CN102798640A - Method for detecting quality of pearl powder by XRD (X-Ray Diffraction) and application thereof - Google Patents
Method for detecting quality of pearl powder by XRD (X-Ray Diffraction) and application thereof Download PDFInfo
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Abstract
The invention relates to a method for detecting the quality of pearl powder and an application thereof. The method for detecting the quality comprises any one or a combination of following methods of: 1) utilizing an XRD diffraction method to analyze a sample to be detected, wherein the content of a calcite phase in the pearl powder is less than or equal to 4.0 wt.% and the content of an aragonite phase is more than or equal to 96.0 wt.%; and/or 2) utilizing a DSC/TGA (Dynamic Stability Control/Thermal Gravity Analysis) to analyze the sample to be detected, wherein the content of organic substances in the pearl powder is 3.5-5.0 wt.%; and/or 3) heating the sample to be detected to any one temperature in a range of 200-450 DEG C and keeping the heat for 5-10 minutes; and after reducing the temperature to a room temperature, taking out the sample to be detected; and utilizing the XRD diffraction method to detect the content of calcite, wherein the content of the calcite in the pearl powder is less than or equal to 15.0 wt.%. The detection method disclosed by the invention has the advantages of strong specificity, good stability and reproducibility, rapidness and sensitivity, simplicity, accuracy, effectiveness, no interferences and the like.
Description
Technical field
The present invention relates to XRD and detect pearl powder method for quality and application thereof,, thereby guarantee its curative effect and security with stability, reappearance, consistance and the controllability of raising pearl powder quality testing.
Background technology
Pearl is famous and precious ornament and famous and precious Chinese crude drug; The calcium activated, 18 seed amino acids, 30 various trace elements and the abundant vitamin B complex composition that contain 91-94%; Have clearing heat and detoxicating, drug effects such as yin-nourishing relieves dizziness, high fever, infantile convulsions, epilepsy, etc., the myogenic that makes eye bright, China is historical to its medication in existing more than 2000 year.
Pearl is divided into sea water pearls and fresh water pearl two big classes.China is the main place of production of pearl and pearl powder in the world, accounts for 75% of Gross World Product.At present; Only there are the high-grade pearl of 8-10% and 30% process level pearl can be processed into jewellery and handicraft in China fresh water pearl; Most pearls are difficult to be processed into artwork Ornament because of influenced by its exterior appearance, size, aberration etc.; But be processed into pearl powder, as the raw material of multiple medicine, health products and cosmetics, to improve its added value.
The outward appearance of pearl is stratiform pearly-lustre color.X-ray diffraction analysis shows; Pearl is the biologic inorganic mineral matter of crystalline state; Lime carbonate by aragonite (Aragonite) and two kinds of homogeneity different crystals of kalzit (Calcite) structure is formed, and organic matter is embedded in and forms inorganic-organic double compound between aragonite phase, the kalzit phase simultaneously.Organic matter in the pearl does not present the crystal structure characteristic, but makes pearl have sparkling, beautiful sparkling and crystal-clear outward appearance of pearly-lustre and hard mechanical property.
Organic matter in the pearl mainly comprises amino acid, bioactive peptide, pearl protein etc.; And maybe be owing to the synergy of inorganic-organic complex in the pearl; Make pearl powder have beauty treatment, improve pharmaceutical properties such as eyesight, enhance immunity, and be used to prepare medicine, health products and cosmetics etc.In addition, factor such as the biologically active of pearl and its composition and composition, job operation, micromechanism (grain size, shape, distribution), noxious material (like lead, mercury, arsenic etc.) content, growth environment is relevant.
At present, pearl powder has been used for preparation medicine, health food, cosmetics etc.The listing product relevant with pearl comprise pearl powder, pearl oral liquid, pearl lozenge, precious chrysanthemum verticilum, Liushen Pills, piece and, pearl soap, pearl tooth-paste etc., and its application also constantly widening, economic worth constantly doubles.The output of China's pearl powder is 600 tons, and the annual value of production of pearl powder and derived product has reached 300,000,000 yuan, estimates that the output value of following 2-3 will be above 1,000,000,000 yuan.
Pearl and parent clam shell thereof are through natural long-term evolution; Progressively develop and become biomineralization material with perfect institutional framework, form and unique excellent properties; And become the self-assembly template of organic macromolecule (protein, polysaccharide, lipid etc.), through molecular recognition, inorganic carbonate calcium molecule is piled up on the self-assembly template and is formed a kind of natural organic/inorganic composite material (" MannS.Nature "; 1988,332:119-124; " Mann S.Nature ", 1993,365; 499-505).Yet the resistance to fracture toughness of aragonite is wanted more than thousand times of Senior Three than anorganogene aragonite in the pearl.Itself there is not the kalzit phase in the pearl.Kalzit in the pearl powder is in mechanical processing process, to be changed mutually by aragonite to form mutually.The clam shell housing is made up of cuticula, prismatic layer and nacre (claiming " pearl shell internal layer " or " shell internal layer " again); Wherein, Contain kalzit in the prismatic layer; And be polygonal aragonite crystal wafer crossing stack structure in the nacre, be organic between the lamella, and show as organic and inorganic crossing stack structure in good order.
Mother-of-pearl and pearl are with the root homology, and the chemical composition of Concha Margaritifera powder is similar with pearl powder.Concha Margaritifera powder is very similar with the appearance characteristics of pearl powder, is difficult to differentiate only according to naked eyes.Existing research adopts thermal analysis system, X-ray diffraction method, microscopic analysis, scanning electron microscope analysis method to be used to differentiate crystal phase structure, form and the content of organic matter difference of Concha Margaritifera powder (oyster shell whiting) and pearl powder.Lin Jinming etc. (" The 2nd Army Medical College journal ", 1994) disclose and have adopted differential thermal analyzer to distinguish the method for pearl powder and nacreous layer powder through measuring heat enthalpy value, and this discovers that the heat enthalpy value of pearl powder is 53-59 △ H/Jg
-1, the heat enthalpy value of nacreous layer powder is 29-30 △ H/Jg
-1, but research shows that the heat enthalpy value of the Concha Margaritifera powder that quality is higher and pearl powder are very approaching, only is difficult to the pearl powder distinguishing pearl powder, high-quality Concha Margaritifera powder or mixed the high-quality Concha Margaritifera powder through the mensuration heat enthalpy value.Chang Linkai etc. (" chemistry world "; 2000) employing thermogravimetric kinetic measurement pearl powder, nacreous layer powder, Concha Margaritifera powder method for quality are disclosed, this discovers that the thermogravimetric analysis of pearl powder and nacreous layer powder is divided into two stages; The weight-loss ratio about 3% of phase one (250 ℃-370 ℃); Reaction order 1.6, energy of activation 105-110KJ/mol is the sex change and the decomposition of organic matter; The weight-loss ratio of subordinate phase (600-770 ℃) is about 40%, the order of reaction 1.3, and energy of activation 280-290KJ/mol is the decomposition of lime carbonate.There is not tangible weightlessness in Concha Margaritifera powder at 250 ℃-370 ℃.But oneself removes destratum corneum the Concha Margaritifera powder that this research institute uses; So do not have organic sex change and decomposition; Only exist lime carbonate to decompose; This method only can be used for differentiating high-quality Concha Margaritifera powder, is difficult to use in discriminating and does not remove cuticular Concha Margaritifera powder and contain prismatic layer and cuticular nacreous layer powder.This research shows that the structure of pearl powder and nacreous layer powder is very similar with composition, and the analysis conclusion of relevant Concha Margaritifera powder (oyster shell whiting) only limits to high-quality Concha Margaritifera powder.In addition; The test sample consumption of thermogravimetry is few; Mostly be several milligrams to more than ten milligrams, thus very high to the uniformity coefficient requirement of test sample, when being mixed with other homologues in the pearl powder; The test result poor reproducibility, and the exothermic peak of the different pearl powder of particle diameter and the position and the peak area of endothermic peak differ greatly.
The cost of Concha Margaritifera powder is low; Often pretend to be pearl powder or be doped in the pearl powder and come into the market; Even still there is like other outer appearnces powder (like shell of seaear powder, talcum powder, Paris white, flour etc.) be doped in the pearl powder or pretends to be pearl powder to come into the market; Mixed powder that these matter are inferior or personation pearl powder have a strong impact on consumer's health and safety, and hinder the sound development of pearl sector.Therefore; Be badly in need of research and set up quick, the easy pearl powder quality determining method of a cover; Be used to differentiate the true and false of pearl powder and estimate its quality, as the evaluation foundation that instructs and organize pearl powder production, acceptance of delivery and supervision and check pearl powder, progressively standard pearl powder market; Guarantee and improve pearl powder or its security of products and validity, promote the sustainable and healthy development of pearl powder industry.
Summary of the invention
The object of the present invention is to provide a kind of quality determining method of pearl powder; It is characterized in that; Adopt the XRD diffraction approach to analyze testing sample, described testing sample is selected from any of pearl powder, Concha Margaritifera powder, nacreous layer powder, mixed powder, other powders, wherein; Content≤the 4.0wt.% of kalzit phase in the pearl powder, the content>=96.0wt.% of aragonite phase.
Inorganic in fresh water pearl and the sea water pearls mainly comprises aragonite phase (Aragonite) and kalzit (calcite) mutually mutually, has six side's spherical calcium carbonate (Vaterite) thing phases individually.If detect other thing phase in the testing sample, can differentiate that this sample is the pure powder of non-pearl (claiming " pure pearl powder " again), but Concha Margaritifera powder, mixed powder or pretend to be other powders of pearl powder.
In the optimal technical scheme of the present invention, aragonite thing phase (Aragonite, CaCO in the pearl powder
3) crystallographic system be quadrature, space group is pmcn, cell parameter does
Z=4, D (calc)=2.92.
In the optimal technical scheme of the present invention, kalzit phase (calcite, CaCO in the pearl powder
3) crystallographic system be tripartite, space group is R-3CH, cell parameter does
Z=6, D=2.73.
In the optimal technical scheme of the present invention, the test condition of XRD diffraction approach is CuK
ArfRadiation, DS/SS:1 ° of RS 0.2mm, diffracted ray bondstone China ink monochromator is removed K
BataRadiation, power are not less than 1.6 kilowatts, and the step scanning mode is gathered diffraction data, promptly gets.
In the optimal technical scheme of the present invention, the preparation method of testing sample comprises any or its combination of following method in the XRD diffraction approach:
1) directly presses the powdery diffractometry sample preparation methods, the testing sample powder is pressed on the specimen holder of XRD diffractometer, again it is inserted diffractometer and detect and collect experimental data; And/or
2) accurately measure texture coefficient sample, earlier powdered samples is processed 1% suspending liquid, drop on the tabular sample panel, insert the XRD diffractometer behind the airing and detect and gather experimental data with dropper.
In the optimal technical scheme of the present invention, the diffraction data that the XRD diffraction approach records carries out data processing with the Jade9 software package.
The object of the present invention is to provide a kind of quality determining method of pearl powder; It is characterized in that; Adopt DSC/TGA to analyze testing sample, described testing sample is selected from any of pearl powder, Concha Margaritifera powder, nacreous layer powder, mixed powder, other powders, wherein; The content of organic matter in the pearl powder is 3.5-5.0wt.%, and preferred described pearl powder is selected from any of pearl meal, pearl fine powder, pearl micropowder.
In the optimal technical scheme of the present invention, the content of organic matter in the pearl meal is 4.3-5.0wt.%.
In the optimal technical scheme of the present invention, the content of organic matter in the pearl fine powder is 4.0-4.3wt.%.
In the optimal technical scheme of the present invention, the content of organic matter in the pearl micropowder is 3.5-4.0wt.%.
In the optimal technical scheme of the present invention, the content of organic matter in the Concha Margaritifera powder is 2.5-4.0wt.%.
In the optimal technical scheme of the present invention, said DSC/TGA detection method comprises the steps:
A) with thermogravimetric analyzer (DSC/TGA) start preheating 30 minutes, connect air;
B) balance reading makes zero after stablizing, and opens stove and takes off dress appearance, with α-Al
2O
3The crucible 10-15mg testing sample of packing into is put back to, and shuts stove;
C) treat that balance reading is stable after, (speed that is preferably 10 ℃/min-15 ℃/min) is warming up to 700 ℃-900 ℃ (being preferably 800 ℃), measures TG/DTA curve and data, promptly gets with 5 ℃/min-20 ℃/min.
In the optimal technical scheme of the present invention,, utilize instrument software to handle with detected DSC/TGA data file deposit.
The present invention discovers that the oxygenolysis temperature of organic matter is far below the decomposition temperature of inorganic mineral phase in the pearl powder.The present invention adopts thermogravimetry to quantize organic oxygenolysis in the record pearl powder sample, indexs such as the content of organic matter, decomposition temperature in the detection by quantitative pearl powder.
The object of the present invention is to provide a kind of quality determining method of pearl powder, it is characterized in that, testing sample is heated to the arbitrary temperature between 200 ℃-450 ℃ after; Be incubated 5-10 minute, treat that it reduces to room temperature after, take out testing sample; Adopt XRD diffraction analysis method to detect kalzit phase content wherein; Described testing sample is selected from any of pearl powder, Concha Margaritifera powder, nacreous layer powder, mixed powder, other powders, wherein, and the kalzit content≤15.0wt.% in the pearl powder; Kalzit content≤10.0wt.% in the preferred pearl powder, more preferably the kalzit content in the pearl powder is 1.0wt.%-9.0wt.%.
In the optimal technical scheme of the present invention, the kalzit content in the Concha Margaritifera powder is 18.0wt.%-60.0wt.%.
In the optimal technical scheme of the present invention, the kalzit content in the nacreous layer powder is 15.0wt.%-45.0wt.%.
In the optimal technical scheme of the present invention, the kalzit content in the mixed powder is 10.0wt.%-25.0wt.%.
In the optimal technical scheme of the present invention; The analysis condition that detects the hot phase transformation of testing sample in the XRD diffraction approach does; With 50 ℃ of-150 ℃/min (be preferably 100 ℃/min) speed, testing sample is heated to the arbitrary temperature in 200 ℃-350 ℃ or 350 ℃-450 ℃ after, be incubated 5-10 minute; (be preferably 100 ℃/min) speed and reduce to normal temperature, gather and analyze the kalzit phase content in the testing sample with 50 ℃ of-150 ℃/min again in 15-70 degree 2 θ scopes.
In the optimal technical scheme of the present invention; (be preferably 100 ℃/min) speed with 50 ℃ of-150 ℃/min; After testing sample is heated to a plurality of arbitrary temperature in 200 ℃-450 ℃; Be incubated 5-10 minute, (be preferably 100 ℃/min) speed and reduce to normal temperature, gather and analyze the kalzit phase content in the testing sample with 50 ℃ of-150 ℃/min again in 15-70 degree 2 θ scopes.
In the optimal technical scheme of the present invention; (be preferably 100 ℃/min) speed with 50 ℃ of-150 ℃/min; With testing sample be heated between 200 ℃-350 ℃ or arbitrary temperature or a plurality of arbitrary temperature between 350 ℃-450 ℃ after; Be incubated 5-10 minute; (be preferably 100 ℃/min) speed and reduce to normal temperature, gather and analyze the kalzit phase content in the testing sample in 15-70 degree 2 θ scopes, the detection phase transition temperature of preferred testing sample is arbitrary temperature or a plurality of arbitrary temperature between 250 ℃-400 ℃ with 50 ℃ of-150 ℃/min again; More preferably the detection phase transition temperature of testing sample is arbitrary temperature or a plurality of arbitrary temperature between 300 ℃-390 ℃, and most preferably the detection phase transition temperature of testing sample is 340 ℃-380 ℃ arbitrary temperature or a plurality of arbitrary temperature.
In the optimal technical scheme of the present invention; The heating arrangement of testing sample is selected from any of environmental sample platform, tube furnace of environmental sample platform, the high temperature annex of the environmental sample platform that contains the low temperature annex, middle temperature annex; After testing sample is heated to the arbitrary temperature or a plurality of arbitrary temperature between 200 ℃-450 ℃, utilize XRD to detect the kalzit content in the testing sample.
In the optimal technical scheme of the present invention; Testing sample is placed the constant temperature section of tube furnace; Feeding inert gas (like argon gas, nitrogen) protects; Flow is 150ml/min-250ml/min (being preferably 200ml/min), (after being preferably 100 ℃/min) speed and being heated to the arbitrary temperature or a plurality of arbitrary temperature in 200 ℃-450 ℃, is incubated 5-10 minute with 50 ℃ of-150 ℃/min; (be preferably 100 ℃/min) speed and reduce to normal temperature, gather and analyze the kalzit phase content in the testing sample with 50 ℃ of-150 ℃/min again in 15-70 degree 2 θ scopes.
In the optimal technical scheme of the present invention; Under air atmosphere, the vacuum condition or charge under the inert gas conditions; With 50 ℃ of-150 ℃/min (after being preferably 100 ℃/min) speed testing sample being heated to the arbitrary temperature or a plurality of arbitrary temperature in 200 ℃-450 ℃; Be incubated 5-10 minute, (be preferably 100 ℃/min) speed and reduce to normal temperature, gather and analyze the kalzit phase content in the testing sample with 50 ℃ of-150 ℃/min again in 15-70 degree 2 θ scopes.
The hot Transformation Kinetics of the present invention detects principle and is; Pearl and shell housing are aragonite calcium carbonate and the organic organic-inorganic composite body that forms of inlaying; Pearl powder and Concha Margaritifera powder roughly the same are difficult to distinguish in the even property of microstructure range of size De Zhuo; But the adhesion between aragonite and organic matter is at sub-micron, nano level significant difference, and this significant difference directly influences its mechanical property, mechanical property and aragonite kalzit inversion of phases speed mutually in opposite directions.Under normal temperature or natural storage condition, in the pearl aragonite transformation rate than the transformation rate of aragonite phase in its parent clam shell slowly many.The present invention discovers; All there is aragonite hot transformation behavior mutually in pearl powder with Concha Margaritifera powder (promptly between 200 ℃-450 ℃) in the phase transition temperature scope; And the hot phase transformation power speed significant difference of the two arbitrary temperature in the phase transition temperature scope; Wherein, the thermokinetics transformation rate of pearl powder significantly is slower than Concha Margaritifera powder.
The object of the present invention is to provide a kind of quality determining method of pearl powder; It is characterized in that; 1) adopt XRD diffraction analysis method to detect testing sample, described testing sample is selected from any of pearl powder, Concha Margaritifera powder, nacreous layer powder, mixed powder, other powders, wherein; Kalzit phase content≤4.0wt.% in the pearl powder, aragonite phase content>=96.0wt.%; And/or
2) adopt the DSC/TGA analytic approach to detect testing sample, described testing sample is selected from any of pearl powder, Concha Margaritifera powder, nacreous layer powder, mixed powder, other powders, and wherein, the content of organic matter in the pearl powder is 3.5-5.0wt.%.
The object of the present invention is to provide a kind of quality determining method of pearl powder, it is characterized in that, 1) testing sample is heated to the arbitrary temperature between 200 ℃-450 ℃ after; Be incubated 5-10 minute, treat that it reduces to room temperature after, take out testing sample; Adopt XRD diffraction analysis method to detect kalzit phase content wherein; Described testing sample is selected from any of pearl powder, Concha Margaritifera powder, nacreous layer powder, mixed powder, other powders, wherein, and the kalzit content≤15.0wt.% in the pearl powder; Kalzit content≤10.0wt.% in the preferred pearl powder, more preferably the kalzit content in the pearl powder is 1.0wt.%-9.0wt.%; Kalzit content in the preferred Concha Margaritifera powder is 18.0wt.%-60.0wt.%; Kalzit content in the preferred nacreous layer powder is 15.0wt.%-45.0wt.%; Kalzit content in the preferred mixed powder is 10.0wt.%-25.0wt.%; And/or
2) adopt the DSC/TGA analytic approach to detect testing sample, described testing sample is selected from any of pearl powder, Concha Margaritifera powder, nacreous layer powder, mixed powder, other powders, and wherein, the content of organic matter in the pearl powder is 3.5-5.0wt.%.
The object of the present invention is to provide a kind of quality determining method of pearl powder; It is characterized in that; 1) adopt the XRD diffraction approach to analyze testing sample, described testing sample is selected from any of pearl powder, Concha Margaritifera powder, nacreous layer powder, mixed powder, other powders, wherein; Kalzit phase content≤4.0wt.% in the pearl powder, aragonite phase content>=96.0wt.%; And/or
2) testing sample is heated to the arbitrary temperature between 200 ℃-450 ℃ after; Be incubated 5-10 minute, treat that it reduces to room temperature after, take out testing sample; Adopt XRD diffraction analysis method to detect kalzit phase content wherein; Described testing sample is selected from any of pearl powder, Concha Margaritifera powder, nacreous layer powder, mixed powder, other powders, wherein, and the kalzit content≤15.0wt.% in the pearl powder; Kalzit content≤10.0wt.% in the preferred pearl powder, more preferably the kalzit content in the pearl powder is 1.0wt.%-9.0wt.%; Kalzit content in the preferred Concha Margaritifera powder is 18.0wt.%-60.0wt.%; Kalzit content in the preferred nacreous layer powder is 15.0wt.%-45.0wt.%; Kalzit content in the preferred mixed powder is 10.0wt.%-25.0wt.%; And/or
3) adopt the DSC/TGA analytic approach to detect testing sample, described testing sample is selected from any of pearl powder, Concha Margaritifera powder, nacreous layer powder, mixed powder, other powders, and wherein, content organic in the pearl powder is 3.5-5.0wt.%.
The application that another object of the present invention is to provide the quality determining method of pearl powder of the present invention to be used for detecting or control the quality of pearl powder or its pharmaceutical products, preferred described pharmaceutical products are selected from any of pearl powder medicine, pearl powder cosmetic, pearl powder health products.
For clear statement protection scope of the present invention, the present invention carries out as giving a definition term:
Testing sample of the present invention is selected from any of pearl powder, Concha Margaritifera powder, nacreous layer powder, mixed powder, other powders.Except as otherwise noted, pearl powder of the present invention comprises any or its combination of pure pearl powder, pearl meal, pearl fine powder, pearl micropowder.
Pearl meal of the present invention is meant that mean grain size does
Degree of orientation p
100Pure pearl powder for 0.5-0.7.
Pearl fine powder of the present invention is meant that mean grain size does
Degree of orientation p
100Pure pearl powder for 0.7-0.8.
Pearl micropowder of the present invention is meant that mean grain size does
Degree of orientation p
100Pure pearl powder for 0.8-1.0.
" texture coefficient " of the present invention is for describing the quantized value of each crystal face nonrandom distributed degrees in sample space in Powdered polycrystalline material or the block polycrystalline material.Usually, the texture coefficient of Powdered each crystal face of texture sample is between 1.0-0.0, and wherein, the texture coefficient is to be complete no TEXTURE STATE at random at 1.0 o'clock.
" no texture powder " of the present invention is meant that the texture coefficient is 1.0 powdered samples, and wherein, each crystal face of no texture sample presents the state of completely random in the distribution of sample space.
" texture sample " of the present invention is meant that each crystal face in the powdered samples in space distribution presenting direction property rather than present the state of stochastic distribution, all shows as 100 texture like pearl powder, Concha Margaritifera powder, nacreous layer powder.
" mother-of-pearl " of the present invention claimed pearl tree peony, pearl oyster again, natural pearls are female, jewel is female; Comprise the shell fleshing of Unionidae animal hydriopsis cumingii Hyriopsis cumingii (Lea), cristaria plicata Cristaria plicata (Leach) or Pteriidae animal Pinctada martensii Pteria martensii (Dunker) and remove impurity; Cleaning, drying and getting.Wherein, the powder that forms is pulverized in mother-of-pearl processing and be called " Concha Margaritifera powder ", " oyster shell whiting " or " shell powder ".
" nacreous layer powder " of the present invention " be with removing the powder that shell internal layer (nacre) that cuticula, prismatic layer only keep mother-of-pearl partly processes, promptly nacreous layer powder is the higher Concha Margaritifera powder of quality of having removed cuticula, prismatic layer.
" mixed powder " of the present invention evenly mixes for the pure powder of non-pearl of pure pearl powder and arbitrary weight; Wherein, The pure powder of described non-pearl is selected from any of Concha Margaritifera powder, nacreous layer powder, other powders, and preferred described other powders comprise talcum powder, flour, shell of seaear powder, quartz sand powder, Paris white etc.
The preparation method of pearl powder according to the invention comprises the steps: pearl is cleaned, and more as required, adopts mechanical-physical methods such as ball milling, air-flow are pulverized, water flies that it is pulverized, to make the pearl powder of different fineness.
The preparation method of Concha Margaritifera powder according to the invention, take any or its combination of following method to prepare:
1) mother-of-pearl is cleaned, as required, adopted mechanical-physical methods such as ball milling, air-flow are pulverized, water flies that it is pulverized, to make the Concha Margaritifera powder of different fineness; And/or
2) with after the aqueous solution soaking processing of mother-of-pearl with alkaline matter, take out, clean with flushing with clean water; After the drying; Again as required, adopt mechanical-physical methods such as ball milling, air-flow are pulverized, water flies that it is pulverized, to make the Concha Margaritifera powder of different fineness; Wherein, described alkaline matter is selected from NaOH, potassium hydroxide, soda mint etc.; And/or
3) behind the cuticula with emery wheel removal mother-of-pearl, more as required, adopt mechanical-physical methods such as ball milling, air-flow are pulverized, water flies that it is pulverized, to make the Concha Margaritifera powder of different fineness.
" XRD diffraction approach " of the present invention claimed " XRD diffraction analysis method ", " XRD analysis method " again; Be meant the XRD diffraction result who adopts the XRD powder diffractometer to measure testing sample (like the crystalline powder material), with indexs such as the thing phase composition that detects testing sample and abundance (content) thereof, micromechanism information (comprising crystal block size, shape, structure etc.), crystallography parameter, crystal parameterses.
DSC/TGA method of the present invention is claimed thermogravimetry, DSC/TGA curve detection method again; This method adopts thermogravimetric analyzer to detect factors such as the heat absorption of testing sample in the heat temperature raising process, heat release, mass change, quantizes the information such as decomposition temperature and changes of contents thereof of testing sample fast.
Except as otherwise noted, when the present invention relates to the number percent between liquid and the liquid, described number percent is volume number percent; When the present invention relates to the number percent between liquid and the solid, said number percent is volume/weight number percent; When the present invention relates to the number percent between solid and the liquid, said number percent is weight/volume percent; All the other are weight/percentage by weight.
XRD analysis method of the present invention and detected parameters thereof and testing conditions comprise:
(1) detecting instrument: the XRD powder diffractometer, θ/θ or θ/2 θ angular instruments, angular instrument resolution, 2 θ do not have wideization of instrument (intrinsic) for about 28 °, standard model (SRM1976 or SRM L
aB
6) halfwidth (FHWM) measured<0.07 ° 2 θ.
(2) testing conditions: CuK
ArfRadiation, DS/SS:1 ° of RS 0.2mm, diffracted ray bondstone China ink monochromator is removed K
BataRadiation, power are not less than 1.6 kilowatts, and the step scanning mode is gathered the diffraction experiment data.
(3) preparation method of testing sample comprises: 1. directly press the powdery diffractometry sample preparation methods, the testing sample powder is pressed on the specimen holder of XRD diffractometer, again it is inserted the diffractometer test and collects experimental data; And/or
2. accurately measure texture coefficient sample, earlier Powdered testing sample is processed 1% suspending liquid, drop on the tabular sample panel, insert the XRD diffractometer behind the airing and detect and collect experimental data, and handle the diffraction data that records with the Jade9 software package with dropper.
DSC/TGA curve detection method of the present invention and testing conditions thereof comprise:
A) with thermogravimetric analyzer (DSC/TGA) start preheating 30 minutes, connect air;
b) Balance zero reading is stable, open the oven off sample loading, with the α-Al
2 O
3 loaded crucible 10-15mg the sample back and shut the stove;
C) treat that balance reading is stable after, (speed that is preferably 10 ℃/min-15 ℃/min) is warming up to 700 ℃-900 ℃ (being preferably 800 ℃), measures the TG/DTA curve, detects the data file deposit and handles with instrument software with 5 ℃/min-20 ℃/min.
Compared with prior art, the present invention has obtained following useful technique effect:
1, the present invention discovers, there is the aragonite phase transformation of kalzit phase in opposite directions in testing sample (pearl powder, Concha Margaritifera powder, nacreous layer powder, mixed powder) (200 ℃-450 ℃) in the phase transition temperature scope; Heating-up temperature is low, and the aragonite transformation rate of kalzit phase in opposite directions is slow; Along with temperature raises, the aragonite transformation rate of kalzit phase is in opposite directions accelerated; Arbitrary temperature in the phase transition temperature scope, the transformation rate of Concha Margaritifera powder is obviously faster than pearl powder.Therefore, the present invention adopts XRD diffraction analysis method and chooses arbitrary temperature or aragonite phase content or the kalzit phase content in a plurality of detected temperatures detection by quantitative testing sample between 200-450 ℃, to differentiate rapidly and sensitively and the quality of detection by quantitative testing sample.
2, the present invention discovers, the texture orientation factor (microstructure) of pearl powder, Concha Margaritifera powder, nacreous layer powder or mixed powder there are differences.No texture orientation can be differentiated to be non-pearl powder in the XRD of testing sample diffractogram.The present invention is detection by quantitative and confirmed the texture coefficient value scope of pearl meal, pearl fine powder, pearl micropowder also.
3, the present invention discovers, the cell parameter value of the lime carbonate of different origins is different.Detection by quantitative of the present invention aragonite is mutually and kalzit cell parameter value mutually in the pearl powder.If the cell parameter value of detection by quantitative testing sample is littler than the standard value that the present invention confirms, can differentiate to be non-pearl powder.
4, the present invention adopts the XRD analysis standard measure to detect kalzit phase content≤4% in the pearl powder.If the kalzit phase content in the testing sample>4%, perhaps detect other thing phases of non-lime carbonate, can differentiate to be the pure powder of non-pearl.
5, the content of organic matter in the present invention's pearl powder that utilized the thermal analysis system detection by quantitative and the oyster shell whiting, wherein, the content of organic matter < 3.5wt.% in the oyster shell whiting; The content of organic matter in the pearl powder is 3.5-5.0wt%.If detect the content of organic matter in the testing sample>5.0wt.% or < 3.5wt.% can differentiate to be the pure powder of non-pearl.
6, the present invention adopts the XRD analysis method to detect the hot transformation behavior of testing sample; After testing sample is heated to the arbitrary temperature or a plurality of arbitrary temperature between 200 ℃-450 ℃; Be incubated 5-10 minute, described testing sample is selected from any of pearl powder, Concha Margaritifera powder, nacreous layer powder, mixed powder, other powders, adopts XRD diffraction analysis method to detect kalzit content or aragonite content in the testing sample; Wherein, Kalzit content≤15.0wt.% in the pearl powder, the kalzit content≤10.0wt.% in the preferred pearl powder, more preferably the kalzit content in the pearl powder is 1.0wt.%-9.0wt.%; Kalzit content in the Concha Margaritifera powder is 18.0wt.%-60.0wt.%; Kalzit content in the nacreous layer powder is 15.0wt.%-45.0wt.%; Kalzit content in the mixed powder is 10.0wt.%-25.0wt.%.
7, detection method of the present invention have that selectivity is strong, stability and favorable reproducibility, rapid sensitive, advantage such as easy, accurate and effective, noiseless.Both can be used for differentiating the true and false of pearl powder, can be used for detecting and monitoring the quality of pearl powder again, even can detect and differentiate the mixed powder that the mixed female powder of 20wt-40% high quality pearl (nacreous layer powder) and pearl powder mix.
Description of drawings
The XRD diffraction testing result of Fig. 1 pearl meal, pearl fine powder, pearl micropowder and no texture powder.
The DSC/TGA testing result of Fig. 2 Concha Margaritifera powder.
The DSC/TGA testing result of Fig. 3 pearl powder.
Fig. 4 pearl powder and the Concha Margaritifera powder hot phase transition property XRD analysis result under air atmosphere.
< Concha Margaritifera powder of 4wt.% is at the XRD phase transformation comparing result of 380 ℃ of insulations after 5-10 minute for Fig. 5 kalzit content.
< pearl powder of 4wt.% is at the XRD phase transformation comparing result of 380 ℃ of insulations after 5-10 minute for Fig. 6 kalzit content.
< mixed powder of 4wt.% is at the XRD phase transformation comparing result of 380 ℃ of insulations after 5-10 minute, and wherein, mixed powder is evenly mixed by pearl powder and Concha Margaritifera powder 1:1 for Fig. 7 kalzit content.
Fig. 8 pearl powder, the Concha Margaritifera powder XRD testing result under vacuum state and under the air atmosphere, wherein, horizontal ordinate is a probe temperature, ordinate is a kalzit content, " She11-" expression Concha Margaritifera powder sample, " Pear1-" expression pearl powder sample, down together.
The hot phase transformation analysis result of the XRD of the even mixed powder of Fig. 9 pearl powder and Concha Margaritifera powder.
The hot phase transformation analysis result of the pearl powder of Figure 10 different mixing proportion and the XRD of oyster shell whiting.
The XRD powder diffraction analysis result of the commercially available pearl powder of Figure 11 (real is Concha Margaritifera powder);
The hot phase transformation analysis result of XRD diffraction of the commercially available pearl powder of Figure 12 (real is Concha Margaritifera powder);
The DSC/TGA testing result of the commercially available pearl powder of Figure 13 (real is Concha Margaritifera powder);
The XRD powder diffraction analysis result of the commercially available pearl powder of Figure 14 (real is Concha Margaritifera powder);
The hot phase transformation analysis result of XRD diffraction of the commercially available pearl powder of Figure 15 (real is Concha Margaritifera powder);
The DSC/TGA testing result of the commercially available pearl powder of Figure 16 (real is Concha Margaritifera powder);
The XRD powder diffraction analysis result of Figure 17 pearl powder (real is mixed powder);
The hot phase transformation analysis result of XRD diffraction of Figure 18 pearl powder (real is mixed powder);
The DSC/TGA testing result of Figure 19 pearl powder (real is mixed powder).
The XRD powder diffraction analysis result of Figure 20 Taiwan pearl powder;
The hot phase transformation analysis result of the XRD diffraction of Figure 21 Taiwan pearl powder;
The DSC/TGA testing result of Figure 22 Taiwan pearl powder.
Embodiment
Below will combine embodiment to specify the present invention, embodiments of the invention only are used to technical scheme of the present invention is described, and non-limiting essence of the present invention.
Embodiment 1The XRD diffraction approach detects the quality of pearl powder, Concha Margaritifera powder and mixed powder
The used testing sample of present embodiment is the pearl powder of various listing brands or adopts the cultured pearl and the parent clam shell thereof that are derived from the production of Zhuji, Zhejiang Province to get according to preparation method's preparation of the present invention.
Present embodiment adopts the XRD diffraction approach to analyze testing sample, through comparative studies, detects the pearl powder quality, confirms to differentiate the quality index of pearl powder.
1, XRD analysis method and test condition
(1) instrument: the XRD powder diffractometer, θ/θ or θ/2 θ angular instruments, angular instrument resolution, 2 θ do not have wideization of instrument (intrinsic) for about 28 °, standard model (SRM1976 or SRM L
aB
6) halfwidth (FHWM) measured<0.07 ° 2 θ.
(2) test condition
CuK
ArfRadiation, DS/SS:1 ° of RS 0.2mm, diffracted ray bondstone China ink monochromator is removed K
BataRadiation, power are not less than 1.6 kilowatts, and the step scanning mode is gathered the diffraction experiment data.
Prepare according to the method described in the present invention and detect testing sample.The result sees table 1.
Visible by table 1, adopt the analysis of XRD diffraction approach, the content≤4.0wt.% of kalzit phase in the pearl powder, aragonite phase content>=96.0wt.%.Compare with Concha Margaritifera powder or mixed powder, the kalzit phase content in the pearl powder is obviously on the low side, and the aragonite phase content is obviously higher, utilizes the kalzit content in the testing sample can pearl powder and Concha Margaritifera powder, mixed powder significantly be distinguished.
Embodiment 2Thermal analysis system detects the quality of pearl powder, Concha Margaritifera powder and mixed powder
1, thermogravimetry and test condition
A) start preheating thermogravimetric analyzer (DSC/TGA) is 30 minutes, connects air;
B) treat that balance reading makes zero after stable, open stove and take off dress appearance, with α-Al
2O
3The crucible 10-15mg testing sample of packing into is put back to, and shuts stove;
C) treat that balance reading is stable after, be warming up to 800 ℃ with the heating rate of 10 ℃/min from room temperature, measure the TG/DTA curve, data file deposit, and with instrument software processing and detecting data, the result sees table 1.
Visible by table 1, to analyze through DSC/TGA, the content of organic matter in the pearl powder is 3.5-5.0wt.%, wherein, the content of organic matter in the pearl meal is 4.3-5.0wt.%; The content of organic matter in the pearl fine powder is 4.0-4.3wt.%; The content of organic matter in the pearl micropowder is 3.5-4.0wt.%; And the content of organic matter≤3.5wt.% in the Concha Margaritifera powder; The content of organic matter≤3.5wt.% in the mixed powder.Compare with Concha Margaritifera powder, mixed powder, the content of organic matter in the pearl powder is higher relatively.
Embodiment 3The XRD diffraction approach is analyzed the hot phase transition property of testing sample
The analysis condition of the hot phase transformation of testing sample is in the XRD diffraction analysis method: under air atmosphere; Testing sample is inserted the high temperature annex environmental sample platform of diffractometer, rise to 360 ℃, be incubated 5-10 minute with the speed of 100 ℃/min; Reduce to normal temperature with the speed of 100 ℃/min again, at 15-70 degree 2
The diffraction data of θ scope collected specimens, the result sees table 1.
The quality testing result of table 1 pearl powder, Concha Margaritifera powder, mixed powder
Visible by table 1, under air atmosphere, testing sample is heated to 360 ℃ with the speed of 100 ℃/min; Be incubated 5-10 minute; Reduce to normal temperature with the speed of 100 ℃/min again, adopt the XRD diffraction analysis, the kalzit content in the pearl powder is 8.8wt.%-12.6wt.%; Kalzit content 33.4wt.%-43.8wt.% in the Concha Margaritifera powder; Kalzit content in the mixed powder is 16.5wt.%-24.6wt.%.Kalzit content after the hot phase transformation of testing sample capable of using is significantly distinguished pearl powder and Concha Margaritifera powder, mixed powder.
Embodiment 4The XRD analysis result of different-grain diameter pearl powder
The pearl that originates from Zhuji is processed the pearl meal of required particle diameter according to preparation method of the present invention, and (mean grain size does
Degree of orientation p
100Be 0.5-0.7), (mean grain size does the pearl fine powder
Degree of orientation p
100Be 0.7-0.8) and pearl micropowder (mean grain size does
Degree of orientation p
100Be 0.8-1.0).Detect pearl meal, pearl fine powder, pearl micropowder and do not have the quality of texture standard flour according to XRD diffraction approach of the present invention, the result sees Fig. 1.
Visible by Fig. 1, the crystallinity of three kinds of different fineness pearl powders is successively decreased from bottom to top, and detects the strong peak of master of kalzit phase only, and content is very low, and wherein, Fig. 1 lower frame has marked the relative intensity of each diffraction peak.Superfine pearl powder is the most approaching with no texture standard flour diffractogram.
Embodiment 5The hot analysis result comparative studies of pearl powder and Concha Margaritifera powder
The pearl that originates from Zhuji and pearl shell thereof are made the pearl powder or the Concha Margaritifera powder of required particle diameter according to preparation method of the present invention, detect according to thermogravimetry of the present invention and testing conditions thereof, the result sees Fig. 2-Fig. 3.
Visible by Fig. 2-Fig. 3; Oxidative pyrolysis figure in air atmosphere is similar for organic matter in pearl powder and the Concha Margaritifera powder; But the two there are differences on pyrolysis oxidizing temperature and organic weightlessness; Organic total amount in the pearl powder is apparently higher than Concha Margaritifera powder, but the content of organic matter that contains in the more Concha Margaritifera powder of gelatinous layer can raise to some extent.The content of organic matter in the Concha Margaritifera powder is 2.5-3.5wt.%, and the content of organic matter in the higher Concha Margaritifera powder of quality is 4.0wt%; The content of organic matter in the pearl powder is 3.5-4.5wt.%.
Embodiment 6The hot phase transition property research of pearl powder and Concha Margaritifera powder
Under vacuum condition or charge under the inert gas conditions, testing sample (pearl powder, Concha Margaritifera powder) is placed the XRD powder diffractometer that contains high temperature annex environmental sample platform, heating rate is 150 ℃/minute, to temperature to be measured, is incubated 5-10 minute; Rate of temperature fall is 150 ℃/minute, be cooled to room temperature after, gather diffraction data, the result sees Fig. 4.
Visible by Fig. 4, there is following rule in the hot transition kinetics behavior of pearl powder and Concha Margaritifera powder:
1) room temperature-200 ℃ (being the I district among Fig. 4), pearl powder and Concha Margaritifera powder have basically no phase transformation, the kalzit phase content≤15wt.% in the Concha Margaritifera powder, the kalzit phase content≤5wt.% in the pearl powder;
2) 200 ℃-450 ℃ (they being II district and the III district among Fig. 4) are the phase change zone, the kalzit content significant difference in pearl powder and the Concha Margaritifera powder, wherein, and the kalzit phase content≤15wt.% in the pearl powder, the kalzit phase content in the Concha Margaritifera powder is 15-40wt.%; Along with temperature raises, the transformation rate of pearl powder is starkly lower than Concha Margaritifera powder; In 200 ℃-350 ℃ (being the II district among Fig. 4) scopes, the kalzit phase content in each sample is more steady with temperature variation; In 350 ℃-450 ℃ (being the III district among Fig. 4) scopes, raise with temperature, the phase velocity between pearl powder and the Concha Margaritifera powder is accelerated, and the kalzit phase content difference in the two is more remarkable; About 450 ℃, the aragonite in the two is phase-changed into the kalzit phase mutually fully.
The present invention discovers, pearl powder is phase-changed into the kalzit phase with aragonite (200 ℃-450 ℃) in the phase transition temperature scope in the Concha Margaritifera powder, and the kalzit phase content obvious difference after the two phase transformation; Along with temperature raises, transformation rate is accelerated; In the phase transition temperature scope (200 ℃-450 ℃; Be preferably 200 ℃-350 ℃ or 350 ℃-450 ℃, more preferably 250 ℃-400 ℃, also be preferably 300 ℃-390 ℃; Most preferably be 340 ℃-380 ℃) arbitrary temperature; The transformation rate of pearl powder significantly is slower than Concha Margaritifera powder, and X-ray diffraction analysis standard measure capable of using detects the kalzit content in pearl powder and the Concha Margaritifera powder, detects the quality of testing sample.
In addition; In the phase transition temperature scope, utilize the X-ray diffraction analysis standard measure to detect the kalzit content difference of same testing sample under a plurality of temperature conditions; Can improve the accuracy of detection, have consuming time, problems such as speed is slow, cost height but detect the kalzit content difference of same testing sample under a plurality of temperature conditions.
Embodiment 7XRD diffraction analysis method detects the hot phase transformation result of testing sample
Kalzit content in the testing sample that present embodiment is chosen is < 4.0wt.% all.Under vacuum condition or charge under the inert gas conditions, as for high temperature annex sample worktable, heating rate is 100 ℃/>minute with testing sample, be heated to 380 ℃ after, be incubated 5-10 minute; Rate of temperature fall is 100 ℃/minute, be cooled to room temperature after, take out testing sample; Be placed on the powder diffractometer; Analyze and gather diffraction data, the result sees Fig. 5-Fig. 7, wherein; Described testing sample is selected from any of pearl powder, Concha Margaritifera powder and mixed powder, and said mixed powder is evenly mixed by pearl powder and Concha Margaritifera powder 1:1.
Visible by Fig. 5-Fig. 7, under vacuum condition or charge under the inert gas conditions, employing XRD diffraction analysis after testing sample is heated to 380 ℃, the kalzit content in the pearl powder is 6.9%; Kalzit content in the Concha Margaritifera powder is 35.0%; Kalzit content in the mixed powder is 19.2%.It is thus clear that, utilizing the kalzit content in the testing sample after XRD detects hot phase transformation, can pearl powder, Concha Margaritifera powder, mixed powder significantly be distinguished.
Embodiment 8The phase changing environment is to the influence of pearl powder and the hot phase transition property of Concha Margaritifera powder
Adopt the method for embodiment 6, the kalzit content after the hot phase transformation under vacuum condition and under the air atmosphere of research pearl powder and Concha Margaritifera powder, the result sees Fig. 8.
Visible by Fig. 8, airborne oxygen can quicken oxygenolysis organic in pearl powder, the Concha Margaritifera powder, quickens phase transformation, increases the kalzit content in the testing sample.Compare with the hot phase transformation under the vacuum condition, pearl powder, the transformation rate of Concha Margaritifera powder under air atmosphere are obviously accelerated.
Embodiment 9The hot phase transformation XRD analysis result of pearl powder and Concha Margaritifera powder
Testing sample placed temperature control is accurate, the constant temperature section of the uniform tube furnace of warm area temperature, feed argon gas or nitrogen and protect, flow is 200ml/min, and heating rate is 100 ℃/minute, be heated to 380 ℃ after, be incubated 5-10 minute; Rate of temperature fall is 100 ℃/minute, be cooled to room temperature after, take out testing sample, be placed on the powder diffractometer, analyze and gather diffraction data, the result sees table 2.
Table 2
Annotate: the blind appearance that " * " provides for Zhuji City Department of Qulity Supervision.
Visible by table 2, the kalzit content in the pearl powder sample is 3.7-8.4wt.%, and the kalzit content in the Concha Margaritifera powder sample is 17.9-26.2wt.%, and the testing result that provides with Zhuji City Department of Qulity Supervision is consistent.
Embodiment 10The hot phase transformation testing result of the XRD of testing sample
Testing sample placed temperature control is accurate, the constant temperature section of the uniform tube furnace of warm area temperature, feed argon gas and protect, flow is 150ml/min, and heating rate is 100 ℃/minute, be heated to 390 ℃ after, be incubated 5-10 minute; Rate of temperature fall is 100 ℃/minute, be cooled to room temperature after, take out testing sample, be placed on the powder diffractometer, analyze and gather diffraction data, the result sees Fig. 9.
Visible by Fig. 9, under the uniform prerequisite of sample mix, kalzit content and blending ratio in the even mixed powder of same pearl powder and same Concha Margaritifera powder have good linear relationship.
Embodiment 11The hot phase transformation XRD analysis result of different breeding zone pearl powder and oyster shell whiting
Present embodiment studied five age the hydriopsis cumingii sample and one age the hydriopsis cumingii sample hot phase transformation XRD branch result.
Cut open freshwater mussel and get pearl; According to the quality of pearl with its be divided into the high-quality pearl, (pearl and clam shell link together sticking shell pearl; With instrument it is peeled off), the pearl that dies of illness (claiming the evil mind pearl again), simultaneously, its clam shell (is used soaking with sodium hydroxide through physics method (emery wheel is clean with the polishing of outer cuticula), chemical method respectively; Remove outer cuticula) handle after, be processed into the testing sample powder according to identical preparation method.
Testing sample placed temperature control is accurate, the constant temperature section of the uniform tube furnace of warm area temperature, feed argon gas and protect, flow is 250ml/min, and heating rate is 100 ℃/minute, be heated to 385 ℃ after, be incubated 5-10 minute; Rate of temperature fall is 100 ℃/minute, be cooled to room temperature after, take out testing sample, be placed on the powder diffractometer, analyze and gather diffraction data, the result sees table 3.
Table 3
Visible by table 3, the kalzit content after the pearl powder that zones of different is cultured is handled by same procedure is 3.8-8.8%, and the kalzit content in the same freshwater mussel body in high-quality pearl, evil mind pearl, the sticking shell pearl raises successively.Kalzit phase content difference is more obvious than pearl powder in the oyster shell whiting in the different places of production.The Concha Margaritifera powder of prepared by physical method is lower than the kalzit content in the Concha Margaritifera powder of chemical method preparation.
Embodiment 12The hot phase transformation XRD analysis result of the pearl powder of different mixing proportion and oyster shell whiting
Testing sample (being numbered 1#-6#) is the potpourri of oyster shell whiting and pearl powder.Testing sample placed temperature control is accurate, the constant temperature section of the uniform tube furnace of warm area temperature, feed argon gas and protect, flow is 200ml/min, and heating rate is 100 ℃/minute, be heated to 400 ℃ after, be incubated 5-10 minute; Rate of temperature fall is 100 ℃/minute, be cooled to room temperature after, take out testing sample, be placed on the powder diffractometer, analyze and gather diffraction data, the result sees Figure 10.
Visible by Figure 10, the oyster shell whiting content in the testing sample among 2#, 3#, 1#, 6#, 5#, the 4# raises gradually, and test result conforms to the actual sample situation, and accuracy rate is 100%, has proved the reliability of detection method of the present invention.
Embodiment 13The universality research of the hot phase transformation XRD analysis of the present invention method
Testing sample placed temperature control is accurate, the constant temperature section of the uniform tube furnace of warm area temperature, feed argon gas and protect, flow is 200ml/min, and heating rate is 100 ℃/minute, be heated to 395 ℃ after, be incubated 5-10 minute; Rate of temperature fall is 100 ℃/minute; After being cooled to room temperature; Take out testing sample; It is delivered to Institute of Analysis of Zhejiang University respectively (is called for short Zhejiang University and divides measured center; Used x-ray diffractometer is Dutch PANalytical), Zhejiang Province's geological and mineral research institute (be called for short Zhejiang Di Kuang grind, used x-ray diffractometer is U.S. Thermo), Chinese Academy of Sciences's Suzhou nanometer carry out analytical test with nano bionic research institute (nanometer institute of the abbreviation Chinese Academy of Sciences, used x-ray diffractometer is German Bruker D8 Advance).The result sees table 4.
Table 4
Visible by table 4, different XRD instrument detecting data all in error range, have further proved the general applicability of the hot phase transformation XRD analysis of the present invention method.
Embodiment 14The testing result of commercially available pearl powder (real is Concha Margaritifera powder)
Purchase commercially available pearl powder, detect according to embodiment 1 described XRD diffraction approach, embodiment 6 or 9 described hot phase transformation XRD analysis methods and embodiment 2 described thermogravimetries and testing conditions thereof, the result sees Figure 11-Figure 13.
1, the XRD diffraction analysis result of sample has detected other thing phase alpha-quartzs, determines that it is Concha Margaritifera powder.
2, to record its kalzit content be 35.0wt.% to the hot phase transformation analysis of the XRD of sample, determines that it is Concha Margaritifera powder.
3, to record its content of organic matter be 3.4wt.% to the thermogravimetric analysis result of sample, determines that it is Concha Margaritifera powder.
Embodiment 15The testing result of commercially available pearl powder (real is Concha Margaritifera powder)
Purchase commercially available pearl powder, detect according to embodiment 1 described XRD diffraction approach, embodiment 6 or 9 described hot phase transformation XRD analysis methods and embodiment 2 described thermogravimetries and testing conditions thereof, the result sees Figure 14-Figure 16.
1, the XRD powder diffraction method of sample records its kalzit content above 4.0%, determines that it is Concha Margaritifera powder.
2, the hot phase transformation analysis result of the XRD of sample records its kalzit phase content up to more than the 50.wt.0%, determines that it is Concha Margaritifera powder.
3, the thermogravimetric analysis result of sample records its content of organic matter < 3.5wt.% determines that it is Concha Margaritifera powder.
Embodiment 16The testing result of mixed powder
Purchase commercially available pearl powder, detect according to embodiment 1 described XRD diffraction approach, embodiment 7 described hot phase transformation XRD analysis methods and embodiment 2 described thermogravimetries and testing conditions thereof, the result sees Figure 17-Figure 19.
Its each item of analysis-by-synthesis detects data, determines that it is the pearl powder that is mixed with the 10-20wt.% Concha Margaritifera powder and the mixed powder of Concha Margaritifera powder.
Embodiment 17The testing result of Taiwan pearl powder
Purchase commercially available Taiwan pearl powder, detect according to embodiment 1 described XRD diffraction approach, embodiment 7 described hot phase transformation XRD analysis methods and embodiment 2 described thermogravimetries and testing conditions thereof, the result sees Figure 20-Figure 22.
Its each item of analysis-by-synthesis detects data, judges that the Taiwan pearl powder that detects is for mixing the have an appointment pearl powder of 20wt.% Concha Margaritifera powder and the mixed powder of Concha Margaritifera powder.
Claims (15)
1. the quality determining method of a pearl powder; It is characterized in that; Adopt the XRD diffraction approach to analyze testing sample, described testing sample is selected from any of pearl powder, Concha Margaritifera powder, nacreous layer powder, mixed powder, other powders, wherein; Content≤the 4.0wt.% of kalzit phase in the pearl powder, the content>=96.0wt.% of aragonite phase.
2. quality determining method according to claim 1; The crystallographic system of aragonite thing phase is a quadrature in the said pearl powder; Space group is pmcn; Cell parameter is
Z=4, D (calc)=2.92.
3. quality determining method according to claim 1; The crystallographic system of kalzit phase is tripartite in the said pearl powder; Space group is R-3CH; Cell parameter is
Z=6, D=2.73.
4. according to each described quality determining method of claim 1-3, the test condition of said XRD diffraction approach is CuK
ArfRadiation, DS/SS:1 ° of RS 0.2mm, diffracted ray bondstone China ink monochromator is removed K
BataRadiation, power are not less than 1.6 kilowatts, and the step scanning mode is gathered diffraction data, promptly gets.
5. according to each described quality determining method of claim 1-4, the preparation method of testing sample comprises any or its combination of following method in the XRD diffraction approach:
1) directly presses the powdery diffractometry sample preparation methods, the testing sample powder is pressed on the specimen holder of XRD diffractometer, again it is inserted diffractometer and detect and collect experimental data; And/or
2) accurately measure texture coefficient sample, earlier powdered samples is processed 1% suspending liquid, drop on the tabular sample panel, insert the XRD diffractometer behind the airing and detect and gather experimental data with dropper.
6. the quality determining method of a pearl powder; It is characterized in that; 1) adopt XRD diffraction analysis method to detect testing sample, described testing sample is selected from any of pearl powder, Concha Margaritifera powder, nacreous layer powder, mixed powder, other powders, wherein; Kalzit phase content≤4.0wt.% in the pearl powder, aragonite phase content>=96.0wt.%; And/or
2) adopt the DSC/TGA analytic approach to detect testing sample, described testing sample is selected from any of pearl powder, Concha Margaritifera powder, nacreous layer powder, mixed powder, other powders, and wherein, the content of organic matter in the pearl powder is 3.5-5.0wt.%.
7. quality determining method according to claim 6, the content of organic matter in the said pearl meal is 4.3-5.0wt.%; The content of organic matter in the preferred said pearl fine powder is 4.0-4.3wt.%; The content of organic matter in the preferred pearl micropowder is 3.5-4.0wt.%; The content of organic matter in the preferred Concha Margaritifera powder is 2.5-4.0wt.%.
8. according to each described quality determining method of claim 6-7, said DSC/TGA detection method comprises the steps:
A) with thermogravimetric analyzer (DSC/TGA) start preheating 30 minutes, connect air;
B) balance reading makes zero after stablizing, and opens stove and takes off dress appearance, with α-Al
2O
3The crucible 10-15mg testing sample of packing into is put back to, and shuts stove;
C) treat that balance reading is stable after, (speed that is preferably 10 ℃/min-15 ℃/min) is warming up to 700 ℃-900 ℃ (being preferably 800 ℃), measures TG/DTA curve and data, promptly gets with 5 ℃/min-20 ℃/min.
9. the quality determining method of a pearl powder; It is characterized in that; 1) adopt XRD diffraction analysis method to detect testing sample, described testing sample is selected from any of pearl powder, Concha Margaritifera powder, nacreous layer powder, mixed powder, other powders, wherein; Kalzit phase content≤4.0wt.% in the pearl powder, aragonite phase content>=96.0wt.%; And/or
2) testing sample is heated to the arbitrary temperature between 200 ℃-450 ℃ after; Be incubated 5-10 minute, treat that it reduces to room temperature after, take out testing sample; Adopt XRD diffraction analysis method to detect kalzit phase content wherein; Described testing sample is selected from any of pearl powder, Concha Margaritifera powder, nacreous layer powder, mixed powder, other powders, wherein, and the kalzit content≤15.0wt.% in the pearl powder; Kalzit content≤10.0wt.% in the preferred pearl powder, more preferably the kalzit content in the pearl powder is 1.0wt.%-9.0wt.%; Kalzit content in the preferred Concha Margaritifera powder is 18.0wt.%-60.0wt.%; Kalzit content in the preferred nacreous layer powder is 15.0wt.%-45.0wt.%; Kalzit content in the preferred mixed powder is 10.0wt.%-25.0wt.%.
10. quality determining method according to claim 9; The analysis condition that detects the hot phase transformation of testing sample in the XRD diffraction approach does; With 50 ℃ of-150 ℃/min (after being preferably 100 ℃/min) speed and being heated to the arbitrary temperature or a plurality of arbitrary temperature in 200 ℃-450 ℃; Be incubated 5-10 minute, (be preferably 100 ℃/min) speed and reduce to normal temperature, gather and analyze the kalzit phase content in the testing sample with 50 ℃ of-150 ℃/min again in 15-70 degree 2 θ scopes.
11. according to each described quality determining method of claim 9-10; The analysis condition that detects the hot phase transformation of testing sample in the XRD diffraction approach does; With 50 ℃ of-150 ℃/min (after being preferably 100 ℃/min) speed and being heated to the arbitrary temperature or a plurality of arbitrary temperature in 200 ℃-350 ℃ or 350 ℃-450 ℃; Be incubated 5-10 minute; (be preferably 100 ℃/min) speed and reduce to normal temperature with 50 ℃ of-150 ℃/min again; Gather and analyze the kalzit phase content in the testing sample in 15-70 degree 2 θ scopes; The detection phase transition temperature of preferred testing sample is arbitrary temperature or a plurality of arbitrary temperature between 250 ℃-400 ℃, and more preferably the detection phase transition temperature of testing sample is arbitrary temperature or a plurality of arbitrary temperature between 300 ℃-390 ℃, and most preferably the detection phase transition temperature of testing sample is 340 ℃-380 ℃ arbitrary temperature or a plurality of arbitrary temperature.
12. according to each described quality determining method of claim 9-11; The heating arrangement of testing sample is selected from any of environmental sample platform, tube furnace of environmental sample platform, the high temperature annex of the environmental sample platform that contains the low temperature annex, middle temperature annex; After testing sample is heated to the arbitrary temperature or a plurality of arbitrary temperature between 200 ℃-450 ℃, utilize XRD to detect the kalzit content in the testing sample.
13. according to each described quality determining method of claim 9-12; Testing sample is placed the constant temperature section of tube furnace; Feeding inert gas (like argon gas, nitrogen) protects; Flow is 150ml/min-250ml/min (being preferably 200ml/min), (after being preferably 100 ℃/min) speed and being heated to the arbitrary temperature or a plurality of arbitrary temperature in 200 ℃-450 ℃, is incubated 5-10 minute with 50 ℃ of-150 ℃/min; (be preferably 100 ℃/min) speed and reduce to normal temperature, gather and analyze the kalzit phase content in the testing sample with 50 ℃ of-150 ℃/min again in 15-70 degree 2 θ scopes.
14. according to each described quality determining method of claim 9-13; Under air atmosphere, the vacuum condition or charge under the inert gas conditions; With 50 ℃ of-150 ℃/min (after being preferably 100 ℃/min) speed testing sample being heated to the arbitrary temperature or a plurality of arbitrary temperature in 200 ℃-450 ℃; Be incubated 5-10 minute; (be preferably 100 ℃/min) speed and reduce to normal temperature, gather and analyze the kalzit phase content in the testing sample with 50 ℃ of-150 ℃/min again in 15-70 degree 2 θ scopes.
15. each described quality determining method of claim 1-14 is used for detecting or control the application of the quality of pearl powder or its pharmaceutical products, preferred described pharmaceutical products is selected from any of pearl powder medicine, pearl powder cosmetic, pearl powder health products.
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| CN201210145993.2A CN102798640B (en) | 2011-05-11 | 2012-05-11 | Method for detecting quality of pearl powder by XRD (X-Ray Diffraction) and application thereof |
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| CN102721713A (en) * | 2011-05-11 | 2012-10-10 | 浙江长生鸟珍珠生物科技有限公司 | Method for detecting quality of pearl powder by thermal analysis method and application |
| CN103411861A (en) * | 2013-08-23 | 2013-11-27 | 中国检验检疫科学研究院 | Determination method for clustering index of pearl powder and shell powder |
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| CN103411861A (en) * | 2013-08-23 | 2013-11-27 | 中国检验检疫科学研究院 | Determination method for clustering index of pearl powder and shell powder |
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| CN107064043B (en) * | 2017-04-19 | 2021-05-07 | 东升新材料（山东）有限公司 | Mid-infrared spectrum identification method of adulterated pearl powder |
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Also Published As
| Publication number | Publication date |
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| CN102721713B (en) | 2015-11-18 |
| CN102798640B (en) | 2015-02-11 |
| CN102706911B (en) | 2014-10-01 |
| CN102798641A (en) | 2012-11-28 |
| CN102721713A (en) | 2012-10-10 |
| CN102323280A (en) | 2012-01-18 |
| CN102798641B (en) | 2015-01-07 |
| CN102706911A (en) | 2012-10-03 |
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