CN1230381C - Potassium titanate powder - Google Patents
Potassium titanate powder Download PDFInfo
- Publication number
- CN1230381C CN1230381C CNB018000282A CN01800028A CN1230381C CN 1230381 C CN1230381 C CN 1230381C CN B018000282 A CNB018000282 A CN B018000282A CN 01800028 A CN01800028 A CN 01800028A CN 1230381 C CN1230381 C CN 1230381C
- Authority
- CN
- China
- Prior art keywords
- potassium titanate
- particle
- major diameter
- less
- minor axis
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/003—Titanates
- C01G23/005—Alkali titanates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/74—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by peak-intensities or a ratio thereof only
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/51—Particles with a specific particle size distribution
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/54—Particles characterised by their aspect ratio, i.e. the ratio of sizes in the longest to the shortest dimension
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
Abstract
The present invention provides potassium titanate powder without risk of carcinogenicity, etc. The powder comprises particles of which the length is less than 2 mu m, and particles of which the ratio of length to width is less than 5; in addition, particles of which the ratio of length to width is less than 2 account for 90% or more and particles of which the ratio of length to width is less than 3 account for 97% by the count based on the quantity ratio of the particles.
Description
Field of the present invention
The present invention relates to potassium titanate powder, particularly pay attention to the potassium titanate powder of the style characteristic relevant with the health aspect as the additive of plastics, friction materials, coating, lubricant, heat-stable material, lagging material, paper etc.
Background technology
It is a few μ m-tens μ m, diameter 1 μ m or the following shape of 1 μ m that potassium titanate had length originally, this shape is generally for example fiber, needle-like, palpus shape etc., can use its fiber shape flexibly, main as strongthener in the practical application in fields such as plastics, coating, friction materials, this extensively popularizes.But, fibrous powder have volume big, mobile poor, be difficult to character such as operation.And fibrous powder is easy to generate dust, has the problem on the Working environment.
The carinogenicity of asbestos has become problem, and the someone thinks that its reason is relevant with its fibrous shape.Be not only asbestos, for filamentary material, according to the hypothesis of Stanton (Stanton), diameter 0.25 μ m or 0.25 μ m are following, length 8 μ m or the above fiber of 8 μ m all have high carcinogenic.But, the industrial fibre material is to use under the standard of setting Working environment.ILO (World Federation of Trade Unions) with diameter 3 μ m or below the 3 μ m, length 5 μ m or more than the 5 μ m and length-to-diameter be that fiber more than 3 or 3 is defined as the imbedibility fiber.AIA (Asbestos International Association), DFG (Deutsche Forschungs Cremeinschaft: association is investigated by Germany) also list such fiber in the row of management as fibrous dust.
Therefore, the objective of the invention is angle, provide a kind of shape, size that does not have the imbedibility fiber, the potassium titanate particle that aspect style characteristic, has superiority from safety.
The present invention is open
The present invention is the result who makes great efforts exploitation in order to achieve the above object, and it provides a kind of is the potassium titanate powder of feature with the length of particle less than 2 μ m.More preferably with the product of length less than the particle composition of 1 μ m.In addition, another feature of potassium titanate of the present invention is that its major diameter/minor axis ratio is less than 5.Further, in the potassium titanate of the present invention, major diameter/minor axis accounts for more than 90% or 90 than the particle less than 2, and major diameter/minor axis accounts for more than 97% or 97% than the particle less than 3, and it consists of K
2OnTiO
2(n=1-12).
Have the of the present invention potassium titanate powder of above-mentioned major diameter, can prepare by the following method: with one or more K that generates by calcining less than the characteristic of 2 μ m
2The K source carbonate of O, oxyhydroxide, nitrate, sulfuric acid etc. and one or more TiO as the Ti source
2, mixing such as titanium hydroxide.Calcine this mixture, make it generate the particle of major diameter, add entry and make its pulp, add the unnecessary K of sour stripping again less than 2 μ m
+Ion is adjusted into required composition with it, dewaters afterwards and thermal treatment.
The shape of particle is to be determined by initial calcining herein, material alterations can not take place in subsequent handlings such as pulp, composition adjustment, thermal treatment.After the calcining of the mixture in K source and Ti source,, and be major diameter/minor axis basically than being particle more than 2 or 2 usually because the crystal growth meeting generates major diameter is 2 μ m or the above potassium titanate particle of 2 μ m.Potassium titanate of the present invention can be approaching with the minimum temperature that can carry out of reaction by making initial calcining temperature, and calcination time is limited in the short period of time that does not have crystal growth obtains.The proportion of composing in K source and Ti source is TiO
2/ K
2The mol ratio of O is in the 1-6 scope.This mol ratio is less than 1 o'clock, generates more major diameter/minor axis than being particle more than 2 or 2; This mol ratio was greater than 6 o'clock, and reaction is difficult to carry out.Calcining temperature is in 750-850 ℃ of scope, and when temperature was lower than 750 ℃, reaction was difficult to carry out, and when temperature was higher than 850 ℃, major diameter/minor axis was than being that the shared ratio of particle more than 2 or 2 will increase.Suitable method for calcinating is to adopt the rotary kiln mode.If adopt and to leave standstill method for calcinating, then will generate the non-uniform temperature part, generate major diameter/minor axis easily than being particle more than 2 or 2.
In addition, in K source and Ti source, add one or more a spot of basic metal such as carbonate of Li, Na, Rb, Cs, oxyhydroxide, nitrate, vitriol, alkali-metal halogenide etc. except that K, after the mixture calcining that gets therefrom, also can generate the particle of major diameter less than 2 μ m.It is believed that this is because the basic metal beyond the K that is added has the effect that reduces the said mixture fusing point when calcining, thereby the building-up reactions under lower temperature is finished easily, suppressed to generate the crystal growth of fiber shape thus.
Basic metal forms a little sosoloid in the crystallization of potassium titanate of the present invention, can use in the scope that satisfies the purpose x-ray diffraction pattern.
The potassium titanate particle of Huo Deing like this, its major diameter is short, and major diameter/minor axis a little less than the x-ray diffraction intensity, shows broad semi-minor axis diffracted ray than little on x-ray diffraction pattern.This shows that this particle has low-crystallinity, is not fibrous.
Form and calcination condition the particle of the flat pattern that can obtain to approach by adjusting raw material.The particle that this is flat carries out X-ray diffraction, and one of the feature that can find its diffractogram is, is 3 or less than 3 with the diffracted intensity of face of (h00) face of the Miller's indices of (hkl) expression/(0k0).We think that this is because crystal plane (0k0) is directed.Existing fibrous potassium titanate stretches at the b direction of principal axis, and is relative with it, and potassium titanate of the present invention is in a axle, the dramatic growth of c direction of principal axis, as viewed from thin flat particle.Such potassium titanate particle does not have fibering, is suitable material at secure context.
If no problem when using, in potassium titanate powder of the present invention, can there be not TiO so on a small quantity with the reaction of K source
2, the TiO that forms by the potassium titanate thermolysis
2, the amount of its existence can qualitative detecting be as the criterion with X-ray diffraction.And, can comprise a certain amount of 2 particles as the powder body commonly used of Industrial products, these 2 particles form after 1 particle is assembled.
The powder that potassium titanate of the present invention is made up of particle, the characteristics with flat, easy orientation can form the slipping plane of homogeneous thus, have excellent sliding properties as stopper material etc.In addition, if be used with plastics, dimensional precision raises, the suitable precise forming product that strengthen and provide surface smoothing etc. as rigidity.In addition, compare with fibrous potassium titanate, expectation with described potassium titanate be used for can flexible Application its field of mixed characteristic at high proportion.
The accompanying drawing summary
Fig. 1 is 10,000 times a microphotograph of potassium titanate powder, and Fig. 2 is 1,500 times a microphotograph of existing potassium titanate powder.Fig. 3 represents the relation of the major diameter/minor axis ratio of particle, and Fig. 4 is the x-ray diffraction pattern of embodiment and existing embodiment.
Implement best mode of the present invention
The particle that major diameter/minor axis is bigger generally waits and represents, but always define than numerical value with concrete major diameter/minor axis with fibrous, needle-like, palpus shape.Therefore, the present invention is based on security and productive balance, regulation major diameter/minor axis ratio is decided to be less than 5.And, with major diameter/minor axis than less than 3, major diameter/minor axis is than less than 2 indexs that distribute as particle shape of the present invention.
Why with major diameter less than 2 μ m as the emphasis of noting, be in order to avoid the suspection that fiber works the mischief to human body from microcosmic angle.For example, it is reported, can be observed by SEM (scanning electronic microscope) in mesothelioma patient's the lung and have the asbestos fragment.Though also do not have clear and definite explanation at present about malignant tumour such as mesothelioma, lung cancer and the relation of asbestos or carcinogenic mechanism, people think as follows usually.Promptly after asbestos arrive alveolar, the scavenger cell of being responsible for eliminating foreign matter comes into play, secrete the proteolytic enzyme (it is plain that Application パ Network matter is decomposed acid) of absorption asbestos thus it is become is safe from harm.But the scavenger cell about 3-5 μ m can't absorb the asbestos that have than its bigger staple length, and asbestos are on the contrary with its film destroy.So, around proteolytic enzyme just begins to leak into, contain proteinic alveolar cell and destroyed, cause inflammation.And on the other hand, even the lower particle of fibering arrives alveolar, if major diameter is 1 μ m or so also can be excreted together along with exhaling below the 1 μ m.Therefore, the invention provides a kind of major diameter less than 2 μ m, less than 1 μ m, major diameter/minor axis is than very little potassium titanate particle under the preferable case.And when being used for not needing fibrous purposes, ideal situation is not contain the imbedibility fiber.Further, not the imbedibility fiber too by the fibrous potassium titanate of the flat pattern of very thin thickness, but suitable material.More particularly, thickness be minor axis 1/2 or comparatively suitable less than 1/2.
Physical propertiess such as potassium titanate has the whiteness height, Mohs' hardness is low, thermal conductivity is low, specific refractory power height are a kind of materials with excellent heat resistance, resistance to chemical reagents, sliding.Therefore, except can be used as strongthener, potassium titanate also can be used as the additive of plastics, friction materials, coating, paper etc., and as lubricant, heat-stable material, lagging material, insulating material, ion exchanger, catalyzer etc.Further, big with the fibrous powder volume, mobile poor, be difficult to operate corresponding, potassium titanate of the present invention improves these defectives, has the scope of application widely.According to application target, can carry out surface treatments such as coupling to it, also can carry out granulation if desired.
After potassium titanate particle and plastics are used, characteristics such as rub resistance abrasion have been endowed, the suitable slide unit etc. that is used as.When as the friction materials of stopper etc., to compare with existing potassium titanate fiber, potassium titanate of the present invention has given play to that frictional coefficient is more stable to wait excellent frictional behaviour.
Embodiment
At K
2CO
3And TiO
2In add basic metal beyond a small amount of K, change proportion of composing, the calcination condition of this mixture, can obtain particle shape, different calcinates distributes.Then, in various calcinates, add entry and make its pulp, further add HCl with stripping K
+Thereby ion is regulated its TiO
2/ K
2The mol ratio of O is heat-treated afterwards, obtains K at last
2O8TiO
2Particle.
With the various K that obtain
2O8TiO
2Micropartical carries out chemical analysis, the basic metal R beyond the K
2(R: content basic metal) is 3wt% or below the 3wt% to O.And then, with K
2O8TiO
2Atomic electron microscope picture carries out dissection process, measure major diameter, minor axis and the major diameter/minor axis ratio of each particle, calculate major diameter/minor axis than less than 3 and major diameter/minor axis than less than the shared ratio of 2 population, and every minimum value, maximum value, mean value.
In addition, in water, carry out ultrasonic dispersing and handle, measure as the laser type particle size distribution device of measuring principle, obtain accumulation undersized 100% diameter (weight %) and 50% diameter (weight %) in order to Fraunhofer diffraction and Mie scattering.
X-ray diffraction adopts the slit of DS=1 °, SS=1 °, RS=0.3mm when measuring, measure with the CuK alpha-ray.Obtain K
2O8TiO
2The diffracted intensity ratio of (200)/(020).Creating conditions of sample is as shown in table 1, and the result is as shown in table 2.
Table 1
| Embodiment | Raw material cooperates | Calcination condition | ||
| TiO 2/K 2The O mol ratio | Basic metal (wt%) | Calcining manners | Calcining temperature ℃ | |
| 1 | 5.2 | Na 2CO 3(5) | Rotary kiln | 750 |
| 2 | 3.1 | NaNO 3(4) | Rotary kiln | 800 |
| 3 | 1.8 | NaCl(3) | Rotary kiln | 850 |
Table 2
| Embodiment | Major diameter (μ m) | Minor axis (μ m) | Major diameter/minor axis ratio | The number ratio % of major diameter/minor axis ratio＜5 | The number ratio % of major diameter/minor axis ratio＜3 | The number ratio % of major diameter/minor axis ratio＜2 | Size-grade distribution (μ m) | X-ray diffraction (200)/(0 20) strength ratio | |||||||
| Minimum | Maximum | On average | Minimum | Maximum | On average | Minimum | Maximum | On average | |||||||
| D100 | D50 | ||||||||||||||
| 1 | 0.06 | 0.74 | 0.23 | 0.04 | 0.50 | 0.16 | 1.00 | 4.56 | 1.45 | 100 | 98.7 | 93.8 | 1.00 | 0.53 | 0.65 |
| 2 | 0.11 | 0.92 | 0.31 | 0.07 | 0.62 | 0.21 | 1.00 | 3.13 | 1.27 | 100 | 99.1 | 97.5 | 1.25 | 0.61 | 1.24 |
| 3 | 0.21 | 1.73 | 0.75 | 0.11 | 1.59 | 0.59 | 1.00 | 2.95 | 1.12 | 100 | 100 | 98.0 | 1.84 | 1.42 | 2.54 |
Potassium titanate particle shape by embodiment 1-3 gained is as shown in table 1, and its major diameter is for being 0.74-1.73 μ m to the maximum, and major diameter/minor axis ratio is 2.95-4.56 to the maximum.In addition, major diameter/minor axis is 100% than the ratio less than 5 particle number, and the ratio of the particle number less than 3 is 98.7-100%, and the ratio of the particle number less than 2 is 93.8-98.0%.(200)/(020) X-ray diffraction intensity is than being 0.65-2.54.
Fig. 1 is representative 10, the 000 times microphotograph by the potassium titanate particle of the present invention of embodiment 1 gained, and as a comparison, Fig. 2 is 1,500 times a microphotograph of existing potassium titanate.Existing potassium titanate shown in Figure 2 presents the shape of fiber, and particle embodiment illustrated in fig. 1, and its major diameter is 1 μ m or below the 1 μ m, and most major diameter/minor axis is below 2 or 2 than all.In addition, can be observed the flat particle shape existence of very thin thickness.
Fig. 3 has drawn out the minor axis of particle of the embodiment of the invention 1 and the relation of major diameter.Write down the line of major diameter/minor axis ratio=1,2,3,4,5 among the figure.Do not exist major diameter/minor axis than the particle that surpasses 5.In addition, expressed in the lump also that major diameter is that 5 μ m or 5 μ m are following, minor axis is 3 μ m or 3 μ m are following, major diameter/minor axis is than the field that is the harmful fiber below 3 or 3.
Fig. 4 is the X-ray diffractogram of Fig. 1, powder shown in Figure 2.Existing 8 potassium titanates present sharp-pointed diffraction peak, and are corresponding with it, and 8 potassium titanates of the present invention have low-crystalline.(200) of existing potassium titanate/(020) diffracted intensity ratio is 6.3, and (200) of the potassium titanate of embodiment 1/(020) diffracted intensity ratio is 0.65.(200) of embodiment 2 and embodiment 3/(020) diffracted intensity is being below 3 or 3 than also.
The possibility of commercial Application
As mentioned above, major diameter of the present invention is less than the potassium titanate powder of 2 μ m, and its major diameter/minor axis also is safe from harm to human body, and does not contain the imbedibility fiber than also little, can be applied to safely various uses, is very useful industrial materials.
Claims (5)
1. potassium titanate powder, this powder is made up of less than the particle of 2 μ m major diameter basically, and the major diameter of described particle/minor axis is than less than 5.
2. the potassium titanate powder of claim 1, wherein major diameter/minor axis accounts for more than 90% or 90% than the particle less than 2, and major diameter/minor axis accounts for more than 97% or 97% than the particle less than 3.
3. the potassium titanate powder of claim 1 is characterized in that being made up of the flats particle of very thin thickness.
4. the potassium titanate powder of claim 3, wherein the diffracted intensity ratio of face of (h00) face/(0k0) is 3 or less than 3 in X-ray diffraction.
5. the potassium titanate powder of any one among claim 1 and the 3-4, it comprises the alkali-metal particle that contains except that K.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/JP2001/000002 WO2002055437A1 (en) | 2001-01-04 | 2001-01-04 | Potassium titanate powder |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1392864A CN1392864A (en) | 2003-01-22 |
| CN1230381C true CN1230381C (en) | 2005-12-07 |
Family
ID=11736873
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB018000282A Expired - Lifetime CN1230381C (en) | 2001-01-04 | 2001-01-04 | Potassium titanate powder |
Country Status (3)
| Country | Link |
|---|---|
| KR (1) | KR100711871B1 (en) |
| CN (1) | CN1230381C (en) |
| WO (1) | WO2002055437A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1304298C (en) * | 2003-06-05 | 2007-03-14 | 中国科学院上海硅酸盐研究所 | Trigonal structure potassium titanate and its preparing method |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000256013A (en) * | 1999-03-08 | 2000-09-19 | Kawatetsu Mining Co Ltd | Potassium titanate fine particle |
| JP2000264692A (en) * | 1999-03-16 | 2000-09-26 | Otsuka Chem Co Ltd | Friction material |
| JP4313458B2 (en) * | 1999-03-16 | 2009-08-12 | 大塚化学ホールディングス株式会社 | Friction material |
| JP2000264689A (en) * | 1999-03-16 | 2000-09-26 | Otsuka Chem Co Ltd | Friction material |
-
2001
- 2001-01-04 WO PCT/JP2001/000002 patent/WO2002055437A1/en active Application Filing
- 2001-01-04 CN CNB018000282A patent/CN1230381C/en not_active Expired - Lifetime
- 2001-01-04 KR KR1020017008161A patent/KR100711871B1/en active IP Right Grant
Also Published As
| Publication number | Publication date |
|---|---|
| WO2002055437A1 (en) | 2002-07-18 |
| CN1392864A (en) | 2003-01-22 |
| KR100711871B1 (en) | 2007-04-25 |
| KR20020085774A (en) | 2002-11-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Baglioni et al. | Soft and hard nanomaterials for restoration and conservation of cultural heritage | |
| Matijević | Preparation and characterization of monodispersed metal hydrous oxide sols | |
| Mädler et al. | Rapid synthesis of stable ZnO quantum dots | |
| EP2891690B1 (en) | Coating composition comprising submicron calcium carbonate-comprising particles, process to prepare same and use of submicron calcium carbonate-comprising particles in coating compositions | |
| EP2684916B1 (en) | Surface modified calcium carbonate containing minerals and its use | |
| DE102007058674A1 (en) | Nanoparticulate composition and process for its preparation | |
| Puvvada et al. | Room temperature synthesis of highly hemocompatible hydroxyapatite, study of their physical properties and spectroscopic correlation of particle size | |
| Cao et al. | Preparation of petal-like magnesium hydroxide particles by adding sulfate ions | |
| CN1284832C (en) | Titanium dioxide pigments with improved gloss and/or durability | |
| CN1230381C (en) | Potassium titanate powder | |
| Wu et al. | Preparation and properties of composite particles made by nano zinc oxide coated with titanium dioxide | |
| Fratzl et al. | Diffracting “stacks of cards”-some thoughts about small-angle scattering from bone | |
| CN103298744A (en) | Process for controlling particle size and additive coverage in the preparation of titanium dioxide | |
| Arantes et al. | Synthesis and optimization of colloidal hydroxyapatite nanoparticles by hydrothermal processes | |
| DE3737839A1 (en) | CORUND-RUTILE COMPOSITE SINTER BODY AND METHOD FOR THE PRODUCTION THEREOF | |
| DE60036504T2 (en) | Fine potassium titanate particles | |
| CN1508072A (en) | Method for preparing nano magnesium oxide | |
| US6036938A (en) | Potassium titanate substantially free of respirable fibers and method for producing the same | |
| DE60024720T2 (en) | potassium titanate | |
| Onoda et al. | Synthesis of titanium phosphates with additives and their powder properties for cosmetics | |
| Kurajica et al. | Mechanochemical synthesis of zincite doped with cadmium in various amounts | |
| Ibrahim et al. | Effect of calcination temperature on (N, Fe) doped TiO2 nanoparticles | |
| CN1151512C (en) | Electrically conducting nano-class sb-contained microparticles and preparing process thereof | |
| Yan et al. | Preparation and characterization of oriented hydroxyapatite bundles in supersaturated solution: ionic interference and charge balance | |
| CN1316895C (en) | Method for preparing inorganic nano-germicide powder |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CX01 | Expiry of patent term |
Granted publication date: 20051207 |
|
| CX01 | Expiry of patent term |