"Thermally Dynamic Examination of Local Order in Nanocrystalline Hydroxyapatite"

Supporting Data

Authors: Emily L Arnold*, Sarah Gosling, Samantha K Davies, Hannah L Cross, 
Dean S Keeble, Paul Evans, Charlene Greenwood, Keith D Rogers
* email: E.L.Arnold@cranfield.ac.uk
Created: 2022-05-19 ; Last revision: 2022-05-26

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ParamaterisedData.xlsx
Holds all parameterised values which were used within this work.

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ATR-FTIR:
All ATR-FTIR data was collected using a Bruker Alpha with a diamond ATR 
crystal, and a scan range from 4000 to 400 cm-1, with 64 averaged scans and 
4 cm-1 resolution. 

A .csv is provided for each sample with the baseline-corrected spectra. Each 
file gives in two columns: wavenumber, absorbance.

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PDF:
Experimental PDFs were acquired from I15-1 beamline at Diamond Light Source, 
using 76.7 keV radiation (wavelength = 0.161669 A). Two data sets were collected 
simultaneously, one used for total scattering analysis (Q-range = 0 A-1 - 
38.86 A-1) and the other used for fitting of Bragg peaks (Q-range = 3.39 A-1 
- 16.82 A-1). DAWN was used to integrate the 2D area data to 1D data. Data 
was collected at 25°C, 100°C, 200°C, 300°C, 325°C, 350°C, 400°C, 450°C, 500°C, 
550°C, 575°C, 600°C, every 10°C to 700°C, 750°C and 800°C. The heating rate 
between temperatures was 10°C min-1, and data was collected at each stated 
temperature for 10 minutes. Decreased steps between temperatures were chosen 
at key intervals based on literature.

The CHA-1 was measured with one frame per temperature, producing a total of 24 
frames covering 24 temperatures. CHA-2 was measured with 10 frames per temperature, 
producing a total of 230 frames. Due to unanticipated shut-down of the beam, 19 of 
these frames held no usable data, leaving a total of 211 frames which were used for 
further analysis, covering 22 temperatures in addition to the single 10 minute 
frame collected at room temperature.

PDFs were processed using GudrunX with a Qmin = 0.5 A-1 and Qmax = 25.6 A-1. 
Composition was calculated with the use of CO32- concentration for all samples 
(assuming no additional substitution, Equation 1 was charge balanced to determine 
HA composition). Density was calculated from HA composition and lattice parameters 
determined by Si-spiked XRD. For CHA-2, all frames from each temperature were used 
to calculate one PDF to improve Qmax. 

An .dofr is provided with the processed PDF for each scan, and is named using the 
following convention:

i15-1-ScanNumber_Detector_FrameNumber.dofr

e.g.  "i15-1-30505_pe2AD_tth_pe2_0.dofr"  has a scan number 30505, a frame number 0, 
and originates from detector 2 (pe2AD_tth_pe2 OR tth_pe2).

Scan Numbers:
 30505 CHA-2 - Room Temperature                                                           
 30506 CHA-2 - Temperature Series                                       
 30514 CHA-1 - Room Temperature                                                                  
 30515 CHA-1 - Temperature Series         

Within each temperature series, (30506 and 30515) temperature is denoted by the 
frame number, with a key given below:
0 -  100°C
1 -  200°C
2 -  300°C
3 -  325°C
4 -  350°C
5 -  400°C
6 -  450°C
7 -  500°C
8 -  550°C
9 -  575°C
10 - 600°C
11 - 610°C
12 - 620°C
13 - 630°C
14 - 640°C
15 - 650°C
16 - 660°C
17 - 670°C
18 - 680°C
19 - 690°C
20 - 700°C
21 - 750°C
22 - 800°C

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WAXS-DLS
All WAXS data from DLS was collected as described above. Multiple scans from each 
temperature were not averaged, and thus there are a total of 230 frames for the temperature 
series from CHA-2, and a total of 23 frames from CHA-1. 

An .xy is provided with the original 1D line integrated using DAWN for each scan 
(each frame of each sample), and is named using the following convention:

i15-1-ScanNumber_Detector_FrameNumber.xy

e.g.  "i15-1-30506_pe1AD_tth_pe1_0.xy"  has a scan number 30506, a frame number 0, 
and originates from detector 1 (pe1AD_tth_det1 OR tth_det1). All .xy files have 
two columns of data: 2Theta (degrees) and Intensity.

Scan Numbers:
 30505 CHA-2 - Room Temperature                                                           
 30506 CHA-2 - Temperature Series                                       
 30514 CHA-1 - Room Temperature                                                                  
 30515 CHA-1 - Temperature Series         

Within each temperature series, (30506 and 30515) temperature is denoted by the 
frame number, with a key given below (0-22 apply to 30515, all frames apply to 30505):
0 -  100°C	23 - 100°C	46 - 100°C	69 - 100°C	92 -  100°C	115 - 100°C	138 - 100°C	161 - 100°C	184 - 100°C	207 - 100°C
1 -  200°C	24 - 200°C	47 - 200°C	70 - 200°C	93 -  200°C	116 - 200°C	139 - 200°C	162 - 200°C	185 - 200°C	208 - 200°C
2 -  300°C	25 - 300°C	48 - 300°C	71 - 300°C	94 -  300°C	117 - 300°C	140 - 300°C	163 - 300°C	186 - 300°C	209 - 300°C
3 -  325°C	26 - 325°C	49 - 325°C	72 - 325°C	95 -  325°C	118 - 325°C	141 - 325°C	164 - 325°C	187 - 325°C	210 - 325°C
4 -  350°C	27 - 350°C	50 - 350°C	73 - 350°C	96 -  350°C	119 - 350°C	142 - 350°C	165 - 350°C	188 - 350°C	211 - 350°C
5 -  400°C	28 - 400°C	51 - 400°C	74 - 400°C	97 -  400°C	120 - 400°C	143 - 400°C	166 - 400°C	189 - 400°C	212 - 400°C
6 -  450°C	29 - 450°C	52 - 450°C	75 - 450°C	98 -  450°C	121 - 450°C	144 - 450°C	167 - 450°C	190 - 450°C	213 - 450°C
7 -  500°C	30 - 500°C	53 - 500°C	76 - 500°C	99 -  500°C	122 - 500°C	145 - 500°C	168 - 500°C	191 - 500°C	214 - 500°C
8 -  550°C	31 - 550°C	54 - 550°C	77 - 550°C	100 - 550°C	123 - 550°C	146 - 550°C	169 - 550°C	192 - 550°C	215 - 550°C
9 -  575°C	32 - 575°C	55 - 575°C	78 - 575°C	101 - 575°C	124 - 575°C	147 - 575°C	170 - 575°C	193 - 575°C	216 - 575°C
10 - 600°C	33 - 600°C	56 - 600°C	79 - 600°C	102 - 600°C	125 - 600°C	148 - 600°C	171 - 600°C	194 - 600°C	217 - 600°C  
11 - 610°C	34 - 610°C	57 - 610°C	80 - 610°C	103 - 610°C	126 - 610°C	149 - 610°C	172 - 610°C	195 - 610°C	218 - 610°C
12 - 620°C	35 - 620°C	58 - 620°C	81 - 620°C	104 - 620°C	127 - 620°C	150 - 620°C	173 - 620°C	196 - 620°C	219 - 620°C
13 - 630°C	36 - 630°C	59 - 630°C	82 - 630°C	105 - 630°C	128 - 630°C	151 - 630°C	174 - 630°C	197 - 630°C	220 - 630°C
14 - 640°C	37 - 640°C	60 - 640°C	83 - 640°C	106 - 640°C	129 - 640°C	152 - 640°C	175 - 640°C	198 - 640°C	221 - 640°C
15 - 650°C	38 - 650°C	61 - 650°C	84 - 650°C	107 - 650°C	130 - 650°C	153 - 650°C	176 - 650°C	199 - 650°C	222 - 650°C
16 - 660°C	39 - 660°C	62 - 660°C	85 - 660°C	108 - 660°C	131 - 660°C	154 - 660°C	177 - 660°C	200 - 660°C	223 - 660°C
17 - 670°C	40 - 670°C	63 - 670°C	86 - 670°C	109 - 670°C	132 - 670°C	155 - 670°C	178 - 670°C	201 - 670°C	224 - 670°C
18 - 680°C	41 - 680°C	64 - 680°C	87 - 680°C	110 - 680°C	133 - 680°C	156 - 680°C	179 - 680°C	202 - 680°C	225 - 680°C
19 - 690°C	42 - 690°C	65 - 690°C	88 - 690°C	111 - 690°C	134 - 690°C	157 - 690°C	180 - 690°C	203 - 690°C	226 - 690°C
20 - 700°C	43 - 700°C	66 - 700°C	89 - 700°C	112 - 700°C	135 - 700°C	158 - 700°C	181 - 700°C	204 - 700°C	227 - 700°C
21 - 750°C	44 - 750°C	67 - 750°C	90 - 750°C	113 - 750°C	136 - 750°C	159 - 750°C	182 - 750°C	205 - 750°C	228 - 750°C
22 - 800°C	45 - 800°C	68 - 800°C	91 - 800°C	114 - 800°C	137 - 800°C	160 - 800°C	183 - 800°C	206 - 800°C	229 - 800°C

Scan 30506 suffered from beam loss during the temperature series, affecting frame 
numbers: 16, 17, 39, 40, 62, 63, 85, 86, 108, 130, 131, 153, 154, 176, 177, 
199, 200, 222, and 223, spanning 650°C, 660°C and 670°C.

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WAXS-Lab:
All WAXS data was collected using a PANalytical XPert PRO Multi-Purpose 
Diffractometer with Cu Kalpha radiation source. A PIXcel strip detector was used 
to collect data from 10° to 80° 2theta. Samples were Si-spiked (2.5 - 5 wt%) to provide 
an internal standard for LP calculation.

All .xy files have two columns of data: 2Theta (degrees) and Intensity.