crystallization the most by weight percentage, initial charge includes being less than 9%, zirconium dioxide (that is, the ZrO less than 5%, less than 2%₂Granule) or even do not include Zirconium dioxide.It is true that the zirconium dioxide of a part or even all of zirconium oxide can originate from The decomposition of zircon during sintering in step g).

In one embodiment, based on crystallization the most by weight percentage, initial charge includes being less than 15%, the mullite less than 10%, less than 5%, or even do not include mullite.? In step g) during sintering, preferably can generate a part in situ from the precursor selected from following material Mullite or even all of mullite:

-glass containing magnesium oxide, it preferably includes SiO₂, and/or

-glass ceramics containing magnesium oxide, and/or

-include MgO and SiO₂Compound, described compound the most also includes Al₂O₃(preferably The described compound in ground is cordierite selected from Talcum and cordierite, the most described compound), and/or

-derive from zircon ZrSiO₄Resolve into zirconium oxide ZrO₂With silicon dioxide SiO₂Aluminium oxide and two Silicon oxide.

By the precursor of mullite mentioned above and/or by including other compounds of magnesium oxide MgO can be provided.

In one embodiment, initial charge includes Y₂O₃And/or the powder of the granule of lanthanide oxide End, preferably Y₂O₃The powder of granule and La₂O₃The powder of granule, preferably Y₂O₃Granule Powder, weight based on initial charge, the amount of the powder of the granule comprised more than 0.1%, preferably More than 0.7%, preferably more than 0.9% and/or preferably less than 3% or even less than 2.5 weights Amount %.

In one embodiment, three embodiments that combination has just described above.

In one embodiment, weight based on initial charge, initial charge includes the two of powder Silicon oxide (that is, SiO₂Granule), its content is preferably greater than 0.5%, preferably greater than 1%, the biggest In 2% and/or less than 10%, preferably smaller than 8%, preferably smaller than 5 weight %.

Preferably, the most deliberately introduce in initial charge except providing ZrO₂+HfO₂、SiO₂、Al₂O₃、 MgO and alternatively Y₂O₃And/or lanthanide oxide and/or B₂O₃And/or CaO and their precursor Raw material outside raw material, other oxides existed are impurity.

Additionally, initial charge can include solvent (preferably water), the amount of solvent is suitable in step d) The method of shaping.

Those skilled in the art knows, and initial charge is suitable to the method for the shaping in step d).

Shape the method that especially may come from gelation.For this purpose, solvent (preferably water) quilt Add initial charge to supending.

Preferably, the weight percent content of the dry that suspension has is between 50% to 70%.

Suspension can also include one or more of following ingredients:

-dispersant, percentage by weight meter based on dry, concentration is from 0 to 10%；

-surface tension modifier, percentage by weight meter based on dry, concentration is from 0 to 3%；

-gellant or " gel ", percentage by weight meter based on dry, concentration is from 0 to 2%.

Those skilled in the art knows dispersant, surface tension modifier and gellant.

For embodiment, it can be mentioned:

-for dispersant, sodium polymethacrylate or ammonium polymethacrylate class, sodium polyacrylate or Ammonium polyacrylate class, polyacrylic acid (sodium or ammonium salt) or other polyelectrolyte class, citric acid salt (such as ammonium citrate), sodium phosphate class and carbonates；

-surface tension modifier, such as, the organic solvent of fatty alcohol；

-gellant, such as, natural polysaccharide.

During manufacturing step subsequently, all these compositions disappear, but they still can keep trace.

Preferably, the powder of oxide and/or precursor is added in ball mill water and dispersant/anti- The mixture of flocculant.After stirring, adding water, wherein, gellant is dissolved to obtain in advance Suspension.

If shaping the result being to extrude, then thermoplastic polymer and thermosetting polymer can be added To initial charge.

In step d), appointing of the shaping for manufacturing sintered particles, especially sintered beads can be used What conventional method.

In these methods, it can be mentioned:

-prilling process, such as, uses comminutor, fluidized bed pelletizer or granulation disc；

-gel method,

-the method that is molded or extrudes, and

-process for stamping.

In gel method, obtained the liquid of above-described suspension by the calibrated hole of suspension flow Drip.Leave in the bath that the drop in hole falls into gel solution (being suitable to the electrolyte reacted with gellant), Wherein, drop essentially become spherical after, drop is hardening.

In step e), alternatively, the rough granule that washing obtains in a previous step, such as, use Water washs.

In step f), alternatively, such as, the rough granule being washed alternatively it is dried in an oven.

In step g), the rough granule being washed alternatively and/or being dried is sintered.Preferably, The most under atmospheric pressure, preferably in electric arc furnace, perform sintering in atmosphere.

More than 1330 DEG C, preferably greater than 1340 DEG C, preferably greater than 1350 DEG C, preferably greater than 1360 DEG C, It is preferably greater than 1370 DEG C and is less than 1410 DEG C, preferably smaller than 1400 DEG C, preferably smaller than 1390 DEG C At a temperature of perform the sintering in step g).Sintering temperature equal to 1375 DEG C is the most suitable.Little The granule with the total porosity less than or equal to 6% can not be obtained in the sintering temperatures of 1330 DEG C, with And, when in-situ preparation mullite, the amount of mullite is more than or equal to 3%.On the contrary, greatly Cause the excessive decomposition of zircon in the sintering temperatures of 1410 DEG C, this is disadvantageous to wearability.

Preferably, sintering duration is between 2 hours to 5 hours.If sintering duration etc. In 4 hours, then it is the most suitable.

The sintered particles obtained preferably has the pearl of the minimum diameter between 0.005mm and 10mm The form of grain.

Following rules well-known to those having ordinary skill in the art can be applied to obtain the sintering according to the present invention Granule:

The amount of-increase zircon in sintered particles: increase the amount of zircon in initial charge and/or reduce sintering Temperature is to limit and zircon resolving into silicon dioxide and zirconium dioxide；

-reduce the amount of zircon in sintered particles: reduce the amount of zircon in initial charge and/or increase sintering temperature Degree；

The amount of-increase corundum in sintered particles: increase the amount of corundum in initial charge and/or reduce burning Junction temperature is to limit the shaped in situ of mullite；

-reduce the amount of corundum in sintered particles: reduce the amount of corundum in initial charge and/or increase sintering Temperature；

-increase the zirconic amount in sintered particles: increase zirconic amount and/or reduction in initial charge and burn Junction temperature is to limit and zircon resolving into silicon dioxide and zirconium dioxide；

-increase the amount of mullite in sintered particles: increase mullite in initial charge amount and/ Or increase sintering temperature to promote the shaped in situ of mullite；

-reduce the amount of mullite in sintered particles: reduce mullite in initial charge amount and/ Or reduce sintering temperature to limit the shaped in situ of mullite；

-reduce the total porosity with the sintered particles limiting initial charge: make sintering temperature close to sintering temperature Preferred scope and/or increase the amount of powdered silica in initial charge and/or increase initial Charging includes MgO and SiO₂The amount of compound.

Sintered particles according to the present invention is particularly suitable for application as abrasive material or the dispersion in humid medium Agent and for surface process.Therefore, the invention still further relates to most granule, especially in accordance with this Beadlet manufactured by bright beadlet or the method according to the invention, as abrasive material or in humid medium The purposes of dispersant.

It is to be noted, however, that the performance of granule according to the present invention (especially they mechanical strength, Their density and the easy degree of their production) other purposes can be made them appropriate for, especially make For proppant or heat exchanging agent or process (particularly by the granule according to the present invention for surface Polishing).

Therefore, the invention still further relates to selected from levitation device, grinder, for surface process equipment and The device of heat exchanger, described device comprises the powder of the granule according to the present invention.

Detailed description of the invention

Embodiment

Following non-limiting examples is given for the purpose of illustrating the invention.

Measurement scheme

Following method is for determining the particular characteristic of the multiple mixture of the beadlet of sintering.They provide The excellent simulation of the truth run in micro-abrasive application.

In order to determine so-called " planetary " wearability, 20ml (is used measured by scale test tube Volume) particle diameter beadlet to be tested between 1.2mm to 1.4mm weigh that (weight is m₀), Then put it into the PM400 type manufactured by RETSCH high speed planetary-type grinding machine, use A bowl in volume is 125ml 4 bowls of fine and close sintered alumina coating.Will The carborundum (median particle diameter D50 is 23 μm) of the 2.2g produced by Presi and the water of 40ml add In the same bowl having accommodated beadlet.This bowl is closed and sets with 400rev/min Speed rotate (planetary motion), direction of rotation reversion per minute once continue 1.5 hours.Bowl Content subsequently 100-μm sieve on wash with remove residual carborundum and during grinding by In the material that abrasion comes off.On the sieve of 100-μm after screening, in an oven by beadlet at 100 DEG C Under be dried 3 hours (weight m of weighing subsequently₁).Described beadlet (weight m₁) it is placed again into that there is SiC Suspension (concentration as hereinbefore and consumption) one of them bowl in, and carry out with The new circulation of the grinding that previous circulation is identical.The content of bowl subsequently 100-μm sieve on wash with Remove the carborundum of residual and the material come off due to abrasion during grinding.Sieve in 100-μm After upper screening, in an oven beadlet is dried at 100 DEG C 3 hours (weight m of weighing subsequently₂)。 Described beadlet (weight m₂) it is placed again into suspension (concentration as hereinbefore and the use with SiC Amount) one of them bowl in and carry out the new circulation of the grinding identical with previous circulation.Bowl-shape The content of thing washs the carborundum to remove residual and subsequently on 100-μm sieve during grinding The material come off due to abrasion.On the sieve of 100-μm after screening, at 100 DEG C, beadlet is existed Baking oven is dried 3 hours, (weight m of weighing subsequently₃)。

Planetary abrasion (PW) represents with percentage ratio (%) and equal to beadlet at the beginning of relative to beadlet The weight loss of starting weight amount, or: 100 (m₀-m₃)/(m₀)；It is given in Table 1 result PW.

It is believed that as fruit product relative to reference to embodiment 1 in planetary abrasion (PW) at least Improve 15%, then result is gratifying.

In order to determine so-called " in alkaline medium (that is, in the pH value medium higher than 8) " Wearability, the charging of beadlet to be tested is screened between 1.8mm to 2mm on square hole screen.Will Apparent volume is that the beadlet of 1.04 liters is weighed (weight m'₀).Beadlet is placed into eccentric steel disk subsequently Netzsch LME1 type horizontal mill (dischargeable capacity of 1.2L) in.Calcium carbonate CaCO₃ The pH value that has of waterborne suspension be 8.2, dry containing 70%, wherein, by volume 40% Microgranule there is the particle diameter less than 1 μm, this suspension with the flow velocity of 5 ls/h continually by grinding Machine.Grinder starts gradually until realizing the linear velocity in the end of dish is 10m/s.Grinder quilt The persistent period t of operation, equal to 6 hours, then stops.Beadlet use water rinses, from grinder carefully Taking-up is washed out and is dried.Then they are weighed (weight m').Rate of depreciation V (with gram/ Hour represent) determine as the following formula: V=(m'₀-m')/t。

The charging of beadlet is collected and supplements (m'₀-m') gram new beadlet with repetitive operation as required Repeatedly (n time) so that the milling time of accumulation at least 40 hours and making in step n and step Difference between the rate of depreciation calculated in n-1 is less than 15% (relatively).Mill in alkaline medium Damaging (BW) is rate of depreciation measured in this steady-state conditions (typically 42 hours).At table 1 In provide BW result.

It is believed that such as fruit product in the wearability (BW) of alkaline medium relative to reference to embodiment 1 Wearability at least improve 20%, then result is particularly satisfactory.

Crystallize present in the sintered particles according to the present invention and measured by X-ray diffraction, example As, by the diffractometer type instrument X'Pert PRO being provided with copper DX pipe from Panalytical company. Use the acquisition performing diffraction pattern on this equipment angular range 2 θ between 5 ° to 80 °, Qi Zhongbu Length is 0.017 °, and gate time is 60s/ step-length.Frontal lens includes fixing use 1/4 ° programmable Dissipating slit, the Soller slit of 0.04rad, mask equal to 10mm and fixing anti-scattering slit is 1/2°.Sample rotates to limit preferred direction around the axis of himself.Rear lens includes fixing making With the programmable anti-scattering slit of 1/4 °, the Soller slit of 0.04rad, and Ni light filter.Obtain Pattern use and there is the High Score Plus software of Rietveld matching process, mullite Section be " Crystal structure and compressibility of 3:2mullite " (Balzar etc., American Mineralogist；In December, 1993；Volume 78；No.11-12；Page 1192-the Page 1196) described in Al_4.5Si_1.5O_9.74Section.Multiple parameters are fitted for " R Bragg " The maximum yojan of value.

By X-ray diffraction (such as, by being provided with copper DX pipe from Panalytical company Diffractometer type instrument X'Pert PRO), measure amorphous phase present in the sintered particles according to the present invention Amount.Use this equipment to perform the acquisition of diffraction pattern, measure in the same way in granule Crystalline phase.Based on the zinc oxide according to the present invention and the weight of the sample of sintered particles, method bag used Include: in the case of the amount that there is zinc oxide is equal to 20%, add the standard holocrystalline of known quantity.

Total porosity (representing with %) uses following formula to evaluate:

Total porosity=100 × (1 (d_Beadlet/d_{The beadlet ground})), wherein,

-d_BeadletIt is the method according to volume based on the gas (being helium in this case) measuring displacement, Use helium density bottle (fromThe AccuPyc 1330 of company) grinding that obtains Beadlet density before, and

-d_{The beadlet ground}Be in the circular dry grinding machine manufactured by Aurec grind beadlet 40s, then sieve The powder density that (making the powder extending only through 160-μm sieve for measuring) obtains.

Fabrication scheme

From specific surface area about 8m²/ g and median particle diameter are equal to the zircon powder of 1.5 μm；Purity is equal to 99.5% and median particle diameter less than the alumina powder of 5 μm；Purity is more than 95% and median particle diameter is less than The cordierite powder of 63 μm；And according to performed embodiment, median particle diameter less than 53 μm and At 1000 DEG C perform calcination loss amount 10% to 15% between and SiO₂+Al₂O₃Total content Clay more than 82%；With based on rare earth oxide purity, more than 99.9% and median particle diameter is less than 10 μm Y₂O₃Powder, prepare the beadlet of sintering.

These powder are mixed and are co-mulled and made in humid medium subsequently until obtaining and having more than in 0.4 μm The particulate mixtures of value particle diameter.It is subsequently dried this particulate mixtures.

The initial charge being made up of waterborne suspension, this aqueous suspension is prepared subsequently from this particulate mixtures Liquid includes: percentage by weight meter based on dry, the dispersant of the carboxylic acid type of 0.5%, 0.6% The dispersant of sodium phosphate type and the gellant (that is, the polysaccharide of alginates) of 0.4%.

Ball mill for described preparation with obtain initial charge good uniformity: first prepare containing The solution of gellant.Then, particulate mixtures and dispersant are added to the water.It is subsequently adding containing glue The solution of solidifying agent.The mixture obtained is stirred 8 hours.By using companyInstitute The Sedigraph 5100 Particle Size Analyzer (sedigraph) sold carrys out the particle diameter of monitor particles by sedimentation (median particle diameter < 0.4 μm), adds appropriate water and has 66% dry and having be less than to obtain The viscosity of 5000 centipoises (uses LV3 axle to measure with the speed Brookfield viscosity of 20rev/min Amount) waterborne suspension.Thus, the pH value of suspension approximates 8.

Suspension is forced through calibration hole with certain flow velocity, and this flow velocity is so that after the sintering The beadlet of acquisition 1.2mm to 1.4mm in the content of this embodiment.The drop of suspension falls into In coagulation bath based on electrolyte (salt of bivalent cation), and react with gellant.Rough pearl Grain is collected, washs, is then dried to remove moisture removal at 80 DEG C.Beadlet is then transferred to sintering Stove, in this sintering furnace, these beadlet are heated to required sintering temperature with the speed of 100 DEG C/h Ts.At temperature Ts after the stabilization sub stage of 4 hours, temperature can be reduced by natural cooling.

Result

The result obtained is summarized in table 1 below.

Is in abrasive application with reference to beadlet (not being the beadlet according to the present invention) in embodiment " with reference to 1 " In the zircon beadlet of conventional sintering, its composition is close to the composition of the embodiment 4 in US 2004/007789.

Surprisingly, these embodiments show, compared with reference beadlet, according to the test beadlet of the present invention Demonstrate significant performance.

The comparison of the product according to embodiment 2, embodiment 4, embodiment 13 and embodiment 14, equal to 1375 DEG C Temperature Ts under and in addition to MgO, there are identical chemico-analytic all sintered products substantially and show: MgO impact in the wearability of beadlet: contain respectively according to the product of embodiment 13 and embodiment 14 The MgO of 0.39% and 0.03%, with respect to the product of reference 1, according to embodiment 13 and embodiment 14 Product be respectively provided with poor wearability PW%.Product according to embodiment 2 and embodiment 4 contains respectively The MgO of 0.69% and 1.03%, with respect to reference to 1 product, according to embodiment 2 and embodiment 4 Product is respectively provided with wearability PW% of improvement.

Comparative descriptions the fact according to embodiment 1 and the product of embodiment 2: if total porosity increases Greatly more than 6%, then no longer improve relative to the Wear Resistance PW% with reference to 1.

The product of embodiment 11 and embodiment 12 shows, if mullite content is equal to 3%, the most wear-resisting Property PW% relative to reference to 1 product improve 17% and 36% respectively.Show according to other embodiments of the invention Illustrating, the mullite content (embodiment 4) for 10%, wearability PW% increases until it reaches Maximum.

Relative to the product from reference 1, according to the product (not being the product according to the present invention) of embodiment 17 At display, the mullite content equal to 17% does not improve wearability PW%.

According to embodiment 7, embodiment 9 and the comparison of the product of embodiment 10, equal to 1375 DEG C of temperature Ts Descend and except Y₂O₃Outside substantially there are identical chemico-analytic all sintered products demonstrate, Y₂O₃ Impact in the wearability of beadlet: if Y₂O₃Content increase, then wearability PW% increase.Relatively In the product of reference 1, according to the Y with 1.09%₂O₃The product of the embodiment 10 of content demonstrates, Improvement 44% in wearability PW%, and, relative to the product of reference 1, Y₂O₃Content respectively equal to The product according to embodiment 7 with according to embodiment 9 of 0.7% and 0.2% improves in wearability PW% respectively 35% and 31%.

Relative to reference 1, embodiment 2, embodiment 3, embodiment 4, embodiment 5, embodiment 7 and reality Executing relatively demonstrating of example 8, sintering temperature Ts equal to 1425 DEG C reduces wearability PW%, but The identical product sintered at temperature Ts equal to 1375 DEG C improves this abrasiveness.

Relative to the product of reference 1, demonstrate according to the product of embodiment 10 and improve in wearability BW% 45%.

In an embodiment, zirconium oxide and hafnium oxide are the monoclinic crystals of approximation 100%.

The product of embodiment 4 and embodiment 10 is preferred product.

Certainly, the invention is not restricted to examples described above and embodiment.Specifically, other gel systems System is suitable to manufacture the ceramic beads according to the present invention.Therefore, US 5466400, FR 2842438 and US 4063856 describe applicable sol-gel technique.FR 2842438 and US 4063856 is suitable for and is similar to The gel systems of the system (based on alginate) that literary composition describes, but, US 5466400 describes the most not Same gel systems.

It is also contemplated that the method described in the US 2009/0036291 and formed by punching press or by pelletize The method of beadlet.

Multiple embodiment can be combined.

Claims

1. a sintered particles,

-it is in terms of 100% by percentage by weight based on oxide and total amount, described granule has following chemical group Become:

22%≤ZrO₂+HfO₂≤ 55%, and HfO₂≤ 2%；

14%≤SiO₂≤ 35%；

6%≤Al₂O₃≤ 60%；

0.5%≤MgO≤6%；

B₂O₃≤ 5%；

Other oxides < 9.0%, and

32%≤zircon≤80%；

3%≤mullite≤15%；

Zirconium oxide+hafnium oxide≤9%；

4%≤corundum≤57%；

Other crystallization phases < 10%, and

-total porosity is less than or equal to 6%.

Sintered particles the most according to claim 1,

30%≤ZrO₂+HfO₂≤ 55%, and HfO₂≤ 2%；

18%≤SiO₂≤ 35%；

6%≤Al₂O₃≤ 40%；

0.5%≤MgO≤6%；

B₂O₃≤ 5%；

Other oxides < 9.0%, and

32%≤zircon≤80%；

3%≤mullite≤15%；

Zirconium oxide+hafnium oxide≤9%；

4%≤corundum≤37%；

Other crystallization phases < 10%, and

-total porosity is less than or equal to 6%.

Sintered particles the most according to claim 1 and 2, wherein: 35%≤ZrO₂+HfO₂。

Sintered particles the most according to claim 3, wherein: 40%≤ZrO₂+HfO₂。

Sintered particles the most according to claim 1 and 2, wherein: SiO₂> 23% and/or Al₂O₃> 10% And/or MgO > 0.6%.

Sintered particles the most according to claim 1 and 2, wherein: SiO₂< 31% and/or Al₂O₃< 36% And/or MgO < 5.0%.

Sintered particles the most according to claim 1 and 2, wherein: 31% > Al₂O₃> 18%.

Sintered particles the most according to claim 1 and 2, wherein: 2.0% > MgO > 0.8%.

Sintered particles the most according to claim 1 and 2, wherein: 3.0 > B₂O₃> 1.0%.

Sintered particles the most according to claim 1 and 2, wherein: B₂O₃< 0.2%.

11. sintered particles according to claim 1 and 2, including more than 0.1% selected from Y₂O₃, lanthanum It it is the oxide in oxide and its mixture.

12. sintered particles according to claim 11, wherein: selected from Y₂O₃, lanthanide oxide and its The content of the described oxide of mixture is between 0.7% and 3.0%.

13. sintered particles according to claim 11, wherein: selected from Y₂O₃, lanthanide oxide and its The described oxide of mixture is Y₂O₃And/or La₂O₃。

14. sintered particles according to claim 13, wherein: selected from Y₂O₃And/or La₂O₃Institute Stating oxide is Y₂O₃。

15. sintered particles according to claim 1 and 2, including the CaO more than 0.1%.

16. sintered particles according to claim 15, wherein: 0.3% < CaO < 4.0%.

17. sintered particles according to claim 16, wherein: CaO < 1.0%.

18. sintered particles according to claim 1 and 2, wherein: except ZrO₂、HfO₂、SiO₂、 Al₂O₃、MgO、B₂O₃、CaO、Y₂O₃It is less than 3.0% with the content of the oxide outside lanthanide oxide.

19. sintered particles according to claim 18, wherein: except ZrO₂、HfO₂、SiO₂、 Al₂O₃、MgO、B₂O₃、CaO、Y₂O₃It is less than 2.0% with the content of the oxide outside lanthanide oxide.

20. sintered particles according to claim 19, wherein: except ZrO₂、HfO₂、SiO₂、 Al₂O₃、MgO、B₂O₃、CaO、Y₂O₃It is less than 1.5% with the content of the oxide outside lanthanide oxide.

21. sintered particles according to claim 1 and 2, wherein: with gross weight based on described granule The percentage by weight meter of amount, the content of described oxide is more than 99.5%.

22. sintered particles according to claim 1 and 2, the zircon content having is more than 45%.

23. sintered particles according to claim 22, wherein: described zircon content is more than 50%.

24. sintered particles according to claim 23, wherein: described zircon content is more than 60%.

25. sintered particles according to claim 1 and 2, the mullite content having is more than 5% And/or less than 14%.

26. sintered particles according to claim 25, wherein: described mullite content is more than 7% And/or less than 12%.

27. sintered particles according to claim 26, wherein: described mullite content is more than 8% And/or less than 11%.

28. sintered particles according to claim 1 and 2, wherein: synthesize described many during sintering Mullite.

Containing of 29. sintered particles according to claim 1 and 2, the zirconium oxide having and hafnium oxide Amount is less than 5%.

30. sintered particles according to claim 1 and 2, the corundum content having is more than 8% and/or little In 35%.

31. sintered particles according to claim 30, wherein: described corundum content more than 12% and/ Or less than 30%.

32. sintered particles according to claim 31, wherein: described corundum content is more than 15%.

33. sintered particles according to claim 1 and 2, the content of " other crystallize phase " that have is less than 8%.

34. sintered particles according to claim 33, wherein: the content of described " other crystallize phase " is little In 5%.

35. sintered particles according to claim 34, wherein: the content of described " other crystallize phase " is little In 3%.

36. sintered particles according to claim 1 and 2, with the weight percent relative to described granule Than meter, the amount of the amorphous phase having is by weight less than 20% with more than 5%.

37. sintered particles according to claim 36, wherein: with the weight hundred relative to described granule Proportion by subtraction meter, the amount of amorphous phase is by weight less than 15% and/or more than 7%.

38. according to the sintered particles described in claim 37, wherein: with the weight hundred relative to described granule Proportion by subtraction meter, the amount of amorphous phase is by weight less than 12%.

39. sintered particles according to claim 36, wherein: the amorphous phase represented in the form of an oxide Including MgO and SiO₂, and/or B₂O₃And/or Y₂O₃And/or lanthanide oxide and/or Al₂O₃And/or CaO And/or Na₂O and/or K₂O and/or P₂O₅。

40. according to the sintered particles described in claim 39, wherein: the amorphous phase represented in the form of an oxide Including MgO, SiO₂、Na₂O、K₂O and P₂O₅。

41. sintered particles according to claim 1 and 2, the total porosity that described granule has is less than 5.5%.

42. sintered particles according to claim 41, the total porosity having is less than 5%.

43. sintered particles according to claim 42, the total porosity having is less than 4%.

44. sintered particles according to claim 1 and 2, the sphericity having is more than 0.6, described sphericity It it is the minimum diameter ratio with the maximum gauge of described granule of described granule.

45. sintered particles according to claim 44, the sphericity having is more than 0.7.

46. sintered particles according to claim 45, the sphericity having is more than 0.8.

47. sintered particles according to claim 1 and 2, the particle diameter having is less than 10mm and is more than 0.005mm。

48. sintered particles according to claim 1 and 2, wherein, zirconium oxide and/or hafnium oxide are by surely Fixedization.

49. 1 kinds of powder, including by weight percentage more than 90% according to claim 1 or claim 2 Granule.

50. 1 kinds of methods manufacturing sintered particles according to claim 1 and 2, described method includes The following step carried out successively:

C) preparing starting material from particulate mixtures, the composition of described starting material is adjusted with in step g) At the end of obtain sintered particles, the composition of this sintered particles meets sintering according to claim 1 and 2 The composition of granule, described starting material has the glass particle containing magnesium oxide and/or the glass containing magnesium oxide Pottery granule and/or include MgO and SiO₂The granule of compound,

D) starting material is configured to the form of rough granule,

G) sinter under more than 1330 DEG C with less than the sintering temperature between 1410 DEG C.

51. methods according to claim 50, wherein, described method is carried out before being included in step c) Following steps a): grind one or more raw-material powder so that they mixes in step c) Particulate mixtures to the median particle diameter having less than 0.6 μm.

52. methods according to claim 51, wherein, described method be included in after step a) and The steps b) carried out before step c): be dried described particulate mixtures.

53. methods according to claim 50, wherein, described method be included in after step d) and The steps e) carried out before step g): washing.

54. methods according to claim 50, wherein, described method be included in after step d) and The steps f) carried out before step g): be dried.

55. methods according to claim 50, wherein, in step c), containing the glass of magnesium oxide The granule of glass granule and/or the glass ceramics containing magnesium oxide comprises the percentage by weight titanium dioxide more than 40% Silicon.

56. methods according to claim 55, wherein: in step c), containing the glass of magnesium oxide The granule of glass granule and/or the glass ceramics containing magnesium oxide comprises the percentage by weight titanium dioxide more than 60% Silicon.

57. methods according to claim 50, wherein, in step c), described compound includes MgO and SiO₂, also include Al₂O₃。

58. methods according to claim 57, wherein: described compound selected from Talcum, cordierite and Its mixture.

59. methods according to claim 58, wherein: described compound is cordierite.

60. 1 kinds of objects, selected from suspension, grinder, the equipment processed for surface and heat exchanger, Described object includes powder according to claim 49.